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\CHARACTERIZATION OF RESINS IN ALTERNATIVE FUEL MIXTURES/

by

Hani Shukri\\Karam11

Dissertation submitted to the Faculty of the

Virginia Polytechnic Institute and State University

in partial fulfillment of the requirements for the degree of

DOCTOR OF PHILOSOPHY

in

Chemistry

APPROVED:

H. M. McNair, Chairman

'.J' L T. Taylor -vy-() < ,. - D"v

P. E. Field >

April, 1986 Blacksburg, Virginia

J. G. Mason

ill. O. Finklea :~

CHARACTERIZATION OF RESINS IN ALTERNATIVE FUEL MIXTURES

by

Hani Shukri Karam

Committee Chairman: H. M. McNair

Chemistry

(ABSTRACT)

"Resins" is a class of compounds believed to play an

important role in the conversion processes of coal and

coal-related materials into oils. Methods currently used to

isolate this fraction, generally lack reproducibility and

yield impure and strongly overlapping fractions which do not

reflect the actual group-type distribution in the liquid

fuel.

A separation method based on liquid column chromatogra-

phy was developed, which divides liquid fuels into eight

distinct and minimally overlapping chemical classes: five

non-polar (saturated, mono-, di-, tri-, and polynuclear aro-

matics), one intermediate polar (resins) and two polar

(asphaltenes and asphaltols) fractions.

Chemical characterization of "resins fractions,"

derived from two alternative fuels (coal-derived liquid and

sugarcane bagasse), was achieved by first subjecting them to

acid-base-neutral separation, followed by analysis of each

subfraction by GC/MS. Identification of the eluted compo-

nents was carried out utilizing a library search system, by

comparing retention times (indices) of 150 model compounds

believed to exist in liquid fuels, on two fused silica

capillary columns ( Carbowax 20 M and SE-54), and by mass

spectral interpretation.

GC/MS results indicate that "resins" are mainly com-

posed of weakly acidic (phenols, indanols, naphthols),

mildly basic (benzoquinolines, chloroanilines, etc.), neu-

tral-nitrogen ( indoles and carbazoles), and oxygen ( carbo-

nyl) compounds, and are free of hydrocarbons.

ACKNOWLEDGEMENTS

I wish to thank Dr. H. M. McNair for serving as the

chairman of my committee and for his continuous support dur-

ing the time spent at Virginia Tech. I also would like to

thank Drs. H. 0. Finklea, L. T. Taylor, P. E. Field and J.

G. Mason for serving as committee members.

Also, I wish to acknowledge the help and support of

research group, particularly

ermasters,

secretary,

to

; and

My thanks and appreciation

, from the University of Sao Paulo/Sao

Carlos/Brazil, a visiting professor of group

1981-1983, for his support and encouragement during the

early stages of my research. Also I wish to thank

and his research group at the University of Sao Pau-

lo/Sao Carlos/Brazil for their support during my stay in Sao

Carlos/Brazil; and the Department of Chemistry at the Fed-

eral University of Sao Carlos for providing the GC/MS facil-

ities.

A strong acknowledgement of the constant support, love

and encouragement, through the years of early education,

iv

high school, college and during the years of this work, pro-

vided by my parents, is simply

inadequate to express the deep gratitude and appreciation I

feel towards them. Also, my deep gratitude to my brothers

and to my cousin Sam for their love and

constant support.

Finally, the sharing of all the moments of my Ph.D.

experience by my fiance, was crucial to the accom-

plishrnent of this effort. Her love, patience and constant

encouragement through the years are strongly acknowledged.

v

TABLE OF CONTENTS

ABSTRACT ii

ACKNOWLEDGEMENTS iv

INTRODUCTION

High Resolution Gas Chromatography/Mass Spectrometry

Alternative Liquid Fuels Definition of "Resins" Statement of Thesis Objectives

HISTORICAL

1

1 2 5 6

8

Separation Methods for Alternative Liquid Fuels 8 Solvent Extraction . . . . . . . . . 8 Liquid Chromatography . . . . . . . 10· Gel Permeation Chromatography (GPC) 13 Thin Layer Chromatography (TLC) 15 High Performance Liquid Chromatography (HPLC) 16 Acid-Base-Neutral Fractionation 18

Characterization of Alternative Liquid Fuels by HRGC/MS 21

EXPERIMENTAL 24

PART 1: Development and Evaluation of a Preparative Scale Liquid Column Chromatographic Fractionation Method . . . . . . . . . 24

A: Development of the Liquid Column Chromatographic Fractionation Method 24

Materials . . . . . . . . . . . . . . . 24 Sample Preparation . . . . . . . . . . 24 Liquid Column Chromatographic Fractionation 26

B: Fractionation of Various Model Mixtures by LC and Analysis of Fractions by HRGC/MS 29

Sample Preparation 29 GC/MS System . . . . . . . . . . . . . 31

Vi

C: Fractionation of a Brazilian Sugarcane Bagasse Liquefaction Products by LC and Analysis of Fractions by HRGC/MS . 31

Sample Preparation . . . . . . . . . 31 GC/MS Conditions . . . . . . . . . . 32

PART 2: Development of an Acid-Base-Neutral Separation Scheme and its Application to Alternative Fuel Mixtures . . . . 36

Preparation of the Packing Materials for Column Chromatography . . . . . . . . . . . . . . 36

Fractionation of Model Mixtures and Liquid Fuel Samples Into Acid-Base-Neutral Components 38

GC/MS Experimental Conditions . . . . . . . 39 PART 3: Analysis of Acidic, Basic and Neutral

Subfractions of Alternative Liquid Fuel-Derived Resins by HRGC/MS 39

Sample Preparation 41 GC/MS Conditions 41

RESULTS AND DISCUSSION 42

PART-1: Development and Evaluation of a Preparative Scale LC Fractionation Method . . . . . . . 42

A: Development of the LC Fractionation Method 42 B: Fractionation of Various Model Mixtures by LC

and Analysis of Fractions by HRGC/MS . . 53 Prep Scale LC . . . . . . . . . . . . . . . . 53 HRGC/MS Analysis of Prep Scale LC Fractions . 56

C: Fractionation of Brazilian Sugarcane Bagasse Liquefaction products by LC and Analysis' of Fractions by HRGC/MS 72

Sugarcane Bagasse: Background . . . . . . 72 Prep Scale LC Fractionation . . . . . . . 85 Hiqh Resolution GC/MS of Bagasse-Derived

Liquids . . . . . . . . . . . . 85 PART-2: Development of an Acid-Base-Neutral

Separation Scheme and its Application to Alternative Liquid Fuel Mixtures 116

PART-3: Analysis of Acidic, Basic and Neutral Subfractions of "Resins" Derived from Alternative Liquid Fuels by HRGC/MS 127

CONCLUSIONS 230

REFERENCES 239

VITAE . . . 254

vii

LIST OF TABLES

Table

1. Composition of Standard Mixtures Employed in the LC Fractionation Method . . . . . . . . . . . 28

2. Eluents and Fractions Collected in the Preparative Scale Fractionation Method . 30

3. Hydrocarbons and Basic Model Mixtures Used to Monitor the Preparative Scale LC Fractionation by GC/MS . . . . . . . . . . . . . . 32

4. Acidic and Neutral Model Mixtures Employed to Monitor the Preparative Scale LC Fractionation by GC/MS . . . . . . . . . . . . . . . . . . . 33

5. Gas Chromatographic Conditions Used in Part-lB of This Study . . . . . .

6. Mass Spectrometric Conditions Employed in This Work

7. Gas Chromatographic Conditions Used in Parts lC, 2 and 3 of This Study . . . . .

8. Percent Distribution of Group Types in a Brazilian "Mina de Leao" Coal Extract Obtained by the LC

34

35

37

Method . . . . . . . . . . . . . . . . . . 51

9. Fraction Distribution of Brazilian "Mina do Leao" THF Coal Extract by Solubility Fractionation Method . . . . . . . . . . . . . . . . . . 52

10. Recovery of Various Liquid Fuels from Preparative Scale LC Columns . . . . . . . . . 55

11. Group Type Distribution of Hydrocarbon, Acidic, Basic and Neutral Standard Mixtures on Prep Scale Silica Gel Columns . . . . . . . . . . . . 57

12. GC Retention and Mass Spectral Characteristics of Hydrocarbon Model Compounds used to Monitor LC Fractionation by GC/MS . . . . . . . . . 61

viii

13. GC Retention and Mass Spectral Characteristics of the Neutral Model Compounds used to Monitor LC Fractionation by GC/MS . . 69

14. GC Retention and Mass Spectral Characteristics of the Acidic Model Compounds used to Monitor LC Fractionation by GC/MS . . . . . 74

15. GC Retention and Mass Spectral Characteristics of the Basic Model Compounds used to Monitor LC Fractionation by GC/MS . . . . . . . . 80

16. Percent Distribution of Group-Types in Brazilian Sugarcane Bagasse Liquefaction Products Obtained by the LC Method 86

17. GC/Mass Spectral Analysis of "Unfractionated" Brazilian Sugarcane Bagasse Liquefaction Products 89

18. Mass Spectral Characteristics and Retention Data of Aromatic Hydrocarbon Standards on SE-54 Capillary GC/MS System . . . . . 93

19. Compounds Identified in "Diaromatics" Fraction of "Brazilian" Sugarcane Baga;:,se Liquefaction Products . 98

20. Compounds Identified in "Triaromatics" Fraction of "Brazilian" Sugarcane Bagasse Liquefaction Products . . . . . . . . 100

21. Compounds Identified in "Polynuclear Aromatics" Fraction of "Brazilian" Sugarcane Bagasse Liquefaction Products . 102

22. Percent Distribution of Compound Classes in Aromatic Fractions of "Brazilian" Sugarcane Bagasse Liquefaction Products . 105

23. Percent Distribution of Aromatic Compounds in Non-Polar Fractions of Brazilian Sugarcane Bagasse Liquefaction Products . . . . . 106

24. Identified Chemical Components in the "Resins" Fraction of "Brazilian" Sugarcane Bagasse Liquefaction Products . 110

25. Identified Chemical Compounds in the "Asphaltenes" Fraction of "Brazilian" Sugarcane Bagasse Liquefaction Products . 113

ix

26. Retention Behaviour of Acidic, Basic, and Neutral Model Compounds on Cation-Exchange and Silica-Modified KOH Columns . . . . 118

27. Elution Order of a Mixture of Acidic, Basic, and Neutral Standards on a Fused Silica Carbowax Capillary Column . . . . 124

28. Distribution of Acidic, Basic, and Neutral Compounds in the "Resins" Fractions Derived from Alternative Fuel Sources 126

29. Day-to-Day Reproducibility of n-Alkanes Retention Data on Carbowax 20 M Capillary Column . . . . 129

30. Day-to-Day Reproducibility of n-Alkanes Retention Data on SE-54 Capillary Column . . . . . . . 130

31. Retention Characteristics of Aromatic Hydroc~:bon Standards on Carbowax 20 M Capillary Column 140

32. Retention and Mass Spectral Characteristics of Neutral Standards on Carbowax Capillary Column 142

33. Retention and Mass Spectral Characteristics of Acidic Standards on Carbowax Capillary Column 144

34. Retention Data and Mass Spectral Characteristics of Basic Standards on Carbowax Capillary Column 146

35. Compounds Identified in the "Acidic Subfraction" of Sugarcane Bagasse-Derived Resins Fraction . . 156

36. Compounds Identified in the 11 Basic Subfraction" of Sugarcane Bagasse-Derived Resins Fraction . 164

37. Compounds Identified in the Neutral Subfraction of Sugarcane Bagasse-Derived Resins Fraction 172

38. Percent Volatiles in the Resins Fraction of Sugarcane Bagasse and its Respective Acidic, Basic and Neutral Subfractions 177

39. Percent Distribution of Identified Compounds in the Acidic, Basic and Neutral Subfractions of Bagasse-Derived Resins 178

40. Compounds Identified in the Acidic Subfraction of Brazilian "Mina do Leao" SRC-Derived Resins 193

x

41. Compounds Identified in the Basic Subfraction of Brazilian "Mina do Leao" SRC-Derived Resins . 196

42. Compounds Identified in the Neutral Subfraction of Brazilian "Mina do Leao" SRC-Derived Resins 199

43. Percent Volatiles in the Resins Fraction of Brazilian SRC and its Respective Acidic, Basic and Neutral Subfractions . . . . . . . . . 201

44. Percent Distr. of Identified Compounds in the Acidic, Basic and Neutral Subfractions of Brazilian SRC-Derived Resins . . . . . 202

45. Retention Characteristics of Neutral Standards on SE-54 Capillary Column . . . 207

46. Retention Characteristics of Basic Standards on SE-54 Capillary Column . . . 211

47. Retention Characteristics of Acidic Standards on SE-54 Capillary Column . . . . 215

48. Compounds Identified in the Acidic Subfraction of Sugarcane Bagasse-Derived Resins Fraction . 220

49. Compounds Identified in the Basic Subfraction of Sugarcane Bagasse-Derived Resins Fraction . . 223

50. Compounds Identified in the Neutral Subfraction of Sugarcane Bagasse-Derived Resins Fraction . . 225

51. Components Identified in the Resins Subfractions of Sugarcane Bagasse Based on Korats Retention Indexes of Model Compounds on SE-54 and Carbowax 20 M Capillary Columns . . . . . . 229

52. Comparison of Fractionation Methods . . 232

xi

LIST OF FIGURES

Figure

1. Separation Scheme Developed for Fractionating Liquid Fuels into Acidic, Basic and Neutral Components. 40

2. Preparative scale liquid chromatogram of a non-polar model mixture. . . . . 44

3. Preparative scale liquid chromatogram of "resins" standard mixture. . . . 45

4. Preparative scale liquid chromatogram of "clay resins" derived from Brazilian "Mina do Leao" coal extract. . . 46

5. Preparative scale liquid chromatogram of asphaltenes derived from solubility fractionation of Brazilian coal extract. . . . . . . . 47

6. Preparative scale liquid chromatogram of asphaltols derived from solubility fractionation of Brazilian coal extract. 49

7. Preparative scale liquid chromatogram of the polar portion of the whole "Brazilian" coal extract. . 50

8. Distribution of preparative scale LC fractions for various liquid fuels. . 54

9. GC-FID chromatogram of total hydrocarbon standards. 60

10. GC-FID chromatogram of LC fraction-1 of the hydrocarbons standard mixture.



xii

.. 62

. . 63

. . 64

13. GC-FID chromatogram of LC fraction-4 of the hydrocarbons standard mixture. . . . . 65

14. GC-FID chromatogram of LC fraction-S of the hydrocarbons standard mixture. . . . . 66

lS. GC-FID chromatogram of total neutral standards. 68

16. GC-FID chromatogram of LC fraction-3 of the neutrals standard mixture. . . . . . 70

17. GC-FID chromatogram of LC fraction-6 of the neutrals standard mixture. 71

18. GC-FID chromatogram of total acidic standards (S°C/min temperature programming rate). . 73

19. GC-FID chromatogram of total acidic standards (2°C/min temperature programming rate). . 7S

20. GC-FID chromatogram of LC fraction-6 of the acidic standard mixture (S°C/min temperature programming rate). 76

21. GC-FID chromatogram of LC fraction-6 of the acidic standard mixture (2°C/min temperature programming rate). . . . . . . . . . 77

22. GC-FID chromatogram of LC fraction-7 of the acidic standard mixture. . . . . . . 78

23. GC-FID chromatogram of total basic standards. 79

24. GC-FID chromatogram of LC fraction-6 of the basic standard mixture. . . 81

2S. GC-FID chromatogram of LC fraction-7 of the basic standard mixture. . . 82

26. GC-FID chromatogram of total (unfractionated) "Brazilian" sugarcane bagasse-derived liquids. . 88

27. GC-FID chromatogram of aromatic hydrocarbon standards. . 92

28. GC-FID chromatogram of "diaromatics" fraction derived from "Brazilian" sugarcane bagasse liquids. . 9S

xiii

29. GC-FID chromatogram of "triaromatics" fraction derived from "Brazilian" sugarcane bagasse liquid products. . . . . . . . 96

30. GC-FID chromatogram of "polynucleararomatics" fraction derived from "Brazilian" sugarcane bagasse liquid products. . . 97

31. GC-FID chromatogram of "resins" fraction derived from "Brazilian" sugarcane bagasse liquid products. . . . 108

32. GC-FID chromatogram of "asphaltenes" fraction derived from "Brazilian" sugarcane bagasse liquid products. . . . 109

33. GC-FID chromatogram of a total mixture of acidic, basic and neutral standards on a carbowax capillary column. . 120

34. GC-FID chromatogram of the acidic fraction after acid-base-neutral separation of the total mixture of standards. 121

35. GC-FID chromatogram of the basic fraction after the acid-base-neutral separation of the total mixture of standards. 122

36. GC-FID chromatogram of the neutral fraction after the acid-base-neutral separation of the total standard s mixture.

37. GC-FID chromatogram of aromatic hydrocarbon standards on carbowax capillary column.

38. GC-FID chromatogram of neutral standards on carbowax

123

132

capillary column. . 133

39. GC-FID of acidic standards on carbowax capillary column.

40. GC-FID acidic standards on carbowax capillary

134

column. 135

41. GC-FID of" some carboxylic acids standards on carbowax capillary column. 136

42. GC-FID chromatogram of basic standards on carbowax capillary column. 137

xiv

43. GC-FID chromatogram of basic standards on carbowax capillary column. . . . . . . . . .

44. GC-FID chromatogram of basic standards on carbowax capillary column. . . . . .

45. GC-FID chromatogram of acidic subfraction of bagasse-derived resins fraction on a carbowax

138

139

capillary column. . . . . . . 152

46. Total ion chromatogram (T.I.C.) of acidic subfraction of bagasse-derived resins fraction. 153

47. GC-FID chromatogram of basic subfraction of bagasse-derived resins fraction on a carbowax capillary column. . 160

48. Total ion chromatogram of basic subfraction of bagasse-derived resins fraction. 161

49. GC-FID chromatogram of neutral subfraction of bagasse-derived resins fraction on a carbowax capillary column. . . . . . 167

50. Total ion chromatogram of neutral subfraction of bagasse-derived resins. . . 168

51. GC-FID chromatogram of acidic subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. . . . . . 183

52. Total ion chromatogram of acidic subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. 184

53. GC-FID chromatogram of basic subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. . . . . . . 186

54. Total ion chromatogram of basic subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. 187

55. GC-FID chromatogram of neutral subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. 190

56. Total ion chromatogram of neutral subfraction of Brazilian "Mina do Leao" SRC-derived resins fraction. 191

xv

57. GC-FID chromatogram of neutral standards on SE-54 capillary column. . 206

58. GC-FID chromatogram of basic standards on SE-54 capillary column. . . . . . . . . . . . 208

59. GC-FID chromatogram of basic standards on SE-54 capillary column. . . . . 209

60. GC-FID chromatogram of basic standards on SE-54 capillary column. . 210

61. GC-FID chromatogram of acidic standards on SE-54 capillary column. . 213

62. GC-FID chromatogram of acidic standards on SE-54 capillary column. . . . . . . . . 214

63. GC-FID chromatogram of acidic subfraction of bagasse-derived resins fraction on an SE-54 capillary column. . . . . . 217

64. GC-FID chromatogram of basic subfraction of bagasse-derived resins fraction on an SE-54 capillary column. . . . . 218

65. GC-FID chromatogram of neutral subfraction of bagasse-derived resins fraction on an SE-54 capillary column. . . . . . . . . . 219

xvi

INTRODUCTION

High Resolution Gas Chromatography/Mass Spectrometry

The combination of High Resolution Gas Chromatography

with Mass Spectrometry {HRGC-MS) is one of the major accom-

plishments in the history of modern analytical chemistry.

The high resolving power of today's fused silica capillary

columns {1,2), their high degree of inertness, the resultant

high sensitivity, high precision and more rapid analysis

over conventional columns {3,5) with their high thermal sta-

bility and low bleeding rates phases (3-5) makes them the

.preferred GC columns. When these columns are combined with

the great sensitivity and selectivity of today's mass spec-

trometers { 6-8), the resultant HRGC/MS system becomes the

instrument of choice for the analysis of complex mixtures

such as cigarette smoke, crude oil, coal-liquids, etc.

HRGC/MS can provide qualitative as well as quantitative

analysis of such complex samples. The mass spectrometer is

capable of detecting the various components in the gas chro-

matographic effluent, based on molecular ions {Chemical Ion-

ization, Field Ionization and Field Desorption MS), and uni-

que fragmentation patterns {Electron Impact MS} (9). High

1

2

Resolution Mass Spectrometers (HRMS), on the other hand, can

provide exact mass measurements and elemental compositions

of the individual GC peaks (10). However, due to their high

cost, HRMS are seldom employed. Evidently, HRGC/Low Resolu-

tion MS provides a compromise between chromatographic reso-

lution and mass resolution.

In spite of the incredible capabilities of the HRGC/MS

technique, and its ever increasing popularity in trace

organic analysis, one of its major limitations is that

solutes have to be thermally stable and volatile in order to

be separated by GC prior to analysis by mass spectrometry.

High molecular weight and high polarity compounds which are

expected to exist in the heavy ends of liquid fuels (heavy

sulfur, nitrogen and oxygen-containing compounds) are not

amenable to analysis by HRGC/MS.

Alternative Liquid Fuels

Fuels, such as coal and shale oil, have gained consid-

erable attention in recent years, both as sources of energy

and chemical feedstocks. Attention has also been focused

lately on sugarcane and other agricultural products (Biom-

ass), as possible fuel sources. The limited supply of

petroleum and the high probability of its depletion within

the next two decades have motivated extensive research on

3

the utilization of alternative fuels as substitutes to

petroleum and its processed derivatives. This substitution

seems likely since the alternative fuels can be easily con-

verted into liquid products through liquefaction (11,12) and

solvent extraction (13,14). An understanding of the chemi-

cal composition of these liquid products is essential to

their efficient use; to control their quality, and to under-

stand the basic chemistry involved in the various conversion

processes.

As a first step towards their chemical characteriza-

ti on, the alternative fuel mixtures must be divided into

simpler fractions, and concentrated with chemically similar

species which are suitabl~ for further analysis.

Fractionation of the liquid fuels under study relied

heavily upon separation procedures originally developed for

the petroleum industry ( 15), despite the fact that these

fuels are much more complex and heterogeneous than petroleum

(16,17). Fractionation was achieved either on solubility

differences (18), or chromatographically, based on such

effects as sorption (19), steric exclusion (20), or ion-ex-

change (21,22). Although these separation methods, and

their modifications, turned out to be inadequate for the .. characterization of the alternative liquid fuels, they indi-

cated, along with other studies ( 23-29), that four major

4

chemical classes (group-types) exist in such fuels, namely:

oils, resins, asphaltenes, and asphaltols. These methods,

however, use similar terms to define dissimilar fractions.

The word "asphaltenes", for example, as related to coal

liquids, can mean a solvent separated material that is ben-

zene or toluene soluble and pentane (30), or hexane (31), or

cyclohexane insoluble (32,33). They can also be defined as

a specific chromatographic fraction with one functional

group present per molecule (34). There are at least three

different methods to isolate the "resins" fraction, and as

many as ten different methods for "asphaltenes" (35), all of

which arrive at supposedly the same product(s).

A need for a standard analytical method has therefore

been created, triggered by the development of liquid fuels

technology. New separation procedures were developed, which

either isolated specific compound types such as alkyl phe-

nols (36-38), basic nitrogen (39,40), neutral nitrogen (41),

carboxylic acids (42,43), etc.; or divided liquid fuels

according to their polarity ( 44, 45), or functional groups

and complexity (34). These new methods, however, failed to

provide the actual group-type distribution which is essen-

tial for an assessment and quality control of the fuel in

question. The group types "oils, resins, asphaltenes, and

asphaltols" are the real chemical classes and not artifacts

5

of the separation procedure ( 46). A standard separation

method, for alternative liquid fuels, that can provide all

four chemical classes, in a pure and discrete form is there-

fore highly in need.

Definition of "Resins"

It is believed that all three chemical classes "asphal-

tols, asphaltenes and resins" play a key role in the conver-

sion processes of the fossil fuel into liquid products

( 47-51). The "resins" class is particularly important,

since it is an intermediate between the undesired polar

chemical classes "asphaltols and asphaltenes", and the

desired non-polar product "oils".

Three separation methods are currently used to isolate

the "resins" in alternative liquid fuels, namely: solubility

fractionation (52), S.A.R.A. (24,53), and clay column frac-

tionation (52).

"Resins" are defined by a solubility criteria as that

portion of the liquid fuel that is soluble in n-pentane, but

insoluble in propane. According to the S.A.R.A. method

(Saturates, Aromatics, Resins, and Asphal tenes), following

the precipitation of "asphaltenes" in a light paraffin

(n-pentane or n-hexane), the "deasphaltened" portion of the

liquid fuel ("maltenes") is divided on silica and/or alumina

6

columns into saturates, aromatics and resins using a

sequence of solvents of increasing polarity. Finally,

"resins" are defined as that portion of the "maltenes" that

is trapped by a clay (Florisil) column and not eluted with

n-pentane.

None of these methods, however, provides a pure

"resins" fraction. Strong overlap between the "resins" and

the "asphal tenes" has been confirmed using several analyt-

ical techniques (52). Also, prior to the isolation of the

"resins" fraction, "asphal tenes" have to be precipitated in

a light paraffin, with the implicit consequences of co-pre-

cipi tating part of the "resins" (54); while the composition

of the precipitated "asphal tenes" (both yield and chemical

nature) strictly depends on the experimental conditions

employed, including the chain length of the precipitating

alkane (55), volume of solvent used for precipitation (56),

or for washing the precipitate (57).

A re-definition of "resins" is therefore essential.

Statement of Thesis Objectives

To date, chemical characterization of "resins" in

alternative liquid fuels has not been attempted. This the-

sis intends to analyze this fraction by High Resolution Gas

Chromatography/Mass Spectrometry. Being an intermediate

7

fraction between "oils" and "asphaltenes", "resins" are

expected to be mildly polar in nature, which suggests that

their analysis by the HRGC/MS technique is quite feasible.

The first logical step prior to analysis, however, would be

to isolate this chemical class as a pure fraction, which is

free of hydrocarbons (oils) or heavy sulfur and nitrogen

compounds (asphaltenes and asphaltols). One objective was

to develop a separation method which defines "resins" chro-

matographically. The method will be based on liquid column

chromatography, which di vi des the alternative liquid fuel

into eight distinct chemical classes: Five non-polar

classes (saturates, monoaromatics, di aromatics, triaromat-

ics, and polynuclear aromatics), collectively referred to as

"oils"; one intermediate polar class ("resins"); and two

polars classes ("asphaltenes and asphaltols").

Fractions of "resins" from two alternative fuel sources

(Sugarcane Bagasse and Coal Liquefaction Products) will be

analyzed by the HRGC/MS technique, and as many as possible

of the eluted components will be identified and quantitated.

HISTORICAL

Separation Methods for Alternative Liquid Fuels

A variety of separation procedures for liquid fuels

have appeared in the literature for the last fifteen years.

All were intended to simplify the complexity of the liquid

fuel in question, by dividing it into a number of fractions,

prior to characterization by instrumental techniques.

Regardless of the basis for the separation (solubility,

polarity, chemical functionality, size, etc.), each of these

methods has contributed, directly or indirectly, to the

understanding of the chemical nature of the liquid fuels

under study. Only those closely related to the present work

are discussed below.

Solvent Extraction

This method is commonly used as a means of fractiona-

tion and characterization of coal-derived liquids, based on

solubility of the liquid fuel in n-pentane (or n-hexane),

benzene (or toluene), and pyridine (or THF). Fractions are

defined operationally: Preasphaltenes (or asphaltols), as

pyridine (or THF) soluble, benzene (or toluene) insoluble;

8

9

asphaltenes, as benzene (or toluene) soluble, n-pentane (or

n-hexane) insoluble; and oils, as n-pentane (or n-hexane)

solubles (35,58,59). Various extraction techniques have

been used, including the time consuming Soxhlet ( 60-63),

ambient temperature ultrasonic baths (64-66), successive

extraction of coal liquids with solvents of increasing or

decreasing polarities (18), and, most recently, the sequen-

tial elution of coal-derived fractions from a glass bead

column (67,68). Regardless of the separation procedure used

or the extractive solvents employed, fractionation methods

based on solubility always generate the same fractions,

namely: oils, asphaltenes and asphaltols, as in one commonly

used classification scheme (15,35,67-71) or asphaltenes and

maltenes as in another scheme (54,55,62,72,73). Fractions

of the same fuel sample obtained by the different methods,

al though given the same names,

composition, as concluded by

differ markedly in chemical

many workers in the field

(18,35,74,75). Evidently, the order in which solvents are

used, solvent polarity, and the many variations in the sepa-

ration procedures are responsible for such inconsistencies

(54,75).

In a

fractions,

search for uniformity

Snape and Bartle ( 76)

in defining coal-derived

and Bal ti sberger et al.

(77), have recently suggested the use of an empirical solu-

10

bility parameter that defines coal-derived oils, asphaltenes

and asphal to ls in terms of average structural properties.

Whether or not these new definitions become operational,

there exists a strong need for a standard method that

divides coal-derived liquids into their component fractions,

as emphasized by Steedman, in a recent review on the subject

(78).

Liquid Chromatography

This method was mainly applied to the study of satu-

rated and aromatic hydrocarbon fractions in the deasphal-

tened liquid fuels, as obtained using silica and/or alumina

columns (19,79,80). Later, following the development of the

S.A.R.A. method (Saturates, Aromatics, Resins, and Asphal-

tenes) by Gulf scientists (53,81), which was a modification

of the API-60 method, developed by the U.S. Bureau of Mines

(19); the deasphaltened coal-liquid (maltenes) was divided

into saturates, aromatic hydrocarbons and resins fractions

using a combination of ion-exchange (cation and anion}, co-

ordination {Fec13 on clay}, and adsorption (silica) chroma-

tography. Various separation procedures have appeared since

then which generally divided solvent refined and liquefac-

tion products of coal into saturate, aromatic and polar

fractions using neutral alumina (82-84), dual-packed columns

of silica gel

chromatography

11

and alumina ( 85, 86)

(87). Silica gel

or clay-gel adsorption

chromatography was also

used to isolate specific compound types, such as alkyl phe-

nols (36), from coal-derived liquids.

The SESC fractionation method (Sequential Elution by

Solvent Chromatography), developed by Farcasiu (34), pro-

vided separation of whole coal liquids on silica gel into

ten distinct fractions, based on different chemical func-

tionalities. Attempts to correlate the "SESC" fractions

with those provided by solubility (oils, asphaltenes and

asphaltols), however, were not successful; overlap among the

fractions has been observed (88).

Other procedures, using sequential elution from silica

columns, either separated coal liquids into a .limited number

of fractions based solely on polarity (44), or divided coal

liquids into hydrocarbons and non-hydrocarbon fractions,

while allowing sub-fractionation of hydrocarbon portion by

ring number (89).

The method described by Odoerfer et al. (90), however,

also based on chemical functionality, separated coal-liquids

on silica gel columns into four major classes, namely hydro-

carbons, heterocyclic, mono-functional and polyfunctional

compounds. It further separated the hydrocarbons, by ring

number, and the monofunctional fraction into basic nitrogen

12

and monophenols, using alumina columns; while dividing the

heterocycles on ion-exchange columns into O,S-heterocyclic

and neutral nitrogen compounds.

Neutral alumina was used by Lee et al. (91) to separate

synthetic fuel products into the chemical classes aliphatic

hydrocarbons, neutral-polycyclic aromatic hydrocarbons (neu-

tral-PAC), nitrogen-PAC and hydroxyl-PAC. A similar

approach was undertaken by Robins et al. (92) who designed a

sequential elution procedure that divided coal-liquids on

silica columns into saturates, aromatics, neutral nitrogen,

basic nitrogen, and polar nitrogen fractions. Wozniak and

Hites (93), on the other hand, used a dual column of picric

acid coated alumina to achieve class separation of coal

liquids into aliphatic hydrocarbons, hydroaromatics, polya-

romatic hydrocarbons (PAH's), and nitrogen PAH's. Boduszyn-

ski et al. ( 94) used an SRC (Sol vent Refined Coal )-coated

Fluoropak and a basic alumina column to obtain four major

compound classes: Hydrocarbons, heterocyclic, hydroxyaro-

matic, and polyfunctional compounds.

The liquid chromatographic separation procedures, dis-

cussed so far, do not provide the actual group-type distri-

bution in the liquid fuel. Many workers in the field have

emphasized the importance of a separation procedure that

leads to the conventional classes of materials (saturates,

13

aromatics, resins, & asphaltenes). The method employed by

Phillips Petroleum (24) provides these classes by dividing

deasphal tened coal-liquids on neutral alumina into satu-

rates, aromatics, and resins. The procedure employed by

Vercier ( 29), and more recently by Coulombe et al. ( 95),

arrives at essentially the same fractions for deasphaltened

synthetic fuels, using dual-packed silica and alumina col-

umns. This procedure, however, provides more fractionation

of the aromatics into mono-, di-, and polynuclear aromatics.

To avoid the problems associated with the precipitation of

asphaltenes, Lancas et al. (96) fractionated whole coal-li-

quids on silica gel columns, using sequential elution, into

the four conventional classes.

Gel Permeation Chromatography (GPC)

This technique, which separates molecules according to

their size in solution, can provide the molecular weight

distribution of the liquid fuel; however, it can give very

little information about the chemical nature of the prod-

ucts. It has been used extensively for preparing specific

cuts of petroleum and coal-liquid fractions.

GPC has been used in a number of cases to assist in the

characterization of coal liquids. Brule ( 97) used GPC to

qualitatively and quantitatively characterize coal derived

14

asphaltenes and maltenes. Bockrath et al. (98) character-

ized coal-derived asphal tenes by acid-base fractionation,

followed by GPC. Chromatography showed a broad distribution

of molecular sizes in the different solvent fractions; oils

and asphaltenes were clearly distinguished despite some

overlap. Ruberto and co-workers (46) used preparative and

analytical GPC procedures to obtain molecular size profiles

of coal liquid fractions. They concluded that molecular

sizes follow the order asphaltols > asphaltenes > oils.

GPC has also been used for the fractionation of whole

coal liquids (99-104) and shale oils (105,106), into molecu-

lar "sized" fractions. GPC was used as a preliminary sepa-

ration step, prior to detailed analysis by ~pectroscopic and

other chromatographic techniques. Furthermore, attempts

were made to separate coal liquids by GPC into fractions

that correspond to the classical solubility fractions of

oils, asphaltenes and asphaltols (107). Philip and co-work-

ers, however, used GPC to separate coal-derived liquids

(108,109), and pyrolytic tar (110), into aromatic, phenolic,

light non-volatiles and alkanes, and heavy non-volatile

(asphaltenes) fractions. Although GPC is considered by many

authors (108-110) as a fast analytical separation technique

of alternative liquid fuels, the problems of adsorption and

calibration are still major drawbacks (111).

15

Thin Layer Chromatography (TLC)

This technique has been used extensively for the class

fractionation of liquid fuels. Hue and Roucache (112) sepa-

rated shale oils on silica gel plates into saturated and

unsaturated hydrocarbons, aromatic compounds, and

N,S,0-compounds. Harvey et al. (113) obtained 14 fractions

for a shale oil, based on chemical classes, starting with

n-alkanes (Rf=0.82) and finishing with highly polar (poly-

functional) compounds, ( Rf=O). Artz and co-workers ( 114)

used TLC to analyze coal-derived liquids and to semi-quanti-

tatively measure the degree of hydrogenation of these prod-

ucts. The order of elution on silica gel plates was: satu-

rates > hydroaromatics > PNA's > phenols ~ ~itrogen bases.

Poirier and colleagues (27,115-117) and Selucky et al. (26)

used TLC with Flame Ionization Detection (FID) to separate

coal-derived liquids into the classical solubility fractions

of oils, asphaltenes and asphaltols. Coal-derived maltenes

were also separated, by Selucky (118), on silica plates,

into hydrocarbons (saturates and aromatics), polar I

(resins) and polar II ( asphal tenes). Both groups of Poi-

rier, Selucky and their co-workers consider TLC/FID a rapid

and quantitative method for hydrocarbon type analysis of

alternative liquid fuels with the added advantage that all

sample components can be measured.

16

High Performance Liquid Chromatography (HPLC)

This technique is becoming increasingly popular and

extensively used for the class separation of alternative

liquid fuels, mainly due to its fast and efficient nature.

Normal Phase (NP) HPLC has been used for the hydrocarbon-

type separations of shale oils (28, 119-123), and coal-de-

rived liquids (111,124-131), into paraffins/olefins; aromat-

ics and polars (111,119-123), and/or for the fractionation

of the aromatics in these liquids by ring number (124-131).

Columns used have included dual columns of silica and silica

impregnated with silver nitrate (119,122), µ-silica

(124,127,131), µ-bonded amino or cyano (28,111,120,121,130),

µ-alumina ( 126), and coupled µ-silica and µ-cyano bonded

columns (128).

NP-HPLC has also been used for

liquids based on chemical functionality.

fractionating coal

Amateis and Taylor

( 132) separated a coal-derived polar fraction on a Polar

Amino-Cyano (PAC) column into two slightly overlaping chro-

matographic profiles of weakly basic (indoles, amines) and

acidic (phenols) compounds, using deuterated chloroform-ace-

tonitrile mobile phases. Chmielowiec (133) separated a wide

variety of compounds, known to be in coal liquids, on sil-

ica, using dimethylsulfoxide-carbon tetrachloride mobile

phases. The procedure, which provided good functional class

17

separation, was applied to coal-liquids. The use of aprotic

dipolar solvents, as effluent additives for moderating sil-

ica surface, has been reported by various authors to promote

functional type selectivity on plain silica columns

(134,135).

HPLC in the Reverse Phase mode (RP-HPLC) has been less

frequently used for group-type or functional class separa-

tions of the liquid fuels. Reichert et al. (25) separated a

heavy crude Bitumen into hydrocarbons (saturates + aromat-

ics), resins, and asphal tenes using coupled c10 and cyano

columns. Novotny and others (136) used microcolumn c8 and

c18 to separate fossil fuels into three distinct chromato-

~~aphic profiles: neutral polyaromatics, aza-arenes and

phenols. Separation of PAH's and nitrogen heterocycles

using a c18 column was also reported by Ruckmick and Hurtu-

bise (137). The usefulness of the RP-HPLC technique, how-

ever, is limited by the low solubility of these complex

organic mixtures (coal liquids, etc.) in the aqueous mobile

phases. Such solubility problems have been reported by sev-

eral authors (137-139).

In spite of their attractive features of great selec-

tivity, high efficiency and fast analyses, HPLC methods can-

not fractionate the fuel samples into the many classes as

well as low pressure column chromatography, or handle large

18

amounts of sample for further characterization of the sepa-

rated fractions. Quan ti ta ti on is also another major draw-

back of the HPLC methods. Universal detectors, such as Dif-

ferential Refractive Index (R.I.), do not respond uniformly

to the different classes of compounds. R.I. response fac-

tors vary with the type of compound and even within the same

C 1 a SS ( 140 I 141 ) • Quanti tation by HPLC is therefore ques-

tionable (95,141).

Acid-Base-Neutral Fractionation

Fractionation of alternative liquid fuels into acidic,

basic, and neutral concentrates is a generally accepted

method of separation that ha~ been widely used for the char-

acterization of coal-derived liquids (34,39,46,53,69,83,91,

98,125,132-139,142-167), shale oils (37,168-176), and heavy

crude oils (43,177-179). Various procedures have been uti-

lized for this kind of separation, among which aqueous

extraction (37,142-144,148,152,153,160,161,l69,170,173-

176,203), ion-exchange chromatography (39,53,145,149,157,

158,167,177), open column silica or alumina chromatography

(34,47,69,83,91,151,l68,l71,l72}, and the selective isola-

tion of nitrogen-containing compounds by HCl precipitation

(39,98,144,146,147,154,l62,l63,l66) or neutral nitrogen com-"

pounds by organometallic co-ordination chromatography

19

(53,149,177,180) have been the most commonly used. Other

procedures are less popular and were developed for the

selective isolation of nitrogen containing compounds using

columns of silica modified with HCl (177,178), non-aqueous

ti trations ( 150) or deri vatization ( 155, 156, 159). For the

specific isolation of phenols and carboxylic acids, silica

"modified with KOH" columns were used (43,179).

Many of the separation procedures above, however, pose

a number of disadvantages and/or limitations. Aqueous acid

extraction, for example, in addition to being time consuming

and requiring large quantities of solvents, tends to form

intractable emulsions with higher molecular weight samples.

Furthermore, it depends upon the solubilities of the proto-

nated bases in the aqueous acid. This solubility decreases

markedly with increasing molecular weight (21,153).

In cation-exchange chromatography weaker bases and some

neutral compounds may be retained by the acidic resin; such

interactions are solvent dependent, being most pronounced in

non-polar solvents (180).

In co-ordination chromatography, using ferric chloride

supported on clay, stronger acids and bases tend to form

stable complexes with the transition metal salts, if not

removed by other methods (165). Also, highly condensed aro-

matic systems tend to form weak TI-bonds with the ferric ion

20

(180,181). Isolation of the N-containing compounds by HCl

precipitation is selective for the aromatic bases. Further-

more, significant amounts of phenolic material may be

adsorbed on the surface of the finely divided precipitating

adduct of HCl bases (39).

Current silica or alumina adsorption methods, on the

other hand, show poor selectivity for the heteroatomic spec-

ies, which are distributed between the aromatic and polar

fractions (165). Even in the most popular "SESC" fractiona-

tion method (34), which provides a more effective separation

of heteroatoms, a considerable overlap between compound

classes still exists (88,165).

Amino and cyano bonded silicas have been successfully

employed, in conjunction with NP-HPLC, for the class separa-

tion of heteroatomic species, as previously discussed. How-

ever, the low capacity of such microparticulate packings and

their high cost, limit their usefulness for preparative or

even semi-preparative scale applications.

In addition to the drawbacks of the existing proce-

dures, various studies have demonstrated that fractions gen-

erated by the different isolation methods, for the same fuel

sample, although given similar names (basic, acidic or neu-

tral fractions), are not identical (39,150,152,165,181) and

in some cases, possess significant structural differences

(39,150).

21

A need for an integrated and standardized

Acid-Base-Neutral (ABN) separation schematic has arisen.

Most recently, Karam and Lancas et al. (182) have developed

this separation procedure using a large number of model com-

pounds that represent the various chemical classes generally

found in liquid fuels. The method, which is a modification

of two of the existing procedures (cation-exchange and KOH-

treated silica chromatography), clearly defines the optimum

conditions for an effective separation of liquid fuels into

(ABN) fractions.

Characterization of Alternative Liquid Fuels !2_y HRGC/MS

HRGC/MS is one of the most powerful analytical techni-

ques that has been used for the characterization of the vol-

atile components. in coal derived liquids and shale oils.

The various fractions generated, .using one or more of the

separation methods previously discussed, have been subjected

to analysis by this High Resolution technique, and a large

number of compounds were positively identified using co-

chromatography with authentic standards and mass spectrome-

try. In many cases, however, only tentative identifica-

tions, based on mass spectrometry alone, were possible.

In the paraffinic/olefinic fractions, straight chain

alkanes, branched alkanes, alkenes and cycloalkanes/cy-

22

cloalkenes were mainly found in shale oils (113,173-174,194)

and to a lesser extent in coal liquids (108,167,184,195).

Hundreds of aromatic hydrocarbons were found in the

aromatic fractions of these fuels, including alkylbenzenes

(108,167,184,187); naphthalenes, biphenyls and indanes

(83,108,110,167,184,187,202); and poly aromatic hydrocarbons

{PAH's) (83,108,110,113,173,187,l90-192,195,202).

Various basic nitrogen and neutral nitrogen hetero-

cyclic compound classes were found in the basic and neutral

fractions of the liquid fuels under study, including poly-

cyclic aromatic amines (153,154,198); anilines and pyridines

(152,159,160-162,171,173,176,197,203); quinolines and higher

aza-arenes (143,152,160,161,163,l64,l73,l81,l88,l89,203) and

pyrroles, nitriles, and carbazoles (83,164,171,173,197).

Also, found in the basic fractions were some sulfur hetero-

cycles (185,194,199,201,204) and mixed S,N-heterocycles

( 186); and in the neutral fractions, carbonyl compounds

(196).

Acidic fractions were rich in phenols (37,143,145,173),

indanols and naphthols (83,108,176,183) and carboxylic acids

( 42, 143, 200). Most recently, hydroxy lated thiophenic com-

pounds were identified in an acidic fraction of a coal

derived liquid (193).

23

Most of the GC/MS studies above utilized mass spectro-

metry in the Electron Impact (EI) mode. Some reports,

employed Chemical Ionization (CI) mode (200,205,206), using

ammonia or isobutane reagents, for reasons of reducing the

complexity of the mass spectra (less fragmentation), enhanc-

ing the molecular ion peak, or analyzing nitrogen heterocy-

cles in the presence of (non-interferring) hydroxyl and sul-

fur compounds (206).

Other modes of mass spectrometry exist, among which

Field Ionization (FI) has been the most widely used for the

analysis of coal derived materials (130,207-210). FIMS,

which provides unfragmented molecular ions, does not require

pre-separation of the sample by GC, and has therefore been

useful for the characterization of high boiling and non-dis-

tillable coal liquids (130,210).

EXPERIMENTAL

PART l: Development and Evaluation of ~ Preparative Scale Liquid Column Chromatographic Fractionation Method

A: Development of the Liquid Column Chromatographic Fractionation Method

Materials. Solvents employed in the preparative scale

studies were reagent grade (Fisher Scientific, Raleigh, NC)

and used as received. High purity terahydrofuran ( THF),

used for GC/MS work, was obtained by treatment of THF with

KOH ( 1 mole/liter) followed by distillation prior to use.

Model compounds, 99%+, were either from Sigma Chemical Com-

pany (St. Louis, Missouri) or Aldrich Chemicals (Milwaukee,

WI).

Sample Preparation. The LC fractionation method was

first developed using, for the most part, extraction prod-

ucts from a high ash Brazilian "Mina do Leao" coal. The

method was then applied to various fuels, including an Indi-

ana V solvent refined coal (SRC), a Brazilian "Mina do Leao"

SRC, and a Brazilian sugar cane bagasse liquid products.

Each solid fuel was ground, sieved through a 60 mesh screen

(A.S.T.M. E-11 specification) then subjected to extraction,

24

25

liquefaction or dissolution as needed. The high ash Brazil-

ian coal (Mina do Leao, Porto Alegre, Brazil) was extracted

with THF (1/10, w/v) by mechanically stirring with the sol-

vent for 1 hour. The insolubles were removed by filtration

through a number 1 Whatman filter paper (Whatman Chemical

Separation, Inc., Clifton, NJ), and the extract stripped of

solvent by a combination of rotary evaporation, for sample

concentration, and complete drying of the extract using a

Reacti Vap® Sample concentrator (Pierce Chemical Company,

Rockford, IL) set at 60°C (±0.5) and under a low nitrogen

flow. Liquefaction of Brazilian 11 Mina do Leao" coal was

carried out in a heated sand bath autoclave at 800°F, in the

presence of an H-donor \tetralin, ratio 2/1; v/w) solvent,

and under 1100 psig hydrogen, for 30 minutes. Liquefaction

products were exhaustively extracted with pyridine, followed

by removal of the extraction solvent as above. Brazilian

sugarcane bagasse (Copersucar, SP, Brazil) was liquified in

a stainless steel autoclave, as described by Lancas (211).

The bagasse was mixed with Cresote oil (ratio 1/5 w/w) and

the resulting suspension was heated to 400°C under an ini-

tial hydrogen pressure of 150 atm. Hydrogenation products

were then extracted with a (1:1) hexane-water mixture for 12

hours, at ambient temperature, under an inert atmosphere

(helium) and with constant stirring. The aqueous layer was

26

discarded while the organic layer stripped of the hexane as

above. Liquefaction products were dried in a vacuum oven at

220°C then weighed and stored under nitrogen in a refrigera-

tor until further analyses. Characteristics of the Brazil-

ian coal and the sugarcane bagasse, and more details about

the liquefaction processes can be found elsewhere (12, 45,

211 and 212, respectively). Indiana V low ash SRC (Cata-

lytic Inc., Wilsonville, AL) was dissolved in THF ( >97%

soluble) to the proper concentration prior to fractionation.

Liquid Column Chromatographic Fractionation. To

achieve the fractionation of the liquid fuels into their

chemical classes (i.e., group types), the liquid column

chromatographic conditions were first optimized for the sep-

aration of mixtures of model compounds that are known to

exist in most liquid fuels. The choice of standard com-

pounds to represent the non-polar fractions of the liquid

fuel is based on references (124,213), while those for the

intermediate polar fraction ("resins") are in accordance

with Suatoni et al. ( 28). For "asphal tenes" and "asphal-

tols", little is known about their chemical composition,

therefore, the fractions of the Brazilian coal extract gen-

erated by the solubility fractionation method (74) and

referred to as "asphaltenes" and "asphaltols" were employed

as model mixtures.

appears in Table 1.

The composition of these model mixtures

27

TABLE 1

Composition of Standard Mixtures Employed in the LC Fractionation Method*

n-PARAFFINS MONOAROMATICS DIAROMATICS

Nonane Decane Undecane Dode cane Tetradecane Hexadecane Octadecane Eicosane Docosane Tetracosane

0-Xylene P-Xylene m-Xylene

Naphthalene .

Ethyl Benzene Diethyl Benzene P-Cymene n-Butyl Benzene n-Hexyl Benzene n-Octyl Benzene n-Decyl Benzene

POLYNUCLEARAROMATICS RESINS

1-Methyl Napathalene 2,6-Di-Methyl Naphthalene Ethyl Naphthalene Acenaphthene

TRIAROMATICS

Anthracene Methyl Anthracene Phenanthrene Fluoranthene 9,10-Di-Me-Anthracene

ASPHALTENES &: ASPHALTOLS

Pyrene Chrysene

Benzoquinoline Phenol

Fractions Obtained by the solubility fractionation method (74)

9-Phenyl Anthracene Benz-a-Anthracene

*

Benz aldehyde Quinoline

Model compounds in each mixture are blended in equal masses to a final concentration of 200 mg/ml of solution.

28

The liquid chromatographic columns utilized were glass,

500 x 11 mm and fitted with a teflon stopcock. Small pieces

of glass wool were used to retain the packing material.

Each column was slurry packed with silica gel, 40-60 mesh

SI-60 (E. Merck, Gibbstown, NJ). The slurry was prepared

by mechanically agitating 20 gms of silica gel (activated at

180°C for 4 hours) in 60 ml n-hexane (dried over 4A 0 molecu-

lar sieve previously heated for 2 hours at 300°C) for 30

minutes.

With the stopcock halfway open and the glass column

one-third full with n-hexane, the slurry was gravity fed, in

small portions, while tapping the column gently to help the

particles to settle and to provide a uniform and reproduci-

ble bed. This process was repeated until all the silica gel

was transferred to the column. The length of the silica bed

in each column measured ex~ctly 37.0 ± 0.1 cm. Finally, the

silica bed was washed with 100 ml of n-hexane and the wash-

ings discarded. Care was taken in keeping the solvent above

the level of the silica gel and never allowing the silica

gel to dry out either prior to or during the chromatographic

process.

Solutions of the model mixtures, prepared in hexane or

THF so as to contain 200 mg/ml, were first chromatographed

individually, then later in mixtures, in order to determine

29

the optimum chromatographic conditions for the minimum over-

lap among the classes.

Real samples (coal extract, SRC, etc.) were also dis-

solved in THF to a concentration of 300 mg/ml. Each chroma-

tographic column was charged with 300 mg sample (1 ml solu-

tion) and the eluents gravity fed to the top of the column,

starting with hexane and increasing the solvent strength as

needed to achieve satisfactory separation among the various

groups. The flow rate at the column outlet was maintained

at 1.2 ml/min and adjusted as necessary by the teflon stop-

cock. Fractions of 3 ml each were collected manually in 4

ml vials and the solvent evaporated to constant weight as

previously described. Table 2 shows the eluents used to

give the best separation of the various group types, the

volume of solvent required and the fractions eluted.

~: Fractionation of Various Model Mixtures !:?_y LC and Analysis of Fractions !:?_y HRGC/MS

Sample Preparation. Four mixtures of model compounds

(hydrocarbons; neutral N, S and 0-containing compounds;

acids; and bases) representing the various functionalities

found in liquid fuels were dissolved in THF to a concentra-

tion of 300 mg/ml. The composition of these standards

appears in Tables 3 and 4. One ml of each mixture was

30

TABLE 2

Eluents and Fractions Collected in the Preparative Scale Fractionation Method

FRACTION ELUTED ELUENT VOLUME (ml)

1. Saturates Hexane (C6) 40

2. Monoaromatics Hexane (C6) 27

3 . Di aromatics 11. 5% benzene in c6 36

4. Triaromatics 32.0% benzene in c6 24

5. Poly nuclear 32.0% benzene in c6 25 aromatics

6. Resins Benzene/Acetone/Methy- 65 lene Chloride (3/4/3)

7. Asphaltenes Acetone/THF (2/8) 60

8. Asphaltols Pyridine 65

31

loaded onto a slurry-packed silica gel column, and, employ-

ing the optimized chromatographic conditions developed in

part-lA, the eight discrete fractions were collected from

each column. Solvents were removed until weight remained

constant. The recovered material in each fraction was then

redissolved in THF for injection into the GC/MS system.

GC/MS System. The Gas Chromatograph/Mass Spectrometer

utilized was a Hewlett Packard model 5995B (Palo Alto, Cali-

fornia) equipped with a library search system, and an HP

3390 laboratory integrator. Fused silica capillary columns

(Hewlett-Packard, Avondale, PA) were interfaced to the ion

source of the mass spectrometer through a gold transfer

line. Chromatogiaphic and mass spectrometric conditions are

displayed in Tables 5 and 6, respectively.

C: Fractionation of a Brazilian Sugarcane Bagasse Liquefaction Products £y LC and Analysis of Fractions £y HRGC/MS

Sample Preparation. The sugarcane bagasse was liqui-

fied as described in part- lA, then the "heavy oil" final

product was fractionated on silica gel columns, under the

optimized chromatographic conditions developed in part-IA

(Table 2). The eight LC fractions provided by the method

were dried to constant weight, then redissolved in high

purity THF to the proper concentration for injection into

the GC/MS system.

32

TABLE 3

Hydrocarbons and Basic Model Mixtures Used to Monitor the Preparative Scale LC Fractionation by GC/MS

HYDROCARBONS

n-Tridecane

n-Hexadecane

n-Octadecane

n-Eicosane

n-Pentyl Benzene

n-Octyl Benzene

Tetralin

Naphthalene

1-Methyl Naphthalene

Acenaphthene

Anthracene

9-Methyl Anthracene

9,10-Dimethyl Anthracene

9-Phenyl Anthracene

Chrysene

BASES

5-Ethyl, 2-Methyl Pryidine

2-Amino Pyridine

2-Phenyl Pyridine

3-Phenyl Pryidine

Aniline

N-Methyl Aniline

N,N-Dimethyl Aniline

m-Toluidine

0-Ethyl Aniline

2,4-Dimethyl Aniline

1-Amino Tetralin

Qui no line

1,2,3,4-Tetrahydroquinoline

8-Methyl Quinoline

2,6-Dimethyl Quinoline

7,8-Benzo Quinoline

Acridine

33

TABLE 4

Acidic and Neutral Model Mixtures Employed to Monitor the Preparative Scale LC Fractionation by GC/MS

ACIDS NEUTRALS

Benzyl Alcohol Cyclohexyl Acetate

1-Indanol Phenetole

Phenol Benzyl-Ethyl-Ether

0-Cresol Diphenyl Ether

P-Cresol 2,3-Dihydrobenzofuran

4-Ethyl Phenol 2,3-Dihydro, 2-Me-Benzofuran

2-Sec-Butyl Phenol Dibenzofuran

3-t-Butyl Phenol Dibenzothiophene

m-Methoxy Phenol Indole

p-Methoxy Phenol 2-Methyl Indole

2-Naphthol 2,3-Dimethyl Indole

Resorcinol Indoline

Capric Acid Carbazole

Benzoic Acid 1,2,3,4-Tetrahydrocarbazole

34

TABLE S

Gas Chromatographic Conditions Used in Part-lB of This Study

Columns: A. SE-30: 2S m x 0.2 mm i.d. (0.2 um) fused silica Initial Temperature: 80°C Isothermal Period: S min Temperature Program: 10°/min Final Temperature: 280°C He Flow Rate: 1.2S ml/min

B. CARBOWAX 20 M: SO m x 0.2 mm i.d. (0.2 um) fused silica

Initial Temperature: 80°C Isothermal Period: 5 min Temperature Program: S°C/min or 2°C/min Final Temperature: 240°C He Flow Rate: 1.0 ml/min

INJECTOR TEMPERATURE: 2S0°C

DETECTOR TEMPERATURE: 300°C

SPLIT RATIO: lS:l

SAMPLE SIZE: 1 ul (O.S mg/ml/component)

35

TABLE 6

Mass Spectrometric Conditions Employed in This Work

Type: Quadruple MS Mode: Electron Impact Interface Temperature: 2S0°c Ion Source: 150° Analyzer Temperature 180°C Ionization Voltage: 70 eV

36

GC/MS Conditions. Mass spectrometric conditions are

identical to those employed in part-lB (Table 6), gas chro-

matographic conditions, however are different. The GC con-

ditions utilized in this part are displayed in Table 7.

PART ~: Development of an Acid-Base-Neutral Separation Scheme and its Application to Alternative Fuel Mixtures

Two columns, one cation-exchange, and "one silica gel

modified with KOH", were employed for the fractionation of

mixtures of model compounds, representing the various func-

tionalities found in liquid fuels, and alternative fuel sam-

ples; into acidic, basic and neutral fractions. These con-

centrates were then characterized by High Resolution Gas

Chromatography/Mass Spectrometry (HRGC/MS}.

Preparation of the Packing Materials for Column Chromatography

Amberlyte 15, the cation-exchanger utilized, and the

silica modified with KOH, were prepared according to the

literature (53,43). Twenty gm of the cation-exchange resin

was first treated with 100 ml of 10% (v/v} HCl in methanol,

followed by washing successively with distilled water to pH

7, followed by methanol (100 ml}, dichloromethane (100 ml}

and finally n-hexane (100 ml). The silica gel modified with

KOH was prepared by mixing the silica (20 gm} with 40 ml of

37

TABLE 7

Gas Chromatographic Conditions Used in Parts lC, 2 and 3 of This Study

COLUMNS

a) CARBOWAX 20 M (H.P.): 50 m x 0.2 mm i.d. (0.2 µm) fused silica

Initial Temperature: 80°C Isothermal Period: 5 min Temp. Program: 2°C/min Final Temperature: 240°C He Flow Rate: 1.0 ml/min

b) SE-54 (J&W): 54 m x 0.32 mm i.d. (0.25 µm) fused silica

Initial Temperature: 60°C Isothermal Period: 5 min Temp. Program: 2°C/min Final Temperature: 280°c He Flow Rate: 2.9 ml/min

INJECTION TEMPERATURE: 250°C

DETECTOR TEMPERATURE: 300°C

SPLIT RATIO: 15:1

SAMPLE SIZE: 1 µl

38

a saturated solution of KOH in isopropyl alcohol (5% wt/v),

and 100 ml of chloroform. The cation resin, slurried in

tetrahydrofuran, and the KOH-treated silica, slurried in the

isopropyl alcohol-chloroform mixture, each was mechanically

stirred for 30 minutes before being introduced into a 500 x

11 mm I.D. glass column, fitted with a teflon stopcock and a

piece of glass wool to retain the packing material. The

modified silica column was then washed with 100 ml of chlo-

reform, while the resin column was washed with 100 ml of

n-hexane. Each wash solvent was the same as initial mobile

phase.

Fractionation of Model Mixtures and Liquid Fuel Samples Into Acid-Base-Neutral Components

Separate mixtures of acids, bases and ·neutrals stan-

<lards were prepared so as to contain 300 mg/ml of THF.

These standard mixtures are the ones utilized earlier for

the evaluation of the preparative scale fractionation method

(c.f. part-lB), whose composition is displayed in Tables 3

and 4. The retention behavior of the mixtures on the

cation-exchange and KOH-treated silica columns was monitored

gravimetrically (and later studied by GC/MS) by injecting 1

ml of each mixture on each of the two columns and collecting

fractions in vials of 5 ml each. These fractions were then

evaporated to constant weight, as described previously.

39

Figure 1 outlines the scheme used to fractionate a total

mixture of the standards, along with the eluents utilized to

provide the optimum conditions for the separation.

"Resins" fractions, as defined by the liquid column

chromatographic method (part lA), and derived from various

fuel sources, were dissolved in THF (~ 500 mg/ml) then sepa-

rated into their acid-base-neutral components using the sep-

aration scheme just described.

GC/MS Experimental Conditions

Standards, employed in this work, were chromatographed

individually and in their respective mixtures of acids,

bases or neutrals to determine their retention characteris-

tics and the best resolution conditions. A Car bow ax 2 OM

capillary column was utilized for this purpose. GC condi-

tions appear in Table 7 while mass· spectrometric conditions

are displayed in Table 6.

PART 3: Analysis of Acidic, Basic and Neutral Subfractions ~~o-f Alternative Liquid Fuel-Derived Resins~ HRGC/MS

Acidic, basic and neutral concentrates of the "resins"

fractions, derived from two liquid fuel sources, namely

sugarcane bagasse and Brazilian "Mina do Leao" SRC, were

subjected to analysis by HRGC/MS. The majority of the vola-

tile components in these subfractions were qualitatively and

quantitatively determined.

40

SAMPLE

,,

0,3 gm standard mix or

~o,5 g liquid fuel

20 gm cation exchange resin

non-retained components eluted with 75 ml n-hexane 1st eluent

trapped components eluted with 100 ml 30% isopropylamine, 10% MeOH in THF 2nd eluent

ACIDS + NEUTRALS COMPOUNDS BASES

f "modified with KOH" column il20 gm silica

. I .

non-retained components eluted with 75 ml CHC13 1st eluent

trapped components eluted with 75 ml 20% Formic Acid in THF 2nd eluent

NEUTRALS ACIDS

Figure 1: Separation Scheme Developed for Fractionating Liquid Fuels into Acidic, Basic and Neutral Components.

41

Sample Preparation

The acidic, basic and neutral subfractions of "resins",

provided by the previously developed separation scheme (c.f.

part-2), were evaporated to constant weight then redissolved

in high purity THF to the proper concentration for injection

onto the GC/MS system.

GC/MS Conditions

The gas chromatographic conditions, displayed in Table

7 and the mass spectrometric conditions, that appear in

Table 6, were followed in this part.

RESULTS AND DISCUSSION

PART-1: Development and Evaluation of ~ Preparative Scale LC Fractionation Method

A: Development of the LC Fractionation Method

The choice of the eluents utilized in this work (Table

2) is based on several considerations. The use of hexane

and hexane modified with benzene (or toluene) to re spec-

tively elute saturated and aromatic hydrocarbons in the liq-

uid fuels is well documented in the literature (34,88). No

preparative scale method reported to date, however, provides

as complete a fractionation of the aromatic hydrocarbons by

ring number, as this method does. Figure 2 shows the gravi-

metric results for the preparative scale chromatographic

fractionation of a mixture of saturated and aromatic hydro-

carbon standards whose composition is displayed in Table 1.

As Table 2 suggests, the key factor that governs the separa-

tion of aromatic fractions is the benzene (toluene) content

of the eluents. For the resins fraction, the solvent system

used is a modification of the one developed by Suatoni et

al. ( 28) to desorb the retained portion of a "mal tenes"

solution from an Attapulgus clay column. Figure 3 shows

42

43

gravimetrically, a chromatogram for the resins standards

whose composition appears in Table 1. Note in this chroma-

togram that elution of the resins standards starts with vial

58 (each vial represents 3 ml), long after the last PNA has

left the column. Elution is complete with vial 68. A simi-

lar chromatographic behaviour is observed for clay-derived

resins (28,214), generated from the maltenes fraction

(54,55,62,72,73) of the Brazilian Mina do Leao coal extract,

as Figure 4 indicates.

The increasing polarity, increasing molecular weight

and complexity going from resins to asphaltenes and asphal-

tols (34,46,88) required eluents of increasing solvent

strength to desorb these chemical species from a mildly

acidic silica surface.

When an asphaltene sample, derived from solubility

fractionation (15,35,67-71) of the Brazilian coal extract,

was chromatographed under the conditions in Table 2, two

discrete fractions were obtained, as the gravimetric results

in Figure 5 show. The first fraction in this figure elutes

in the region of vials 58-70, and coincides with the resins

standards (Figure 3) and the clay derived resins (Figure 4)

and is therefore named "resins". The second fraction, which

is only 13% by weight of the original sample and elutes

between vials 75 and 90 is the real asphaltenes.

Figure 2: Preparative scale liquid chromatogram of a non-polar model mixture. Composition appears in Table 1. Conditions appear in Table 2. Each vial represents 3 ml of eluent. Peak identities: 1. Saturates 2. Monoaromatics 3. Diaromatics 4. Triaromatics 5. Polynuclear Aromatics.

"' e

70

60

50

40

30

20

10

-------~~'"--~-~-=·=-=,.

L-- ................. .

10 20 30 1,0 50 60 70

Vial Number

Figure 3: Preparative scale liquid chromatogram of "resins" standard mixture. Sample is 1 ml of 200 mg solutes/ml benzene. Composition appears in Table 1. Conditions as in Table 2. Each vial represents 3 ml of eluent.

ii::. U1

"' E

Figure 4:

r1:::

JO

28

26

24

22

20

18

16

14

12 I I I I

10 ' ' ' '

8

6

4

............... .-.-. .. -----.-lO 20 JO 40 50 60 70

Vial Number

Preparative scale liquid chromatogram of "clay resins (28)" derived from Brazilian "Mina do Leao" coal extract. Sample is 1 ml of 80 mg solutes/ml of THF. Conditions as in Table 2. Each vial represents 3 ml of eluent.

ii::. O'I

kesins I n

28

26

24

22

20

18

16

"' ~ 14

12

10

8

Asphaltenes

.... ...... I' ' •,-•• ··-·····- '... I ..... ' I 30 40 50 60 70 80 90

Vial Numhcr

Figure 5-: Preparative scale liquid chromatogram of "asphaltenes" derived from solubility fractionation (74) of the Brazilian coal extract. Conditions as in Table 2. Each vial represents 3 ml of eluent. Sample is 1 ml of 120 mg solutes/ml of THF.

"'° ....J

48

An asphaltols sample, derived from solubility fraction-

ation of the same fuel, gave three discrete fractions repre-

senting 19%, 42% and 23% of the original sample by weight

(Figure 6). The first fraction coincides with the resins

(vials 58-70); the second with asphaltenes (vials 74-90);

and the third is termed asphaltols (vials 90-104). A sample

of the whole coal extract (Mina do Leao) was fractionated

under the optimized conditions (Table 2) and the gravimetric

results for the polar portion of this extract shows the

three discrete chemical classes: resins, asphal tenes and

asphaltols (Figure 7). Table 8 displays the results of a

reproducibility study of the preparative scale fractionation

method as applied to the Brazilian coal extract. Table 9

shows the results of fractionation by solubility

(15,35,67-71) as applied to the same coal extract. The

non-polar content of the fuel extract (fractions 1-5, Table

8) is much lower than the oils content (Table 9) suggesting

that the alkanes-soluble portion of the coal extract must be

contaminated with some resins.

The major part of this chemical class, "resins", is

distributed between the asphaltenes and the asphaltols, as

the results in Figures 5 and 6 confirm. Figure 8 displays

the distribution of the fractions for various liquid fuels

under the optimized preparative scale chromatographic condi-

00 s

Figure 6:

11 Asphaltenes

10

9 • Asphaltols

8

(,

: 1

Resins

~ I \ /. l I

3 .J I I .,. 2

I t ~ • .... ---.. ~ -......... __ -\.

-.--so 60 70 80 90 100

Vial Number

Preparative scale liquid.chromatogram of "asphaltols" derived from solubility fractionation of the "Brazilian" coal extract. Sample is 1 ml of 120 mg solutes/ml THF. Conditions as in Table 2. Each vial represents 3 ml of eluent.

~ l.O

30

27

211

21

t.O

" 18

15

12 2

9

6

3

I ' ..... 60 70 80 90 100

Vial Number

Figure 7: Preparative scale liquid chromatogram of the polar portion of the whole Brazilian coal extract. Conditions as in Table 2. Peak identities: 1. Resins 2. Asphaltenes 3. Asphaltols. Each vial represents 3 ml of eluent.

lTI 0

COLUMN

1

2

3

4

x

a

RSD(%)

TABLE 8

PERCENT DISTRIBUTION* OF GROUP TYPES

IN A BRAZILIAN "MINA DO LEAO" COAL EXTRACT

OBTAINED BY THE LC FRACTIONATION METHOD

wt% wt% wt% wt% wt% wt% SATURATES MONO- DI- TRI- POLYNUCLEAR- RESINS

AROMATICS AROMATICS AROMATICS AROMATICS

1. 22 0.66 4.7 7.5 2.6 56.1

1.17 0.75 3.1 8.3 2.6 54.8

1.13 0.58 4.1 7.9 2.5 54.l

1. 23 0.55 4.9 7.1 2.3 55.1

1.19 0.64 4.2 7.7 2.5 55.0

0.04 0.08 0.7 0.4 0.1 0.7

3.4 l.2xl0' 1. 7Xl0 I 5.2 4.0 1. 3

x = Average wt% a = Standard Deviation

RSD = Relative Standard Deviation *Relative to Unfractionated Material

wt% wt% ASPHALTENES ASPHALTOLS

19.3 5.1

18.9 5.4 U1

18.3 5.2 I-'

18.4 5.2

18.7 5.2

0.4 0.1

2.1 1. 9

52

TABLE 9

Fraction Distribution of Brazilian "Mina do Leao" THF Coal Extract by Solubility Fractionation Method

SAMPLE wt% ASPHALTOLS wt% ASPHALTENES wt% OILS

1 38.5 35.2 26.3

2 38.5 32.9 29.1

3 37.8 36.9 25.4

4 36.4 37.6 26.0

5 42.1 34.8 23.1

x 38.7 35.4 26.0

CJ 2.1 2.0 2.1

RSD 5.4 5.7 8.3

53

tions. In this Figure, it is noticed that in the case of

the coal liquids, the resins fraction is the major chemical

class; while for the liquefaction products of the Brazilian

sugarcane bagasse, the triaromatic fraction is the major

group-type. Had it acquired the geological age of the

coals, the sugarcane bagasse may have demonstrated a much

higher distribution of the polar fractions. Recovery of the

various liquid fuels from the preparative scale silica col-

umns is shown in Table 10. Except for the "Mina do Leao"

SRC, the other fuels exhibited high percent recoveries

(>88%), with an overall relative standard deviation of less

than 1. 5%. The low recovery in the case of the Brazilian

SRC could be due to incomplete solubilization in tetrahydro-

furan, as a result of its partial repolymerization, prior to

the chromatographic separation, a situation commonly encoun-

tered with coal liquids (74).

g: Fractionation of Various Model Mixtures Qy LC and Analysis of Fractions £y HRGC/MS

The LC fractionation method developed in Part-lA is

evaluated here. Various features of the separation method

are considered including purity of the fractions and the

nature of their chemical composition.

Prep Scale LC. Table 11 displays the gravimetric

results of the group-type fractionation of the various model

bl) s

A -160

140-

120

100

80

603

40 In. 20J

11 I I I I 2345678 Fraction No.

1603 B '"f I I 14

1201 120

n ~ j I I bl) s bO 80 80 80 s

40j I I - 60

4 40

J_ J In rll 20

12345678 12345678 Fraction No. Fraction No.

A) Indiana V solvent refined coal (SRC) (97% soluble in THF).

B) Brazilian "Mina do Leao" SRC (90% s.oluble in THF).

C) Extraction products from the Brazilian coal (100% soluble in THF).

D) Brazilian sugarcane bagasse liquefaction products (100% soluble in THF).

1 D

I _JI I IL. 17~4'i..:.7R

Figure 8: Distribution of preparative scale LC fractions for various liquid fuels. Original sample was 300 mg THF solubles.

U1 ii::.

55

TABLE 10

Recovery of Various Liquid Fuels from Preparative Scale LC Columns

LIQUID FUEL

Mina do Leao Coal Extraction Products

Mina do Leao SRC

Indiana V SRC

Sugar Cane Bagasse

*

* % RECOVERY a

1.3

1.0

1. 3

1.2

Relative to unfractionated, THF soluble material

a4 columns

b3 columns

RSD

1.4%

1. 4%

1.5%

1.3%

56

mixtures. As shown, the recovery of the hydrocarbon and

acidic fractions is quantitative, while approximately 25% of

the basic and neutral mixtures are lost. This could be due

to loss during the evaporation step. For the hydrocarbon

mixture, it is noticed that saturated and monoaromatic

hydrocarbons (F1 and F2 ) have undergone weight losses, while

the diaromatics, triaromatics and the polynuclear aromatics

(F3 , F4 and F5 ) have gained some weight. For the hydrocar-

bon fractions the recovery was based on the weight of the

individual compound classes blended in the total mixture.

It is also noticed that the major portion of the acidic,

basic and neutral mixtures coincides with the resins frac-

tion (F6 ), while less than 15% by weight of the acids and

bases elutes as asphaltenes. For these mixtures, fractions

F 1-F 5 are virtually free of acids and bases, while in the

case of the neutrals, 20% by weight of this mixture coin-

cides with the diaromatics fraction (F3 ).

HRGC/MS Analysis of Prep Scale LC Fractions. All model

compounds incorporated in this work were injected individu-

ally on the GC/MS system, to determine their retention

behaviour, purity, and mass fragmentation characteristics

(base peak ion, etc.). All compounds were then blended into

their respective mixtures of hydrocarbons, acids, bases or

neutrals to determine the best conditions for optimum reso-

TABLE 11: GROUP-TYPE DISTRIBUTION OF HYDROCARBQNS, ACIDIC, BASIC AND NEUTRAL

STANDARD MIXTURES ON PREPARATIVE SCALE SILICA GEL COLUMNS

GROUP

TYPE

SATURATES

MONOAROMATICS

DI AROMATICS

TRI AROMATICS

POLYNUCLEAR AROMATICS

RESINS

AS PHA L'rENES

MODEL MIXTURE

FRACTION

F-1

F-2

F-3

F-4

F-5

F-6

F-7

ASPHALTOLS F-8

*WT. Recovered In Each Fraction

HYDROCARBONS ACIDS * ** * ** wt. (mg) % wt. (mg) %

76.6 90.5

52.4 75.9

76.4 109

48.3 108

34.4 109 5.0 1. 67

243.7 81. 2

40.0 13. 3

286.0 96.1 288.7 96.2

**% Recovery = [WT. Recovered Per Fraction/WT. Applied Per Class] X 100%

fl';'.

BASES NEUTRALS * ** * ** wt. (mg) % wt. (mg) %

53.6 17.9

5.7 1. 9

194.5 64.6 166.4 55.5

35.5 11.B 3.0 1.0

230 76.6 228.7 76.3

VI -..J

58

lution. Hydrocarbon and neutral mixtures were chromato-

graphed on an SE-30 (100% methyl silicone) capillary column,

while acidic and basic mixtures were eluted on a Carbowax 20

M capillary column. The optimum chromatographic and mass

spectrometric conditions employed are those displayed in

Tables 5 and 6, re spec ti vely. Figure 9 is a chromatogram

for the total hydrocarbon mixture prior to fractionation.

The chemical composition is di splayed in Table 12, along

with the retention times and mass spectral characteristics

of the resolved compounds. Component (8), in this Figure,

was identified by GC/MS as diethyl phthalate, an additive

generally found in GC rubber septa. Fractions F1-F5 for

hydrocarbon mixture (Table 11) were chromatographed under

the same conditions as given in Figure 9.. Such fractions

were prepared so as to have equal concentrations for compar-

i son purposes. Figure 10 displays a chromatogram for the

saturates fraction which is shown to be free of aromatics.

Figure 11 displays a chromatogram for the monoaromatics

fraction which is slightly contaminated with the saturates,

but is free of diaromatics. Tetralin, a component exhibit-

ing an intermediate behaviour between a monoaromatic and a

diaromatic, partially elutes with the monoaromatics fraction

(component 1, Figure 11) but is mainly present in the diaro-

matics fraction (Figure 12). A similar behaviour is

59

observed for acenaphthene (component 6 of Figures 12 and 13)

which shows an intermediate behaviour between a diaromatic

and a triaromatic compound, as Figures 12 and 13 confirm.

Figure 12 demonstrates that the diaromatics fraction is free

of triaromatic species, whereas for F4 and F5 , the triaro-

matics. fraction is slightly contaminated with polynuclear

aromatics (Figure 13), while a partial overlap between tria-

romatics and polynuclear aromatics is observed for the PNA's

fraction (Figure 14).

Figure 15 shows a chromatogram of the total neutral

mixture whose composition and related characteristics of the

separated compounds appear in Table 13. All 14 components

could be well resolved using a fast temperature programming

rate (c.f. Table 3) with a run time under 20 minutes. Fol-

lowing fractionation of the neutral mixture, the two frac-

tions with appreciable recoveries, F 3 and F 6 ( c. f. Table

11), were chromatographed under the same conditions as Fig-

ure 15. The chromatogram in Figure 16 for fraction-3 of the

neutral mixture shows that it contains three components:

diphenyl ether (peak 8), dibenzofuran (peak 10), and diben-

zothiophene (peak 12). The rest of the neutral components

elute as fraction-6 (resins), except for component 1 (phene-

tole) which was not detected in either fraction, as Figure

17 confirms. This component (phenetole) could have eluted

60

1 2 3 4 5 6 7 9 11 13 15

14

10 12

8

16

2 4 6 8 10 12 14 16 18 20 22 Retention Time (min)

Figure 9: GC-FID chromatogram of total hydrocarbon standards. Peak numbers refer to compound identLfication in Table 12. Conditions: 25 m SE-30 fused silica capillary column tempera-ture programmed from 80°C to 280°C at 10°C/ min with 5 min initial hold.

61

TABLE 12

GC Retention and Mass Spectral Characteristics of Hydrocarbon Model Compounds used to Monitor LC Fractionation

by GC/MS

BASE PEAK RETENTION MOLECULAR PEAK

* NO. TIME (min) COMPONENT WEIGHT ION

1 5.33 Tetralin 132 104

2 5.45 n-Pentyl Benzene 148 91

3 5.79 Naphthalene 128 128

4 8.52 1-Methyl Naphthalene 142 142

5 8.99 n-Tridecane 184 57

6 11. 32 Acenaphthene 154 154

7 11.43 n-Octyl Benzene 190 92

9 13.43 n-Hexadecane 226 43

10 15.13 Anthracene 178 178

11 15.83 n-Octadecane 254 57

12 16.99 9-Methyl Anthracene 192 192

13 17.94 n-Eicosane 282 57

14 18.62 9,10-Dimethyl Anthracene 206 204

15 21. 06 9-Phenyl Anthracene 254 254

16 21.60 Chrysene 228 228

* Numbers correspond to the Chromatograms in Figures 9-14.

62

5 9 11 13

4 6 8 10 12 14 16 18 Retention Time (min)

Figure 10: GC-FID chromatogram of LC fraction-1 of the hydrocarbons standard mixture. Condi-tions as in Figure 9.

63

2 7

1

9 11 13

2 4 6 8 10 12 14 16 18 Retention Time (min)

Figure 11: GC-FID chromatogram of LC fraction-2 of the hydrocarbons standard mixture. Condi-tions as in Figure 9.

64

1 3 4 6

2 4 6 8 10 12 Retention Time (min)

Figure 12. GC-FID chromatogram of LC fraction-3 of the hydrocarbons standard mixture. Conditions as in Figure 9.

65

6 10 12 14

15 8

2 4 6 8 10 12 14 16 18 20 22

Figure 13: GC-FID chromatogram of LC fraction-4 of the hydrocarbons standard mixture. Conditions as in Figure 9.

66

15

14 16

12

I 2 4 6 8 10 12 14 16 18 20 22

Figure 14: GC-FID chromatogram of LC fraction-5 of the hydrocarbons standard mixture. Conditions as in Figure 9.

67

with the triaromatics fraction (not studied). This behav-

iour of neutral oxygen and sulfur compounds (dibenzofurans,

arylethers, dibenzothiophenes, etc.) coeluting with the aro-

matic hydrocarbons, is well documented in the literature

(110,126,215-216).

Figure 18 shows a chromatogram for the total acidic

mixture, prior to LC fractionation. Table 14 shows the

chemical composition along with retention times and mass

spectral information. A temperature programming rate of

S°C/minute could not resolve all the components in the

acidic mixture (Figure 18). A slower rate of 2 °C/minute

provided the necessary resolution. The acidic mixture was

not derivatized prior to GC/MS; this explains their long

retention times on the Carbowax column and the broad peaks

for two of the strongly retained components, capric and ben-

zoic acids (peaks 8 and 14, Figure 19). Following the LC

fractionation of the acidic mixture, equal concentrations of

the two major fractions F6 and F7 (Table 11) were chromato-

graphed using both a 5 °C/minute and 2 °C/minute ( F 6 only)

temperature programming rates, and, as shown in Figures 20

and 21 all the acidic components (except for capric and ben-

zoic, peaks 8 and 14) elute as fraction-6 (the resins). Low

levels of these same acids have been detected in the asphal-

tenes fraction (Figure 22). The presence of capric and ben-

68

1 2 3 4 5 6 1 s 9 10 n 12 13 14

2 4 6 8 10 12 14 16 18 Retention Time (min)

Figure 15: GC-FID chromatogram of total neutral stand-ards. Peak numbers refer to compound identi-fication in Table 13. Conditions as in Figure 9.

69

TABLE 13

GC Retention and Mass Spectral Characteristics of the Neutral Model Compounds used to Monitor LC Fractionation by

GC/MS

PEAK

*

* NO.

1

2

3

4

5

6

7

8

9

10

11

12

13

14

RETENTION TIME (min) COMPONENT

3.94 Phenetole

5.40 Cyclohexyl Acetate

5.94 Benzyl-Ethyl-Ether

6.18 2,3-Dihydrobenzofuran

7.02 2,3-Dihydro,2-Methyl Benzofuran

10.68 Indole

12.16 2-Methyl Indole

12.40 Diphenylether

13.62 2,3-Dimethyl Indole

13.98 Dibenzofuran

16.32 Indoline

16.78 Dibenzothiophene

17.28 1,2,3,4-Tetrahydrocar-bazole

17.66 Carbazole

MOLECULAR WEIGHT

122

142

136

120

134

117

131

170

145

168

119

184

171

167

Peak numbers correspond to the Chromatograms in Figures 15-17.

BASE PEAK ION

94

43

91

91

134

117

130

51

144

168

117

184

143

167

70

8 10 12

2 4 6 8 10 12 14 16

Retention Time (min)

Figure 16: GC-FID chromatogram of LC fraction-3 of the neut~al standard mixture conditions as in Figure 9.

71

2 3 6 9 13 14

5 11

4

7

2 4 6 8 10 12 14 16 18


Figure 17: GC-FID chromatogram of LC fraction-6 of the neutrals standard mixture. Conditions as in Figure 9.

72

zoic acids in the asphaltenes fraction (F7 ), however, could

not be confirmed under these conditions.

The chromatogram in Figure 23 is for the total (unfrac-

tionated) basic mixture whose composition appears in Table

15 along with related characteristics of the individual com-

ponents. Following the LC fractionation, the two fractions,

F 6 and F 7 , recovered for the basic mixture were chromato-

graphed under conditions identical to Figure 23. As shown

in Figure 24, F 6 (the resins fraction) contains all the

basic components except for 2-amino pyridine (component 8,

Table 15) which showed up in F7 (the asphaltenes) as indi-

cated in Figure 25. Also, low levels of quinoline ( compo-

nent 9) were detected in F7 (Figure 25). Impurities from

some of the standards (or solvents) or artifacts formed dur-

ing the fractionation process, are responsible for the unla-

beled peaks in Figures 20-25.

f: Fractionation of Brazilian Sugarcane Bagasse Liquefaction products Qy LC and Analysis of Fractions Qy HRGC/MS

Sugarcane Bagasse: Background. Bagasse, which is the

fibrous residue remaining after the milling of the sugar-

cane, is considered a potential fuel source. Conversion of

bagasse into gaseous or liquid fuels (217-220) or to organic

chemicals (221-222) has been a major concern. Bagasse, as

1 2, 3 4 ,5 6 7 8,9

11 10

12

10 20 30 40


Figure 18: GC-FID chromatogram of total acidic standards. Peak numbers refer to compound identification in Table 14. Conditions: 50 m carbowax 20 M capillary fused silica column temperature programmed from 80°C to 240°C at 5°C/min with 5 min initial hold.

13

....J w

74

TABLE 14

GC Retention and Mass Spectral Characteristics of the Acidic Model Compounds used to Monitor LC Fractionation by GC/MS

RET.TIME RET.TIME BASE PEAK (min) (min) MOLECULAR PEAK

* 5°C/min 2°C/min NO. COMPONENT WEIGHT ION

1 23.24 38.23 Benzyl alcohol 108 77

2 25.96 44.83 Phenol 94 94

3 26.00 45.05 0-Cresol 108 108

4 27.60 48.49 1-Indanol 134 115

5 27.60 48.72 P-Cresol 108 107

6 29.Ll4 53.28 4-Ethylphenol 122 107

7 29.66 54.12 2-Sec-Butylphenol 150 121

8 31.66 58.84 Capric Acid 172 43

9 31. 74 58.91 3-t-Butylphenol 150 135

10 33.42 62.95 P-Methoxy Phenol 124 109

11 34.18 64.72 m-Methoxy Phenol 124 124

12 42.52 83.98 2-Naphthol 144 144

13 44.84 89.16 Resorcinol 110 110

* Peak numbers correspond to the Chromatograms in Figures 18-22.

l 40

Figure 19:

o:::

2 3 4 5 6 7 8,9 10 11

12

lJ

\___ 14 A u '--- \... - "' . . . \ - -

1 · · 1----i -,--,---, - r --r--1 ,-- -.- 1 -1 50 60 70 80 90


GC-FID chromatogram of total acidic standards. Conditions: Same as Figure 18 except column temperature programming rate 2°C/min.

-..J U1

1 2,3 4,5 6,7 9 10 11

10 20 30 40


Figure 20: GC-FID chromatogram of LC fraction-6 of the acidic standard mixture. Conditions as in Figure 18.

12

13 -...]

°'

-

1 2 3 4 7 9

5

10

1

.----,---.----, I I I I I I r ,--T--T I I I I I r--r-r--,- , - I I I 40 50 60 70 80



90

.._J

.._J

1 2,3 4,5

7 9

10 20 30



12 13

40

.......i 00

1 2 3 6 9 10 11 12 13 14 16 17

7

8

4

5 15

10 20 30

--,---r,- I I I 40


Figure 23: GC-FID chromatogram of total basic standards. Peak numbers refer to compound identification in Table 15. Conditions as in Figure 18.

-i \0

80

TABLE 15

GC Retention and Mass Spectral Characteristics of the Basic Model Compounds used to Monitor LC Fractionation by GC/MS

BASE PEAK RETENTION MOLECULAR PEAK

* NO. TIME (min) COMPONENT WEIGHT ION

1 10.80 5-Ethyl,2-Methyl Pyridine 121 106

2 14.82 N,N-Dimethyl Aniline 121 120

3 19.64 N-Methyl Aniline 107 106

4 20.40 Aniline 93 93

5 22.64 m-Toluidine 107 107

6 23.06 0-Ethyl Aniline 121 106

7 23.34 2,4-Dimethyl Aniline 121 120

8 23.56 2-Amino Pyridine 94 67

9 24. 36 Quinoline 129 129

10 25.00 8-Methyl Quinoline 143 143

11 27.42 1,2,3,4-Tetrahydro- 133 129 quinoline

12 27.60 2,6-Dimethyl Quinoline 157 157

13 30.50 2-Phenyl Pyridine 155 155

14 30.68 3-Phenyl Pyridine 155 155

15 32.60 1-Amino Tetralin 147 119

16 39.92 7-8-Benzoquinoline 179 179

17 40.36 Acridine 179 179

* Peak numbers correspond to the Chromatogram in Figures 23-25.

2 3 4 5,6,7 9 10 11,12 13,14 16,17

1

10 20 30 40


Figure 24: GC-FID chromatogram of LC fraction-6 of the basic standard mixture. Conditions as in Figure 18.

00 ......

8

9

10 20 30 40 Retention Time (min)

Figure 25: GC-FID chromatogram of LC fraction-7 of the basic standard mixture. Conditions as in Figure 18.

co I\)

83

any other lignocellulosic material, undergoes degradation

into smaller molecules through thermochemical processes,

such as pyrolysis (221-223), t-irrdiation (224-225), and

liquefaction (12,226-227). Complete conversion of the

bagasse into a heavy oil has been achieved most effectively

through liquefaction, with the proper choice of experimental

conditions (12,226-227).

Utilization of this liquid product as a transportation

fuel, among other applications, is feasible. However, a

knowledge of its chemical composition is a prerequisite for

the production of an environmentally safe fuel.

To date, no detailed characterization of liquefaction

products of sugarcane bagasse has been reported. Bagasse-

deri ved liquids, like many other non-fossil (pyrolytic tars)

and fossil (coal liquids, shale oils) liquid fuels, are com-

plex organic mixtures (12), expected to be composed of hun-

dreds of individual components and numerous functionalities.

Single analytical techniques such as High Performance Liquid

Chromatography (HPLC) may therefore be unsuitable for the

characterization of such complex mixtures.

Both preparative scale LC and Normal and Reversed Phase

HPLC techniques have been utilized recently by Karam et al.

84

(228) for the analysis of a Brazilian bagasse liquid crude.

Al though prep scale LC and Normal Phase HPLC yielded well

defined chemical classes (214, 228), Reversed Phase HPLC

could not provide sufficient resolution to allow accurate

identification of individual components.

It is expected, therefore, that the method of choice

for the efficient separation and identification of the vola-

tile compounds in bagasse liquid crude would be Capillary

Gas Chromatography/Mass Spectrometry (GC/MS). This techni-

que has been successfully applied recently to the character-

ization of liquefaction and pyrolysis products of bagasse-

related wood residues (110,229).

In this section, detailed characterization of Brazilian

sugarcane bagasse liquefaction products is discussed. The

bagasse derived liquids are first fractionated, using previ-

ously developed separation methods, on silica columns (c.f.

Part-lA), into group-types, followed by identification and

quantification of the aromatic fractions by High Resolution

GC/MS. Analysis of bagasse fractions will serve two pur-

poses: first, the actual chemical composition of this

important fuel source is determined; and second, the effi-

ciency of the LC fractionation method in providing minimally

overlapping chemical classes is proven by GC/MS results.

85

Prep Scale LC Fractionation. A typical distribution of

the chemical classes in bagasse-derived liquids is displayed

in Table 16. Recovery from the LC columns is high, with

only approximately 5% by weight of the liquid crude being

irreversibly adsorbed. The non-polar fractions (F1-F5 ) of

Table 16 constitute more than 65% by weight of the crude,

with triaromatic and polynucleararomatic species being the

major components. The intermediate polar species (F6 ), how-

ever, represent less than 20% by weight, while the polar

species (F7 and F8 ) constitute less than 10% by weight of

bagasse liquid crude.

Bagasse liquids may be similar in their physical

appearance and complexity to coal liquids, however earlier

work (Part-lA) and the results in Table 16 indicate that the

major difference between the two is that bagasse-derived

liquids have a much higher content of aromatic species.

High Resolution GC/MS of Bagasse-Derived Liquids. Fig-

ure 26 shows a gas chromatogram of "unfractionated" bagasse

liquid product. Identities of the major peaks are listed in

Table 17. Aromatic hydrocarbons are the major volatile con-

stituents, as suggested by Table 16. Although a number of

components in total bagasse liquid are identified, many oth-

ers are not identified due to their low concentration levels

and the overlapping between hydrocarbons and aromatic heter-

86

TABLE 16

* Percent Distribution of Group-Types in Brazilian Sugarcane Bagasse Liquefaction Products Obtained by the LC Method

** CHEMICAL wt% ± a FRACTION CLASS (RELATIVE STANDARD DEV)

F-1 Saturates 0.80±0.04 (4.6%)

F-2 Monoaromatics 0.55±0.01 ( 1. 3%)

F-3 Di aromatics 3.5±0.3 (8.9%)

F-4 Tri aromatics 44.6±0.7 ( 1. 4%)

F-5 Polynucleararomatics 16.7±0.6 (3.4%)

F-6 Resins 19.5±0.5 (2.4%)

F-7 Asphaltenes 7.0±0.2 (2.8%)

F-8 Asphaltols 2.76±0.05 ( 1. 6%)

* Relative to unfractionated material (100% soluble in THF)

** Standard deviation for 3 determinations

87

oatomic species. Mass spectral studies revealed that many

of the peaks in Figure 26 contained more than one component.

Efficient LC separation of the aromatic hydrocarbons from

phenolic and other heterocyclic compounds, however, can

solve these problems and facilitate better detection and

identification of the latter species by GC/MS. Fortunately,

the LC fractionation method, does provide this kind of sepa-

ration, as has been demonstrated in Part-lB of this thesis.

The method also provides separation among the aromatics

themselves into one-ring, two-ring, three-ring and four or

more-ring aromatics.

A mixture of di-, tri-, and polynuclear aromatic stan-

dards was chromatographed for monitoring the respective

fractions of bagasse-derived liquids. A capillary column,

coated with SE-54 (5% phenyl 95% methyl polysiloxane) was

chosen, since this phase can provide sufficient resolution

to separate many isomeric PAH's (163). Figure 27 shows a

gas chromatogram of the aromatics model mixture. Peak iden-

tities are displayed in Table 18 along with the three most

abundant masses ( m/z) of each individual compound. Also

shown are the Kovats retention index values, calculated by

established techniques (230,231).

The di-, tri-, and polynuclear aromatic fractions of

bagasse liquids were then analyzed by GC/MS as 2 wt% solu-

2

10 20

& 7-e ·--34 51•!9 - Ln L111 nd

19 2~ ._,H L 20 l 23 J J 24

14i l J J "

i.j t1 '\~ ] ·~ [b Tn "Jl i 351 40

T

30 • • ' 40 50 60 70 80


43,44

L

Figure 26: GC-FID chromatogram of total (unfractionated} "Brazilian" sugarcane bagasse-derived liquids. Conditions: 50 m x 0.2 mm carbowax 20 M fused silica capillary column temperature programmed from 80°C to 240°C at 2°C/min with 5 min initial hold. Other conditions appear in Table 7. Identities of numbered peaks are given in Table 17.

co co

89

TABLE 17

GC/MASS SPECTRAL ANALYSIS OF "UNFRACTIONATED" BRAZILIAN SUGARCANE

BAGASSE LIQUEFACTION PRODUCTS.

PEAK RETENTION MOST POSSIBLE COMPOUND(S) METHOD OF NO.* TIME ABUNDANT OR IDENTIFICATION

(min) MASS COMPOUND TYPE(S) (m/Z)

1 12.46 104 Tetralin aC,bMS;cR

2 21. 8 6 128 Naphthalene C;MS;R

3 27.56 142 Methyl Naphthalene C;MS

4 29.14 142 1-Methyl Naphthalene C;MS;R

5 31. 86 129 Quinoline C;MS;R

6 32.30 156 Dimethyl Naphthalene C;MS

7 33.16 156 2,6-Dimethyl Naphthalene C;MS;R

8 34.54 154 Bi phenyl C;MS;R

9 34.92 156 C 2-Alkyl Naphthalene MS

10 36.56 156 c 2-Alkyl Naphthalene MS

11 38.01 107 c 2-Alkyl Phenol MS

12 38. 35 121 C 2-Alkyl Phenol MS

13 39.82 168 Methyl Biphenyl MS

14 40.24 153 Acenaphthene C;MS

15 40. 96 153 Acenaphthene C;MS;R

16 43.74 107 P-Ethyl Phc=nol C;MS;R

17 4 5. 66 121 c 3-Alkyl Phenol MS

18 46. 84 168 Methyl Acenaphthene MS

19 4 7. 3 0 16 8 Dibenzofuran C;MS;R

20 47.64 168 Methyl Acenaphthene MS

90

TABLE 17 CONTINUED

PEAK RETENTION MOST POSSIBLE COMPOUND(S) METHOD OF NO.* TIME ABUNDANT OR IDENTIFICATION

MASS COMPOUND TYPE(S) (m/Z)

21 47.82 168 Methyl Acenaphthene MS

22 50.32 166 Fluorene C;MS;R

23 51. 00 165 Methyl Fluorene MS

24 52. 70 182 Dimethyl Acenaphthene+Naphthonitrile MS

25 53. 72 180 Methyl Fluorene MS

26 54.34 182 c 2-Alkyl Acenaphthene + Indole MS

27 55 .16 180 Methyl Fluorene MS

28 56. 0 4 180 C2-Fluorene MS

29 56. 32 180 c 2-Fluorene MS

30 56.50 130 Methyl Indole C;MS

31 63.22 184 Dibenzothiophene C;MS;R

32 64.34 184 Methyl Dibenzothiophene MS

3 3' 3 4 65.50 178 Phenanthrene+Anthracene C;MS;R

35 68.42 179 Benzoquinoline Isomer C;MS

36 70.00 192 2-Methyl Anthracene C;MS;R

37 70.58 192 Methyl Anthracene/Phenanthrene MS

38 71. 28 192 C2-Alkyl Anthracene/Phenanthrene MS

39 72. 84 191 c 2-Alkyl Anthracene/Phenanthrene MS +Benzo Quinoline Isomer

40 7 5. 50 206 c 2-Alkyl Anthracene/Phenanthrene MS

PEAK RETENTION MOST NO.* TIME ABUNDANT

MASS ( m/Z)

41,42 82.12 202

43 84.68 202

44 86.44 167

45 86.68 215

46 88.06 228

47 88. 46 228

91

TABLE 17 CONTINUED

POSSIBLE COMPOUND(S) OR

COMPOUND TYPE(S)

Flouranthene+c 2-Alkyl Anthracene/ Phenanthrene+c 3-Alkyl Anthracene/ Phenanthrene

Pyrene

Carbazole

Methyl Pyrene

Chrysene

Benz-a-Anthracene

aC = Computer Match b MS = Mass Spectral Analysis

cR = Retention Time of Authentic Standard

*Peak numbers refer to GC/FID Chromatogram in Figure 26.

METHOD OF IDENTIFICATION

C;MS;R

C;MS;R

C;MS;R

MS

C;MS;R

C;MS;R

11 12 19 2-.., 4 "' 3

5 6 13 7118

1-16 17 18 2.0 23

2.1 14 9 1---. 15- 28


Figure 27: GC-FID chromatogram of aromatic hydrocarbon standards. Conditions: 54 m x 0.32 mm SE-54 fused silica capillary column temperature pro-grammed from 60°C to 280°C at 2°C/min with 5 min initial hold. Other conditions are displayed in Table 7. Peak identities are revealed in Table 18.

\0 N

93

TABLE 18

MASS SPECTRAL CHARACTERISTICS AND RETENTION DATA OF AROMATIC

HYDROCARBON STANDARDS ON SE-54 CAPILLARY GC/MS SYSTEM

PEAK RETENTION REV:NTION INDEXa NO.* TIME (min) ;ta (RSD) c

l

2

3

4

5

6

7

8

9

9.45

9.89

10.31

12.61

16.20

17.60

25.89

26.52

30.47

MODEL COMPOUND

Indane

Indene

Trans-Decalin

Cis-Decalin

Tetralin

Naphthalene

1-Me-Naphthalene

Cyclohexyl Benzene

Bi phenyl

MOLECULAR WEIGHT

118

116

138

138

132

128

142

10

11

12

32.02

1003.9±0.3(0.03%)

1012.6±0.5(0.05%)

1019.8±0.4(0.04%)

1060.8±0.4(0.04%)

1125.0±0.5(0.04%)

1148.6±0.5(0.04%)

1297.0±0.8(0.06%)

1308.9±0.5(0.04%)

1379.3±0.5(0.04%)

1407.0±0.7(0.05%)

1444.0±0.4(0.03%)

1494.8±0.3(0.02%)

1541.9±0.2(0.01%)

1604.5±0.5(0.03%)

1800.4±0.3(0.02%)

1808.5±0.2(0.01%)

1921.8±0.5(0.03%)

1963.5±0.6(0.03%)

2017.9±0.7(0.04%)

2,6-Di-Me-Naphthalene

160

154

156

168

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

34.14

37.01

39.62

43.15

54.12

54.60

60.94

63.25

66. 33

68.02

70.50

71. 49

74.44

81. 38

83.83

84.84

85.22

99.91

2048.2±0.5(0.02%)

2091.6±0.3(0.01%)

2109.5±1.0(0.05%)

2162.0±0.6(0.03%)

2285.1±0.5(0.02%)

2328. 7±0.6 (0.03%)

2347.0±0.6(0.03%)

2358.8±1.0(0.04%)

>2400

Diphenyl Methane

Acenaphthene

1,2-Diphenyl Ethane

Fluorene

Phenanthrene

Anthracene

2-Me-Anthracene

9-Me-Anthracene

Triphenyl Methane

Fluoranthene

Pyrene

9,10-Di-Me-Anthracene

m-Terphenyl

9-Phenyl Anthracene

1, 1-Binaphthyl

Chrysene

Benz-a-anthracene

Benzo-a-Pyrene

aCalculated By Interpolation Between n-Paraffins.

bStandard Deviation For 3 Determinations. =

cRelative Standard Deviation.

*Peak numbers refer to GC/FID Chromatogram in Figure 27.

154

182

166

178

178

192

192

244

202

202

206

230

254

254

228

228

252

THREE MOST ABUNDANT MASSES (m/Z)

11 7 ; 118 ; 115

116; 115; 117

67;138;68

67;81; 138

104;132;91

128;127;129

142; 141; 115

104;117;160

154;153;152

15 6; 14 1; 15 5

Ui7;168;165

153; 154; 152

91;182;65

166; 165;83

178;76;176

178;76;89

192;191;189

192; 191; 189

165;167;166

202;101;100

202; 101; 203

206;202;101

23 0; 11 5; 23 l

126;253;254

254; 126; 253

228;113;226

2,2 8 ; 11 3 ; 11 4

2 52; 126; 12 5

94

tions in tetrahydrofuran, containing 1.0 mg/ml of cyclohexyl

benzene and octadecane (di- and tri-fractions), or dibenzyl

and triphenyl methane (Polynuclear fraction) as internal

standards. The resulting chromatograms are shown in Figures

28, 29, and 30, respectively. Identifications of the num-

bered peaks in these Figures are revealed in Tables 19, 20

and 21, respectively. Concentrations of the identified com-

ponents, expressed as wt% of the respective fraction, have

been calculated assuming response factors of unity relative

to the internal standards (232).

As indicated in Table 19, two and two-and-a half ring

aromatic hydrocarbons (naphthalenes and acenaphthenes) are

the major constituents of the diaromatics fraction, while

three ring (phenanthrenes and anthracenes) and four-ring

aromatic hydrocarbons (fluoranthens and pyrenes) are major

components in tri- and polynuclear aromatic fractions, as

shown in Tables 20 and 21, respectively. Compound class

distribution in these aromatic fractions is summarized in

Table 22. Co-elution of acenaphthenes and fluorenes with

the triaromatics fraction, as indicated in Table 22, and the

overlap between three ring aromatics (phenanthrenes and

anthracenes) and the PNA' s, have also been obtained with

model compounds (c.f. Part-lB). Co-elution of some neutral

oxygen and sulfur heterocyclic compounds with the aromatic

i 1

l r-

L 24

! 26

! !

I B

J

l I I I I 1b I I I I 2b I I I I ab I I I I 4b I I I I sb I I I I 60 I I I I io I


Figure 28: GC-FID chromatogram of diaromatics fraction derived from "Brazilian" sugarcane bagasse liquids. Conditions as in Figure 27. Identities of numbered peaks are revealed in Table 19. Peaks A and Bare for internal standards cyclohexyl benzene and octadecane, respectively.

\.0 U1

Jt I

Li 2

1 l

4l1 l t~'L~Ui ."lnlr ·1 ial LI 11 I J I ~

111 ~I \I HML

9

10 2·0 30 40 50 I 60 . r--r--r-t -7ou-,- I I I e'o


Figure 29: GC-FID chromatogram of "triaromatics" fraction derived from "Brazilian" sugarcane bagasse liquid products. Conditions as in Figure 27. Identities of numbered peaks are given in Table 20. A and B refer to internal standards cyclohexyl benzene and octadecane, respectively.

l.O

°'

l 11

.J

D

l -I l -r-20 I I I I 3'o I I I I 4'o I I I I SO I I I I &O I I I I 7o I I I I Bo I I I ---r

Figure 30: GC-FID chromatogram of "polynucleararomatics" fraction derived from "Brazilian" sugarcane bagasse liquid products. Conditions as in Figure 27. Identities of the numbered peaks are given in Table 21. Peaks labelled C and D are internal standards dibenzyl and triphenyl methane, respectively.

\0 -..J

98

TABLE 19

COMPOUNDS IDENTIFIED IN DIAROMATICS FRACTION OF "BRAZILIAN" SUGARCANE

BAGASSE LIQUEFACTION PRODUCTS.

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND OR CONCEN- METHOD OF NO.* TIME (min) INDEX ABUNDANT COMPOUND TYPE TRATION IDENTIFI-

MASSES (m/Z) (wt%)** CATION

l 16.26 1125.4 104;132;91 Tetralin 0.04 ac;bMS;CR

2 l 7. 57 1148. 8 128;127;129 Naphthalene 0.98 C;MS;R

3 24.81 1277 .6 142;141;115 2-Me-Naphthalene 3.20 C;MS

4 25.86 1296.4 142;141;115 1-Me-Naphthalene 2.89 C;MS;R

5 30.52 1379.5 154;153;152 Biphenyl 0.66 C;MS;R

6 31. 37 13 94. 7 141; 156; 115 c 2-Alkyl Naphthalene 1. 40 C;MS

7 31. 53 1397.5 141;156;115 c 2-Alkyl Naphthalene 0.54 C;MS

8 3 2 .10 1407.7 156;141;155 2,6-Di Me-Naphthalene 1. 63 C;MS;R

9 33.03 1424.2 141;156;155 c 2-Alkyl Naphthalene 1. 86 MS

10 33.22 1427.5 156;141;155 c 2-Alkyl Naphthalene 1.16 MS

11 34.20 144 5. 0 141; 156; 155 c 2-Alkyl Naphthalene 0.58 MS



14 3 5. 16 1462.2 141;156;115 C 2-Alkyl Naphthalene 0.37 MS

15 35.42 1466. 8 15 6; 14 l; 15 5 c 2-Alkyl Naphthalene 0.16 MS

16 37.57 150 5 .1 153;154;152 Acenaphthene 35.96 C;MS;R

17 37.69 15 07. 2 154;153;152 Acenaphthene 13. 0 4 C;MS

18 38.63 1524.0 153;154;155 Me-Acenaphthene 0.28 MS

19 39.00 1530.7 153;152;154 Me-Acenaphthene 4.34 MS

20 39.21 1534.3 168; 139; 169 Dibenzofuran 1.64 C;MS;R

99

TABLE 19 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND OR NO.* TIME(min) INDEX ABUNDANT COMPOUND TYPE

MASSES (m/Z)

21 43 .13 1604.1 166;165;83 Fluorene

22 44.25 1624.l 168;153;167 Me-Acenaphthene

23 44.65 1631. 2 168;153;167 Me-Acenaphthene

24 45.05 1638.4 168;153;167 Me-Acenaphthene

25 45.41 1644.9 182;181;152 c 2-Alkyl Acenaphthene

26 50.95 1743.6 153;152;165

27 52.56 1772. 2 184;182;152

28 54 .15 1800.6 178;76;176

29 54.52 1807.1 17 8 i 7 6; 1 76

aC = Computer Match b MS = Mass Spectral Studies

c 3-Alkyl Acenaphthene

Dibenzothiophene

Phenanthrene

Anthracene

cR = GC Retention Time (Index) Of Authentic Standard

*Peak numbers refer to GC-FID Chromatogram in Figure 28.

CONCEN- METHOD OF TRATION INDENTIFI-

(wt%)** CATION

0.77 C;MS;R

4.52 MS

2.52 MS

0.91 MS

0.74 MS

0.65 MS

4.22 C;MS;R

6.41 C;MS;R

1.10 C;MS;R

**Concentrations determined by GC-FID and expressed as wt% of diaromatics fraction.

100

TABLE 20

COMPOUNDS IDENTIFIED IN TRIAROMATICS FRACTIONS OF "BRAZILIAN"

SUGARCANE BAGASSE LIQUEFACTION PRODUCTS

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND OR CONCEN- METHOD OF NO.* TIME(min} INDEX ABUNDANT COMPOUND TYPE TRATION IDENTIFI-

MASSES (m/Z} (wt%}** CATION***

1 16.26 1125.4 104;132;91 Tetralin aN C;MS;R

2 17.51 114 7. 6 128;127;129 Naphthalene 0.24 C;MS;R

3 24.60 1274.0 141;142;115 2-Me-Naphthalene 0.54 C;MS

4 25.63 1292.4 142;141;115 1-Me-Naphthalene 0.99 C;MS;R

5 30.47 1378.6 154;153;152 Bi phenyl 1.44 C;MS;R

6 31. 37 13 94. 7 141;156;ll5 c2-Alkyl Naphthalene N MS

7 31. 53 1397. 5 14 1 ; 15 6 ; 115 c 2-Alkyl Naphthalene N MS

8 31. 93 1404.5 156;141;155 2,6-Di-Me-Naphthalene 0.18 C;MS;R

9 33. 00 1423.7 141;156;155 c2-Alkyl Naphthalene 0.13 MS

10 33.44 1431.6 156; 141; 155 C 2-Alkyl Naphthalene N MS

ll 34.03 144 2 .1 141;156;155 c 2-Alkyl Naphthalene 0.13 MS

12 34.40 1448.7 15 6 ; 115; 12 8 c 2-Alkyl Naphthalene N MS

13 34.69 1453.8 15 6; 141; 155 c 2-Alkyl Nap.hthalene N MS

14 35.00 1459.3 141;156;ll5 c 2-Alkyl Naphthalene 0.04 MS

15 35.42 1466.8 156; 141; 155 c 2-alkyl Naphthalene N MS

16 37.00 1494.8 153; 154; 152 Acenaphthene 8. 7 5 C;MS; R

17 37.30 1500.3 168;167;153 Methyl Acenaphthene o. 72 C;MS

18 38.63 1524.0 168; 153; 167 Methyl Acenaph thene N C;MS

19 39.00 1530.7 168;153;167 Methyl Acenaphthene N C;MS

20 39.10 153 2. 4 168;139;169 Dibenzofuran 9.09 C;MS;R

101

TABLE 20 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND OR CONCEN- METHOD OF NO.* TIME (.min) INDEX ABUNDANT COMPOUND TYPE TRATION INDENTIFI-

(wt%) **CATION***

21 43.17

22 44.04

23 44.36

24 44.50

25 45.37

26 46.13

27 49.19

28 49.70

29 52.49

30 54.50

31 54.58

32 54.83

33 59.97

34 60.27

35 6 0. 97

36 61.17

37 61. 41

38 63.92

39 68.06

40 70.40

aN = Negligible

1604.9

1620.3

1626.0

1628.6

1644.1

1657.6

1712.2

1712.3

1771.0

1806.7

1808.3

1812.7

1904.3

1909.5

192 2. 1

1925.7

1929.9

1974.6

2048.3

2090.1

MASSES (m/Z)

166;165;83 Fluorene 8.50 C;MS;R

168;153;167 Methyl Acenaphthene 0.58 MS

165;180;83 Methyl Fluorene 1.09 MS


181;182;152 C2-Alkyl Acenaphthene 1.06 MS

182;181;152 c 2-Alkyl Acenaphthene 1.17 MS



184;139;92 Dibenzothiophene 1.97 C;MS;R

178;76;176 Phenanthrene 26.94 C;MS;R

178;176;76 Anthracene 8.82 C;MS;R

178;76;176 Anthracene 3.62 C;MS

192;191;189 Me-Phenanthrene/ 0.78 MS Anthrancene


192;189;95 2-Me-Anthracene 1.63 C;MS;R


192;191;95 c 2-Alkylphenan/ 0.42 MS Anthrancene

204;203;202 Phenyl naphthalene 0.13 MS

202;101;100 Fluoranthene 2.58 C;MS;R

202;100;101 Pyrene 3.16 C;MS;R


**Concentrations determined by GC-FID and expressed as wt% of The Triaromatics fraction.

***See Table 17

102

TABLE 21

COMPOUNDS IDENTIFIED IN POLYNUCLEAR AROMATIC FRACTION OF "BRAZILIAN"

PEAK RETENTION NO.* TIME(min)

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

36.78

39 .10

43. 07

4 4. 28

45.30

46.08

48.56

49.20

49.70

54.31

54.60

59.95

60.25

6 0. 94

61.16

61. 40

64.01

SUGARCANE BAGASSE LIQUEFACTION PRODUCTS

RETENTION THREE MOST POSSIBLE COMPOUND OR COMPOUND TYPE

CONCEN- METHOD OF TRATION IDENTIFI-

(wt%) ** CATION*** INDEX ABUNDANT

1490.9

1532.6

1603.1

1624.8

1642.9

1656.8

1700.9

1712.3

1721.2

1803.3

1808.5

1903.8

1909.2

1921.5

1925.4

1929.8

1976.5

MASSES ( m/Z)

153;154;152 Acenaphthene 0.37 C;MS;R

168;139;169 Dibenzofuran 1.76 C;MS;R

166;165;83 Fluorene 5.76 C;MS;R

165;180;44 Methyl Fuorene 0.51 C;MS

182;181;44 c2-Alkyl Acenaphthene 0.22 MS

181;182;152 c 2-Alkyl Acenaphthene 0.76 MS



16 5; 180; 178 Methyl Fluorene O. 54 MS

178;76;179 Phenanthrene 21.20 C;MS;R

178;76;176 Anthracene 2.25 C;MS;R

192;191;189 Me-Phenanthrene/ 0.66 MS Anthracene

192;191;189 Me-Phenanthrene/ 0.96 MS Anthracene

190;189;95 2-Me-Anthracene 1.40 C;MS;R



204;202;203 Phenyl Naphthanlene 1.96 C;MS

103

TABLE 21 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND OR CONCEN- METHOD OF NO.* TIME(min} INDEX ABUNDANT COMPOUND TYPE TRATION IDENTIFI-

18

19

20

21

22

23

24

25

26

27

28

29

30

31

68.33

68.43

70.47

70.85

71.62

72. 35

73.66

74.81

75.01

. 75.78

76.41

77 .13

84.80

85.24

20 53. 2

2054.9

2091. 4

2098.1

2111. 5

2124. 9

2148.2

2168.6

2172. 2

2185.9

2197.2

2210.l

23 46. 7

2354.5

MASSES (m/Z} (wt%} ** CATION***

202;101;200 Fluoranthene 10.31 C;MS;R

202;101;200 Fluoranthene 9.21 C;MS

202;101;200 Pyrene 6.57 C;MS;R

218;189;95 Me-Phenyl Naphthalene 1.58 MS



215;216;44 Me-Fluoranthene/ 0.71 C;MS Pyrene




216;215;44 Me-Fluorahthene/ 1.68 C;MS Pyrene


228;226;114 Chrysene 2.23 C;MS;R

228;114;226 Benz-a-Anthracene 2.72 C;MS;R


**Concentrations determined by GC-FID and expressed as wt% of the PNA's fraction.

***See Table 17.

104

hydrocarbons (mostly Di- and Tri-, Table 22) was inevitable,

due to their highly non-polar nature, as previously investi-

gated (Part-lB).

The relative distribution of aromatic species identi-

fied in the respective aromatic fractions, is also demon-

strated in Table 22, while the distribution, as compound

classes, in unfractionated bagasse-derived liquids, is sum-

marized in Table 23. These chemical species represent more

than 54% (by weight) of total bagasse liquids and about 84%

(by weight) of the non-polar fractions (F1-F5 , Table 16).

As for the saturates and monoaromatics fractions of

bagasse-derived liquids, they were not studied by GC/MS due

to their low levels (Table 16).

The intermediate polar fraction (resins) and the polar

fractions (asphaltenes and asphaltols) derived from bagasse

liquids, were analyzed by GC/MS as 27. 5 wt% solutions in

THF. Figures 31 and 32 show GC-FID chromatograms of the

resins and asphaltenes fractions, peak identities of which

are given in Tables 24 and 25, respectively. Attempts were

made to analyze the asphal to ls fraction, however, it must

have contained highly nonvolatile compounds that could not

be analyzed by GC since no peaks were observed.

A number of compounds have been identified in the vola-

tile portion of the resins and asphaltenes fractions, based

105

TABLE 22

Percent Distribution of Compound Classes in Aromatic Fractions of "Brazilian" Sugarcane Bagasse Liquefaction

Products

DI- TRI- POLY-COMPOUND AROMATICS AROMATICS AROMATICS

CLASS FRACTION FRACTION FRACTION (wt%) (wt%) (wt%)

2-Ring Aromatic Hydrocarbons 16.03 3.68 0.00 (Naphthalenes)

2.5-Ring Aromatic Hydrocarbons 63.73 23.39 9.90 (Acenaphthenes+Fluorenes)

3-Ring Aromatic Hydrocarbons 5.86 44.76 32.91 (Anthracenes+Phenanthrenes)

More Than 3-Rings 0.00 5.74 39.73 (Fluoranthenes, Pyrenes)

Oxygen, Sulfur-Heterocyclic 7.51 11. 06 1. 76 Aromatic (Dibenzofurans, Dibenzo-

thiophenes)

Total % by wt Identified 93.13 88.63 84.30

106

TABLE 23

Percent Distribution of Aromatic Compounds in Non-Polar Fractions of Brazilian Sugarcane Bagasse Liquefaction

Products

Concentrations determined by GC-FID and expressed as wt% of total bagasse liquid crude

Tetralin

Naphthalene

2-Me-Naphthalene

I-Me-Naphthalene

Bi phenyl

c2 -Alkyl Naphthalenes

Ac enaph thene~

Methyl Acenaphthenes

c2 -Alkyl Acenaphthenes

c3-Alkyl Acenaphthenes

Dibenzofuran

Fluorene

Methyl Fluorene

Dibenzothiophene

Phenanthrene

Anthracene

Methyl Phenanthrenes/Anthracenes

c2 -Alkyl Phenanthrenes/Anthracenes

0.00

0.14

0.35

0.54

0.66

0.50

5.66

0.77

1.54

0.02

4.39

4.76

0. 63

1.02

15.72

4. 33

3.07

0.06

107

TABLE 23 Continued

COMPOUND OR COMPOUND TYPE

Phenyl Naphthalene

Methyl Phenyl Naphthalenes

Fluoranthene

Pyrene

Methyl Fluoranthenes/Pyrenes

Chrysene

Benz-a-Anthracene

CONCENTRATION (wt%)

0.33

0.52

4.39

2.50

1.45

0.37

0.46

i

30 I I I I 40 I I I I s'o I I I I 60 I I I I 7b I I I I e'o I I I I 90 I .---.-- '--100-,---'


Figure 31: GC-FID chromatogram of "resins" fraction derived from "Brazilian" sugarcane bagasse liquid products. Conditions as in Figure 26. Identities of numbered peaks are given in Table 24.

._. 0 (X)

A 2 3 4 10 11 14 21 23 25.26 / 28

/ 31.32 5

B C 29

L r • 1 I I I I I I I I I I -1 --- l T

.-.---.-i 3o I I I I 4o I I I I s'o I I • I 6b I • ' ' 70 80 90 100

Figure 32.


GC-FID chromatogram of "asphaltenes" fraction derived from sugarcane bagasse liquefaction products. Conditions as in Identities of the numbered peaks are revealed in Table 25. labelled A, B and C are solvent contaminants.

"Brazilian" Figure 26. Peaks

....... 0 \0

110

TABLE 24

IDENTIFIED CHEMICAL COMPONENTS IN THE "RESINS" FRACTION OF "BRAZILIAN"

SUGARCANE BAGASSE LIQUEFACTION PRODUCTS.

PEAK RETENTION THREE MOST POSSIBLE COMPOUND OR METHOD OF NO.* TIME(min) ABUNDANT COMPOUND TYPE IDENTIFICATION

MASSES ( m/Z) **

1 32.07 .129;102;51 Qui no line C;MS;R

2 33.89 143; 115; 142 2-Me-Quinoline C;MS;R

3 36.54 94;66;65 Phenol C;MS;R

4 39.39 107;122;77 P-Cresol C;MS;R

5 39.69 107; 122; 121 Dimethyl Phenol C;MS

6 42.62 121;136;91 Trimethyl Phenol MS

7 43.38 152;151;76 Unidentified

8 43.87 107;121;122 P-Ethyl Phenol C;MS;R

9 45.66 121;136;91 Trimethyl Phenol MS

10 47.87 121;150;135 c4-Alkyl Phenol MS

11 52.82 153;126;154 Cyano Naphthalene C;MS - 12 54.41 117;90;89 In dole C;MS;R

13 55.84 167;166;153 Methyl Cyanonaphthalene MS

14 56.53 130;131;77 Methyl Indole MS

15 59.76 144;145;130 c 2-Alkyl Indole MS

16 6 0. 07 144;145;130 c 2-Alkyl Indole MS

17 60. 30 130; 14 5; 114 c 2-Alkyl Indole MS

18 61. 60 149;43;41 Phthalic Acid Dialkyl Ester C;MS

19 61.88 170;169;141 Phenyl Phenol Isomer C;MS

111

TABLE 24 CONTINUED

PEAK RETENTION THREE MOST POSSIBLE COMPOUND OR METHOD OF NO.* TIME {min) ABUNDANT COMPOUND TYPE IDENTIFICATION

MASSES(m/Z) **

20 G3.G7 184;139;152 Dibenzothiophene C;MS;R

21 G4.20 184;183;169 Methyl Dibenzothiophene MS

22 G4.97 130;172;158 c6-Alkyl Indolea MS

23 G5.20 144;117;173 CG-Alkyl Indolea MS

24 65.3G 178;7G;l7G Phenanthrene C;MS;R

25 G5.57 178;7G;l7G Anthracene C;MS;R

2G G8.08 130;173;131 CG-Alkyl Indolea MS

27 68.37 179;178;151 Benzoquinoline Isomer C;MS

28 G9.32 179;178;151 Benzoquinoline Isomer C;MS

29 71. 78 179;178;151 5,G-Benzoquinoline C;MS;R

30 72. 9G 115;144;11G 1-Naphthol C;MS;R

31 74.15 192;193;189 9-Me-An thrac .cne C;MS;R

32 74.84 144;ll5;11G 2-Naphthol C;MS;R

33 81. 44 152;180;208 Anthraquinone C;MS;R

34 82.06 202;170;101 Fluoranthene C;MS;R

35 82.83 170;169;141 m-Phenyl Phenol C;MS;R

36 83.74 170; 1G9; 141 Phenyl Phenol Isomer C;MS

37 85.45 184;183;149 Methyl Phenyl Phenol MS

38 8G.94 1G7;1G6;139 Carbazole C;MS;R

39 88.20 215;216;180 Methyl Pyrene C;MS

40 90.41 181;180;90 Methyl Carbazole C;MS

PEAK RE TENT ION NO.* TIME(min)

41 91. 69

42 92.31

aTentative


195;194;180

181;180;90

112

TABLE 24 CONTINUED

POSSIBLE COMPOUND OR COMPOUND TYPE

Dimethyl Carbazole

Methyl Carbazole


** See Table 17

METHOD OF INDENTIFICATION

**

MS

MS

113

TABLE 25

IDENTIFIED CHEMICAL COMPONENTS IN THE "ASPHALTENES" FRACTION OF


1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

32.64

34.48

35.64

38.32

40. 7 6

42.96

43. 40

47.40

50. 48

54.22

56.22

58.50

58.68

61. 30

64.40

69.34

71. 60

71. 90

72.12

"BRAZILIAN" SUGARCANE BAGASSE LIQUEFACTION PRODUCTS.


129;102;51

14 3; 115; 14 2

143; 115; 116

143;115;116

143; 142; 115

157;143;156

115;143;157

157;51;142

169;57;43

105;77;122

118;91;136

91;136;119

119;136;91

149;57;41

184; 91; 139

184;139;119

179; 151; 178

180;153;50

179;178;151


Quinoline

2-Me-Quinoline

6-Me-Quinoline

4-Me-Quinoline

3-Me-Quinoline

Dimethyl Quinoline

Dimethyl Quinoline

Dimethyl Quinoline

4-Amino Biphenyl

Benzoic Acid

0-Me-Benzoic Acid

Methyl Benzoic Acid

Methyl Benzoic Acid

Phthalic Acid Dialkyl Ester

Methyl Dibenzothiophene

c 2-Alkyl Dibenzothiophene

Benzoquinoline Isomer

Diazaphenanthrene/Anthracene

5,6-Benzoquinoline


**

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C; MS

C;MS

MS

MS

MS

MS

MS

MS

MS

C;MS

C;MS

C;MS;R


20 72. 80

21 73.14

22 74.48

23 7 5. 84

24 83.52

25 85.86

26 87. 7 8

27 88.66

28 88.82

29 8 9. 56

30 93.20

31 93. 7 4

32 94.20

THREE MOST ABUNDANT MASSES(m/Z)

179;151;178

115;117;116

126;180;117

43;41;179

43;41;51

149;43;41

127;172;155

127;172;155

172;127;155

152;181;198

203;150;87

203;150;87

203;88;204

114

TABLE 25 CONTINUED


Benzoquinoline Isomer

1-Naphthol

Diazaphenanthrene/Anthracene

Hexadecanoic Acid

Octadecanoic Acid


cx-Naphthoic Acid

B-Naphthoic Acid

B-Naphthoic Acid

c 2-Alkyl Naphthoic Acid

Azafluoranthene/Pyrene




**See Table 17


**

C;MS

C;MS;R

C;MS

C;MS;R

C;MS;R

MS

MS

MS

MS

MS

MS

MS

MS

115

on retention data of model compounds and mass spectral char-

acteristics of the individual components. Among those iden-

tified in the resins fraction, neutr~l-nitrogen classes

( indoles, carbazoles and ni tri les), basic-nitrogen classes

(quinolines, and benzoquinolines) and weakly acidic classes

(phenols), are the major compound classes; while strong

bases (quinolines), heavy aza-PAH's and strong acids (both

aliphatic and aromatic carboxylic acids) are the major chem-

ical species present in the asphaltenes fraction. Quino-

lines are distributed between both the resins and the

asphal tenes fractions, as was also shown with model com-

pounds (Part-lB), however, quinolines are more abundant in

the asphaltenes fraction as Figure 32 suggests. Carboxylic

acids are expected to be retained more strongly than phenols

by the silanol groups of the silica surface. The absence of

phenols (except for 1-naphthol) in the asphaltenes fraction

(Table 25) confirms this assumption. Phthalates, a possible

source of contamination during sample preparation steps

(233), were also found in the resins and asphaltenes frac-

tions (Tables 24 and 25).

Many of the chromatographic peaks in Figure 31 (the

resins fraction) and to a lesser extent in Figure 32 (the

asphaltenes}, are insufficiently resolved to allow for accu-

rate identification and quantitation of the individual com-

116

ponents. Further fractionation of these fractions is there-

fore necessary in order to realize those objectives. By

subjecting such fractions to acid-base-neutral separation,

more distinct chemical classes can be obtained. Such a sep-

aration procedure has been developed recently ( 182) using

various mixtures of model compounds. Results of this work

and its application to "resins" from different fuel sources

(including sugarcane bagasse) are the subject of the next

two sections of this chapter.

PART-2: Development of an Acid-Base-Neutral Separation Scheme and its Application to Alternative Liquid Fuel

Mixtures

Table 26 displays the retention behavior of the various

model mixtures on the cation exchange and the KOH-treated

silica gel columns as monitored by GC/MS. As Table 26 indi-

cates, all acidic standards (>80% by weight), except resor-

cinol, are non-retained by the cation exchanger. A few

acids (benzyl alcohol, p-methoxy phenol, m-methoxy phenol

and ~-naphthol) are partially retained by the strong acid

exchanger. Such compounds are very weak acids that may be

retained on the resin by alternative mechanisms such as

dipole-dipole interactions, hydrogen bonding, or weak cova-

lent bonding (165). All basic standards were retained by

the strong cation exchanger while all neutral model com-

117

pounds ( >85% by weight) were non-retained on the acidic

resin except for 2-methyl indole. This compound is a weak

base ( 234) that can easily be trapped by a strong cation

exchanger.

The interaction of the model mixtures with the KOH-

treated silica surface was quite interesting, as shown in

Table 26. For the acidic mixture, one component was non-re-

tained (2-sec-butyl phenol); one was partially eluted

(1-indanol); while the majority of the components (>90% by

weight) were retained. The non-retention of 2-sec-butyl

phenol may be due to the steric hindrance of the bulky butyl

group to adsorption on the basic silica surface.

Except for 2-amino-pyridine, the majority of the base

standards (>90% by weight) were eluted from the alkali-modi-

fied silica column. This component (2-amino pyridine) was

also retained on a mildly acidic .silica surface ( c. f. Fig-

ure 24 and Table 15). The only possible explanation for

such an irregularity is that the compound has an amphoteric

behaviour, acting as an acid on a basic substrate, and as a

base on an acidic substrate (silica surface). All the neu-

tral standards, however, were virtually non-retained on the

KOH-based silica surface. ~

Table 26 also shows that recoveries from both columns,

for the various mixtures of standards, are 71% or better.

TABLE 26: RETENTION BEHAVIOR OF ACIDIC, BASIC AND NEUTRAL MODEL COMPOUNDS ON

CATION-EXCHANGE RESIN AND SILICA-MODIFIED WITH KOH COLUMNS,

COMPOUNDS COMPOUNDS COMPOUNDS TOTAL COLUMN SAMPLE ELUTED wt%* PARTIALLY TOTALLY wt%* RECOVERED

RETAINED RETAINED %**

Cation Acids-Standard All Model 81. 0 Benzyl Alcohol Resorcinol 77.0 Exchange Mixture Compounds p-Methoxy Phenol Resins (Table 4) m-Methoxy Phenol

Except 2-Naphthol Resorcinol

Bases-Standard None None All Model >99.0 88.0 Mixture Compounds

(Table 3) 1--' 1--'

Neutrals- All Model 86.0 None 2-Methyl 71.0 00 Standard Compounds Indole Mixture (Table 4)

Except 2-Methyl Indole

Silica Acids-Standard 2-Sec-Butyl · 1-Indanol All Model 92.2 81. 0 Modified Mixture Phenol Compounds w/KOH Except 2-Sec-

Butyl Phenol

Bases Mixture All Model >90 None 2-Amino 80.0 of Standards Compounds Pyridine

Except 2-Amino Pyridine

Neutrals- All Model >95 None None 77.0 Mixture of Compounds Standards

• Relative To Recovered Material ** Based On 300 mg Sample Load

119

Non-quantitative recoveries are due, primarily, to losses

during the evaporation step. This was confirmed by subject-

ing the substrates, following each separation, to extraction

with a stronger solvent. The extracts were virtually free

of standard compounds, as indicated by GC/MS.

A total mixture of the acidic, basic and neutral stan-

dards was subjected to separation using the optimum condi-

tions shown in Figure 1. The chromatogram in Figure 33 is

for this mixture before fractionation, while the chromato-

grams in Figures 34, 35 and 36 are for the acidic, basic and

neutral fractions, respectively, after the mixture has been

successively separated on cation-exchange and silica modi-

fied columns. These chromatograms (Figures 33 to 36) were

generated under identical chromatographic conditions for

comparison purposes. Identities of the numbered peaks in

these Figures appear in Table 27 ..

The chromatogram in Figure 33, in addition to being

complex, shows that co-elution of several of the components

is inevitable, even with the slow temperature program

employed. These separation problems are overcome after the

total mixture is fractionated, as Figures 34 to 36 confirm.

The chromatogram in Figure 34 shows that the acidic

fraction is pure, no overlap of basic or neutral components

has been detected by GC/MS. The chromatogram in Figure 35

2 4 5 6 7 8 40 28,29,30 33 34 35 36 ':r1 10, 12 14 15 16,17 18

llJ 3 27 j I 31

19 3 42

38 39 1 f I I L.....J

90 98


Figure 33: GC-FID chromatogram of a total mixture of acidic, basic and neutral standards before fractionation. Conditions: 50 rn x 0.2 mm i.d. fused silica carbowax 20 M capillary column tem-perature programmed from 60°C to 240°C at 2°C/min with 5 min initial hold. Peak numbers correspond to compound identifi-cation in Table 27.

I-' N 0

16 17

L1J 21 23 29

L 33

31 39

12 22 24

L 70 ~r '~-L.J


Figure 34: GC-FID chromatogram of the acidic fraction after acid-base-neutral separation of the total mixture of standards. Conditions same as Figure 33.

~ N ~_,

5 8, ,, ,1r i 11 19 20

i126 :J7

II I 38 L I I I I II Ill

3, 34

33I1 ~ Ill II II Ill - 111 I

l 3 I \ II II I ll I... • .... . ..

J,\J) l~~\J~I"~- '-'V\ I "'' VU\J......JA- "' ... '-..J • -.- I 30 40 50


Figure 35: GC-FID chromatogram of the basic fraction after the acid-base-neutral separation of a total standards' mixture. Conditions same as Figure 33.

I-' N r...i

6 11 f7

~I ~ i i 40

1 LIJ I 42

·1 , i I \ I I 11

2 I I I · · l 1 . 11 1 IA 11 n 1. 11 11 11 11 1 .- r 4I>J -, I ,- b I -, :r f [ c,-=-'lb:=i I I li,.,, ~ ir g-- so r


Figure 36: GC-FID chromatogram of the neutral fraction after the acid-base-neutral separation of a total standards' mixture. Conditions same as Figure 33.

I-' Iv w

TABLE 27: ELUTION ORDER OF A TOTAL MIXTURE OF ACIDIC, BASIC AND NEUTRAL STANDARDS ON A CARBOWAX FUSED

SILICA CAPILLARY COLUMN. CHROMATOGRAPHIC CONDITION APPEAR IN TABLE 7. NUMBERS CORRESPOND

TO PEAKS IN CHROMATOGRAMS 33-36.

PEAK COMPONENT PEAK COMPONENT PEAK COMPONENT NUMBER NUMBER NUMBER

1 Cyclohexyl Acetate 15 8-Methyl-Quinoline 29 3-t-Butyl Phenol

2 Phenetole 16 Phenol 30 2-Amino Teralin

3 5-Ethyl I 2-Methyl Pyridine 17 0-Cresol 31 P-Methoxy Phenol

4 Benzyl-Ethyl-Ether 18 Diphenyl Ether 32 Indole I-'

5 N, N Dimethyl Aniline 19 1,2,3,4-Tetrahydro- 33 m-Methoxy Phenol N Quinoline ""'

6 2,3-Dihydro,2-methyl- 20 2,6-Dimethyl-Quinoline 34 2-Methyl Indole Benzofuran

7 2,3-Dihydro Benzofuran 21 P-Cresol 35 2,3-Dimethyl Indole

8 N-Methyl Aniline 22 1-Indanol 36 Dibenzothiophene

9 Aniline 23 4-Ethyl Phenol 37 7,8-Benzoquinoline

10 2,4-Dimethyl Aniline 24 2-Sec-Butyl Phenol 38 Acridine

11 0-Ethyl Aniline 25 2-Phenyl-Pyridine 39 2-Naphthol

12 Benzyl Alcohol 26 3-Phenyl-Pyridine 40 1,2,3,4-Tetrahydro-Carbazole

13 2-Amino Pyridine 27 Dibenzofuran 41 Resorcinol

14 Quinolin2 28 Capric Acid 42 Carbazole

125

demonstrates that the basic fraction is slightly contami-

nated with some weakly acidic components (peaks 31, 33, 39

and 41) identified as p-methoxy phenol, m-methoxy phenol,

2-naphthol and resorcinol, respectively. Their concentra-

ti on levels are low, as indicated by relative peak areas

measurements. The only contamination of the neutral species

comes from 2-methyl indole (peak 34). This is further

emphasized in the chromatogram of Figure 36, for the neu-

trals fraction, which shows the complete absence of 2-methyl

indole.

The chromatogram in Figure 36 for the neutral fraction,

shows a strong overlap from 2-sec-butyl phenol (peak 24) and

3-t-butyl phenol (peak 29) as expected. Also, low levels of

benzyl alcohol (peak 4) and 1-indanol (peak 22) have been

found in this fraction.

Application of the optimized separation scheme to liq-

uid fuel samples was then attempted. Table 28 shows the

percent distribution of acids, bases and neutrals in the

"resins" fraction derived from different alternative fuel

sources. This Table also indicates that among the three

fuels studied, sugarcane bagasse is highly rich in neutral

species; Mina do Leao SRC is high in acidic compounds; and

Amax SRC is high in basic compounds. Analysis of resins

subfractions for "sugarcane bagasse" and "Mina do Leao" SRC

by HRGC/MS is described in the next section.

126

TABLE 28

Distribution of Acidic, Basic, and Neutral Compounds in the "Resins'' Fractions Derived from Alternative Fuel Sources

% BASES FUEL % RESINS* IN RESIN % ACIDS % NEUTRALS

Mina do Leao SRCa 54.83 67.26 10.63 22.10

Amax SRCb 52.28 76.55 7.38 16.08

c Sugarcane Bagasse 19.50

*

63.37 7.87

Relative to unfractionated, THF soluble material

a90% soluble in THF

b75% soluble in THF

c100% soluble in THF

28.76

127

PART-3: Analysis of Acidic, Basic and Neutral Subfractions of "Resins" Derived from Alternative Liquid Fuels !2_y

HRGC/MS

It has been demonstrated in Part-lC that Direct High

Resolution GC/MS analysis of the ITcrude" resins fraction,

derived from alternative liquid fuels, provided insufficient

resolution for accurate quanti tation and identification of

the individual components. It was obvious that chromate-

graphic fractionation of the "resins" prior to GC/MS was

essential.

Throughout this work, it has been confirmed, using both

model compounds and real samples, that the "resins" fraction

is essentially composed of acidic (phenols), basic (quino-

lines, pyridines, anilines and amines) and neutral (indoles

and carbazoles) components. Therefore, separation of the

"crude resins" into these three chemical species is a log-

ical step. Separation into acidic, basic and neutral frac-

tions was carried out utilizing the procedure developed in

Part-2. Results of this subfractionation process of the

"resins fraction", derived from various fuel sources, have

been presented in Table 28.

Prior to subjecting each "resins" subfraction to an in

depth characterization by High Resolution GC/MS, chromato-

graphic conditions had to be optimized for the various

acidic, basic and neutral mixtures of model compounds. Most

128

of these had been proven earlier to be possible constituents

of the "resins fraction". All model compounds incorporated

in this work were injected individually on the GC/MS system,

to determine their retention characteristics; then blended

into their respective mixtures, to determine the best condi-

tions for optimum resolution.

Retention behaviour of all model compounds was studied

on two fused silica capillary columns: A Carbowax 20 M, and

an SE-54 (5% phenyl, 95% methyl polysiloxane polymer).

Al though the Carbowax column provided superior selectivity

towards models and real samples as well, retention informa-

tion from both columns, particularly Kovats retention

indexes, was essential in the characterization of the vari-

ous fractions. The optimized gas chromatographic and mass

spectrometric conditions utilized in this study appear in

Tables 7 and 6, respectively. These conditions were main-

tained throughout the work to guarantee reliability of the

results and day-to-day reproducibility.

Kovats retention indexes on both columns were calcu-

lated by interpolation between n-alkanes.

raffinic mixture was daily injected prior to any other sam-

ple. Reproducibility of the retention data of the normal :;·

paraffins was within an acceptable range, as indicated in

Tables 29 and 30, for both capillary columns.

129

TABLE 29

Day-to-Day Reproducibility of n-Alkanes Retention Data on Carbowax 20 M Capillary Column

Chromatographic Conditions Appear in Table 7

RETENTION RETENTION RETENTION TIME TIME TIME AVERAGE

n-PARA- (min) (min) (min) RETENTION TIME FFIN FEB.5 FEB.8 FEB.28 ± STAND. DEV.

C-12 4.96 4.88 4.86 4.90±0.04 (0.8%)

C-13 6.96 6.88 6.85 6.90±0.05 (0.7%)

C-14 10.17 10.09 10.04 10.10±0.05 (0.5%)

C-15 14.47 14.40 14.36 14.41±0.05 (0.3%)

C-16 19.57 19.51 19.49 19.52±0.04 (0.2%)

C-17 24.97 24.92 24. 94 24.94±0.02 (0.08%)

C-18 30.47 30.44 30.46 30.46±0.01 (0.04%)

C-20 40.94 40.96 40.85 40.92±0.05 (0.1%)

C-22 50.48 50.53 50.41 50.47±0.05 (0.09%)

C-24 59.26 59.34 59.31 59.30±0.03 (0.06%)

C-26 67.40 67.50 67.72 67.54±0.13 (0.2%)

C-28 75.03 75.17 75.35 75.18±0.13 (0.2%)

C-30 82.22 82.38 82.56 82.38±0.14 (0.2%)

130

TABLE 30

Day-to-Day Reproducibility of n-Alkanes Retention Data on SE-54 Capillary Column

Chromatographic Conditions Appear in Table 7.

RETENTION RETENTION RETENTION TIME TIME TIME AVERAGE

n-PARA- (min) (min) (min) RETENTION TIME FFIN MAR.4 MAR.19 MAR.31 ± STAND. DEV.

C-10 7.58 7.76 7.75 7.70±0.08 ( 1. 1%)

C-11 12.83 12.94 12.92 12.90±0.05 (0.4%)

C-12 19.07 19.17 19.22 19.16±0.06 (0.3%)

C-13 25.81 25.80 25.90 25.84±0.05 (0.2%)

C-14 32.54 32.51 32.51 32.52±0.02 (0.05%)

C-15 38.95 38.93 38.83 38.91±0.05 (0.1%)

C-16 45.04 45.08 44.98 45.03±0.04 (0.1%)

C-17 50.82 50.82 50.78 50.81±0.02 (0.04%)

C-18 56.31 56.22 56.27 56.26±0.04 (0.7%)

C-20 66.44 66.33 66.34 66.37±0.05 (0.7%)

C-22 75.50 75.55 75.42 75.49±0.05 (0.07%)

C-24 83.95 83.94 83.81 83.90±0.06 (0.07%)

C-26 91. 81 91.70 91. 62 91. 71±0. 08 (0.08%)

C-28 99.12 99.07 98.95 99.05±0.07 (0.07%)

C-30 105.91 105.96 105.83 105.90±0.05 (0.05%)

C-32 112.33 112.37 112.26 112.32±0.05 (0.04%)

131

Results presented from now on, for model mixtures and

the "resins" subfractions, have been obtained, unless stated

otherwise, using the Carbowax 20 M capillary column. Figure

37 shows a chromatogram of aromatic hydrocarbon standards.

Peak identities are displayed in Table 31 along with the

retention data of the individual components. Mass spectral

characteristics of these standards have been presented ear-

lier (Table 18). Figure 38 shows· a chromatogram of some

neutral standards. Identities of the numbered peaks in this

Figure are given in Table 32 along with retention data and

the three most abundant and characteristic masses (m/z) of

the individual components. The chromatograms in Figures 39

to 41 are for acidic standards. Table 33 displays identi-

ties, and related retention and mass spectral characteris-

tics of the individual compounds in these Figures. The

chromatograms in Figures 42 to 44 are for basic standards.

Identities of the numbered peaks in these Figures are

revealed in Table 34 along with retention data and the three

most abundant and characteristic masses (m/z) of the indi-

vidual components.

Acidic, basic and neutral subfractions of "resins",

derived from Brazilian sugarcane bagasse liquid products and

Brazilian Mina do Leao SRC, were then analyzed by HRGC/MS as

27.5% solutions in tetrahydrofuran (THF), containing 1.0

12 10

_ll_ 17

8 9 II

'--....

1) Jo ~'-- 2/ 2.4

_JU~

-.--~-r--r-r-r20-,----,-~


Figure 37: GC-FID chromatogram of aromatic hydrocarbon standards. Condi-tions: 50 m x 0.2 mm i.d. carbowax 20 M capillary column temperature programmed from 80°C to 240°C at 2°C/min with 5 min initial hold. Other conditions are displayed in Table 7. Peak identiti~s are revealed in Table 31.

I-' w N

2

11 13 16 18

21 22

15 19 9 12 14

10 1 5 7

3 6

24

F 4 e 12 16 20 24 2e 32 16 40 ' 44 ' 4B ' s02 ' s16 ' 60 ' 6~ ' 6B ' 1~ ' 16 ' eo ' el. '

Figure 38:

rt·;:


GC-FID chromatogram of neutral standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are given in Table 32.

-

...... w w

s 9,10 14 18 20

2 I n; ; I I 29

25 I 33

I 32 '---JL 11 ~ 11 11 ~ I\ I

---r--ir-.--.-,~-.--r--r--ir-.--.-r~.---.---.---..---.--.------.-~,...--.----.-~.---.---.---.r-.--.--.~,...--.---.-~.--.---.---.~-.--.---.~.--

8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 80 84

Figure 39:


GC-FID chromatogram of acidic standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are given in Table 33.

~ lJ) .i::..

Figure 40:

4 8 19

18 3 7 13

-- :

28

4 -,- t.'6 T 52 1 ~6 I 60--,-6~ 1 6~ I 72 I 7~ I


GC-FID chromatogram of acidic standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are revealed in Table 33.

I-' w V1

21 30

26 'O

.~.-.--,,--,--,~-.--.~.--.-~.--.-~'r--.-~-r--..-~.....--..-~-r----r-~.---.-~.----~~~

~ ~ ~ m • Retention Time "(min)

Figure 41: GC-FID Chromatogram of some carboxylic acids standards on carbC"wax 20 M ·column. Conditions as in Figure 37. Peak identities are revealed in 'I'able 33.

...... t.J

°'

3 7 15 16 19 20 21 24 31 34 35 38

29 5 6

3

\ ' \.__ \. '- '- '- \.

..__J --

1- 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72


Figure 42: GC-FID chromatogram of basic standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are given in Table 34.

I-' w -...J

33

2

23

37 11 13 26

17

F 4 I 8 I i2 I l6 I 210 I 24 I 28 I 3~ I 316 I 4b I 414 I 4h I 5~ I 5~ I 6b I 6L I 6h h I


Figure 43: GC-FID chromatogram of basic standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are given in Table 34.

~ w C')

_1 I ' I :. 4 --,. 8

Figure 44:

22 25 28

10 38

41 29 14 32 11

40 8

Retention Time (r.iin)

GC-FID chromatogram of basic standards on carbowax 20 M column. Conditions as in Figure 37. Peak identities are given in Table 34.

....... w ~

140

TABLE 31

Retention Characteristics of Aromatic Hydrocarbon Standards * on Carbowax 20 M Capillary Column

RETENTION PEAK TIME RETENTION MODEL

NO.** (min) INDEX*** COMPOUND

1 5.03 Decal in

2 7.44 1317.3 Indane

3 10.65 1386.7 Indene

4 12. 42 1425.0 Tetralin

5 18.79 1562.7 Cyclohexyl Benzene

6 21.46 1620.4 Naphthalena

7 28.84 1780.0 1-Methyl Naphthalene

8 32.90 1867.8 2,6-Dimethyl Naphthalene

9 34. 24 1896.8 Bi phenyl

10 35.81 1930.8 Di phenyl Methane

11 40.06 2022.6 1,2-Diphenyl Ethane

12 40.87 2040.2 Acenaphthene

13 49.67 2230.4 Fluorene

14 64.93 2560.4 Phenanthrene

15 65.16 2565.4 Anthracene

16 69.98 2669.6 2-Methyl Anthracene

17 70.63 2683.7 Triphenyl Methane

18 73.57 2747.2 9-Methyl Anthracene

19 81. 49 2918.5 Fluoranthene

141

TABLE 31 Continued

RETENTION PEAK TIME RETENTION MODEL

NO.** (min) INDEX*** COMPOUND

20 81. 70 2923.0 9,10-Dimethyl Anthracene

21 84.11 2975.2 m-Terphenyl

22 84.58 2985.3 Pyrene

23 93.08 9-Phenyl Anthracene

24 97.43 Chrysene

* Mass spectral characteristics are given in Table 18 ** Peak Nos. correspond to the chromatogram in Figure 37

*** Calculated by interpolation between n-alkanes (average of 2 determinations)

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

142

TABLE 32

RETENTION AND MASS SPECTRAL CHARACTERISTICS OF NEUTRAL STANDARDS ON

RETENTION TIME (min)

6. 71

7.00

7.82

9.52

11. 65

13. 98

14.95

24.62

35.44

4 0. 43

43.22

46.28

47.90

48. 7 5

54.25

54. 8 6

56.30

56.66

CARBOWAX 20M CAPILLARY COLUMN

RETENTION MODEL COMPOUND MOL. wt. INDEX**

1301.5 Anisole 108

1307.8 Cyclohexyl Acetate 142

1325.5 Phenetole 122

1362.3 Benzyl-Ethyl-Ether 136

1408.3 Pyrrole 67

1458.7 2,3-Di-Hydro, 2-Me 134 Benzofuran

1479.7 2,3-Di-Hydro, 120 Benzofuran

1688.8 Benzothiophene 134

1922.7 Diphenyl Ether 170

2030.6 m-Phenoxy Toluene 184

2091. 0 2-Methoxy 158 Naphthalene

2157.1 Dibenzofuran 168

2192.2 0-Methoxybiphenyl 184

2210.6 Diphenylsulphide 186

2329.5 Indole 117

2342.7 2-Methyl Indole 131

2373.8 Benzophenone 182

2381.6 7-Methyl Indole 131

THREE MOST ABUNDANT MASSES (m/Z)***

108;65;78

43;82;67

94;66;122

91;79;77

67;41;68

134; 91; 119

91;120;63

134;89;63

51;170;141

184;91;51

115; 158; 128

168;139;63

184; 141; 169

186;185;51

117;90;89

130;131;77

10 5; 7 7; 18 2

130;131;77

143

TABLE 32 CONTINUED

PEAK RETENTION RETENTION MODEL COMPOUND MOL. wt. THREE MOST ABUNDANT NO.* TIME (min) INDEX** MASSES (m/Z)***

19 59.81 2449.7 2,3-Di-Me-Indole 145 144;145;130

20 61. 84 2493.6 5-Ethyl-Indole 145 13 0; 14 5; 77

21 62. 71 2512.4 Dibenzothiophene 184 184;139;92

22 76.43 2809.1 1,2,3,4-Tetra 171 14 3; 16 7; l 71 Hydro Carbazole

23 80.46 2897.9 Anthraquinone 208 152;208;180

24 86.16 3021. 4 Carbazole 167 167;143;835

*Most of these numbers correspond to the chromatogram in Figure 38

** Calculated by interpolation between n-Alkanes (Average of two Determinations)

*** First mass is base peak ion.

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

144

TABLE 33

RETENTION AND MASS SPECTRAL CHARACTERISTICS OF ACIDIC STANDARDS ON

ON CARBOWAX 20M CAPILLARY COLUMN


8.06

28.55

28.68

30.42

35.10

35.11

35.80

38.79

38.96

39.06

39.26

42.28

43.33

44. 26

44.37

4 5. 45

45.89

47.00

48. 86

48.94


1330.7 Cyclohexanol 100

1773.8 2,6-Di-t-Butyl 206 Phenol

1776.6 Benzyl Alcohol 108

1814.2 2,6-Xylenol 122

1915.4 Phenol 94

1915.6 0-Cresol 108

1930.6 2-t-Butyl,6-Me- 164 Phenol

1995.2 P-Cresol 108

1998.9 1-Indanol 134

2001.0 2,5-Xylenol 122

2005.4 2,4-Xylenol 122

2070.6 2,3-Xylenol 122

2093.4 P-Ethyl Phenol 122

2113.5 2-Sec-Butyl Phenol 150

2115.8 2-t-Butyl Phenol 150

2139.2 3,4-Xylenol 122

2148.7 2,3,5-Tri-Me- 136 Phenol

2172.7 2,t-Butyl,4-Me- 164 Phenol




57;82;67

191;57;41

77;57;79

107;122;121

94;66;65

108;107;77

121;149;164

107;108;77

116;115;63

10 7; 12 2; 121

107; 122; 121

107;122;77

107;122;77

121;77;150

107;135;150

10 7; 12 2; 121

121;136;91

121;149;91

135;107;44

13 5; 10 7 i 15 0

PEAK NO.*

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36


49.58

51. 03

51. 94

52.96

54.98

58. 95

67.53

72. 37

74.33

75.60

76.42

79.50

8 2. 18

83.17

83.92

84.98

145

TABLE 33 CONTINUED


2228.5 Decanoic Acid 172

2283.9 2,4-Di-t-Butyl 206 Phenol

2259.9 3,4,5-Tri-Me- 136 Phenol

2301.6 P-Methoxy Phenol 124

2345.3 m Methoxy Phenol 124

2431.1 Dodecanoic Acid 200

2616.6 Tetradecanoic Acid 228

2721.3 1-Naphthol 144

2763.7 2-Naphthol 144

2791.1 Hexadecanoic Acid 256

2808.9

2875.5

2933.4

2954.8

2971. l

2994.0

9-Hydroxy Fluorence 182

Resorcinol

m-Phenyl Phenol

Octadecanoic Acid

4,6-Di-t-Butyl Resorcinol

2,5-Di-t-Butyl Hydroquinone

110

170

284

222

222

* Peak Numbers Correspond To Chromatograms In Figures 39-41


41;60;43

191;57;41

121;136;91

109;124;81

12 4; 94; 4 4

41;43;60

41;43;60

115;144;116

14 4 ; 115; 116

43;41;126

152; 181; 180

44;110;82

170;115;141

43;73;41

207;41;44

41;163;207

** Calculated by Interpolation Between n-alkanes (Average Of 2 Determinations)

*** First Mass Is For The Base Peak Ion.

146

TABLE 34

RETENTION DATA AND MASS SPECTRAL CHARACTERISTICS OF BASIC STANDARDS

ON CARBOWAX 20M CAPILLARY COLUMN


1 5.12 N.D.+ 2,6-Di-Me-Pyridine 107 107;106;66

2 5.67 N.D. 2-Ethyl Pyridine 107 106;107;79

3 5.88 N.D. 3-Me-Pyridine 93 93;66;65

4 8.91 135 0 .1 3,5-Di-Me-Pyridine 107 107; 106;79

5 8.92 1350.3 5-Ethyl,2-Me- 121 106;121;77 Pyridine

6 10.77 1390 .1 3,4-Di-Me-Pyridine 107 107;106;79

7 13.19 1442.5 N,N-Di-Me-Aniline 121 120;121;77

8 14.19 1465.1 4-Ethyl,3-Methyl 121 121;120;106 Pyridine

9 17.38 1532.9 N,N-Diethyl Aniline 149 134;77;106

10 21. 01 1611.8 N-Methyl Aniline 107 106;107;77

11 22.55 1644.4 Aniline 93 93;66;65

12 22. 80 1649.9 2,3-Cyclohexeno 133 132;133;105 Pyridine

13 25.02 1697.7 m-Toluidine 107 10 7; 10 6; 7 7

14 28.16 17 65. 6 0-Ethyl Aniline 121 106;121;77

15 28.87 1780.8 2,4-Di-Me-Aniline 121 120;106;121

16 29.68 1798.4 Quinoxaline 130 130;103;76

17 29.92 1803.6 2-Amino Pyridine 94 67;94;41

18 31. 21 1831. 3 Quinoline 129 129;102;128

19 32.54 1860.2 8-Me-Quinoline 143 143;142;115

~

147

TABLE 34 CONTINUED


20 37.98 1977.6 1,2,3,4-Tetra-H 133 129; 133;51 Quinoline

21 38.30 1984.6 2,3-Di-Me- 158 117;76; 15 8 Quinoxaline

22 38.92 1997.8 2,7-Di-Me-Quinoline 157 15 7 ; 15 6 ; 11 5

23 39.04 2000.5 2,6-Di-Me-Quinoline 157 157;156;115

24 44.44 2116. 9 2-Benzyl Pyridine 169 16 8; 16 7; 51

25 45.40 2137.8 2-Phenyl Pyridine 155 155;154;77

26 46.14 2153.7 3-Phenyl Pyridine 155 15 5; 154; 51

27 47.33 2179.3 4-Phenyl Pyridine 155 155;154;51

28 50.53 2248.5 1-Amino-Tetralin 147 119;147;146

29 51. 48 2268.9 Azobenzene 182 77;51;105

30 55.03 2 34 5. 5 2-Hydroxy Pyridine 95 67;95;41

31 58. 9 6 2430.5 4-Aza-Fluorene 167 167;166;139

32 60.80 2470.3 O-Ni tro-Aniline 138 138;65;92

33 61. 38 2482.8 Diphenyl Amine 169 169;168;167

34 63.51 2528.6 Phenazine 180 180;179;50

35 63.70 2532.8 1-Naphthyl Amine 143 143; 115; 116

36 67.64 2617.7 7,8 Benzoquinoline 179 17 9 ; 17 8; 151

37 69.06 2648.5 Acridine 17 9 179;89;178

38 71. 27 2696.3 m-Nitro-Aniline 138 65;92;138

39 71. 93 2710. 3 5,6-Benzoquinoline 17 9 179;178;151

40 83.70 2964.5 P-Nitro-Aniline 138 65;138;108

PEAK NO.*

41


89.64

148

TABLE 34 CONTINUED


3092.8 N-Phenyl,1-Naphthyl 219 Amine

*Peak Numbers Correspond To Chromatograms In Figures 42-44


219;218;217

**Calculated By Interpolation Between n-Alkanes (Average of 2 Determinations)

*** First Mass(m/Z) Corresponds To Base Peak Ion

+N.D. Not Determined (Below 1300)

149

mg/ml of triphenyl methane (acidic subfractions), anthracene

(basic subfractions), or diphenyl methane (neutral subfrac-

tions) as internal standards. For identification of the

numerous components in these subfractions, three well-estab-

lished techniques were employed: 1) Comparison (matching)

of the mass spectrum of each peak, eluted from the gas chro-

matograph and detected by the mass spectrometer, against the

library of the GC/MS system utilizing the computer search

facilities; 2} matching retention times (Kovat retention

indexes) of the individual components along with their base

peak ions, as determined by the Selected Ion Monitoring

(S.I.M.) approach, against authentic standards (Tables 31 to

34), and 3) careful manual inspection of the mass fragmenta-

tion pattern of each individual component. Computer match-

ing was considered "likely" whenever the·correlation coeffi-

cient for the comparison against the ten most abundant

masses (m/z) of the compound in question was 0.95 or better.

Identification is considered positive when the same result

is obtained by at least two independent techniques, other-

wise it is tentative. In many cases, however, mass spectra

were compared against reference tables (235-238) and availa-

ble literature (42, 110, 143, 145, 152, 160, 161, 163-165,

171, 173, 174, 176, 179, 181, 183, 185, 186-188, 216, 239).

Quanti tation of the individual components in the various

150

subfractions was carried out by considering an average

F. I. D. response factor of 11 0. 75" for the aromatic heteroa-

tomic species, relative to aromatic hydrocarbon internal

standards, in accordance with the literature (110,232).

Figure 45 shows a chromatogram of the acidic subfrac-

tion of resins derived from sugarcane bagasse liquid prod-

ucts, while Figure 46 shows the Total Ion Chromatogram (TIC)

of the same subfraction. The upper trace in Figure 46 rep-

resents the Single Ion Monitoring (SIM) chromatogram. Ion

107 (m/z=107) was monitored throughout the run. This ion is

the base peak of many alkyl phenols (c.f. Table 33). The

"SIM" chromatogram would therefore show a peak for every

component that has this selected ion. The area of the peak

would reflect the total abundance of that particular ion in

the component of interest. The shaded area in the "TIC"

chromatogram reflects the concentration level of the peak in

question. Identities of the numbered peaks in Figure 45 are

given in Table 35. As expected, this subfraction is com-

posed exclusively of acidic species (except for component

30, identified as carbazole). This subfraction is rich in

alkyl phenols, naphthols and most prominently phenyl phe-

nols. Concentrations of the identified components are

expressed as wt% of the acidic subfraction. As indicated in

Figure 45, identification of approximately 25% of the com-

151

pounds was based on mass spectral studies alone. Such com-

pounds were tentatively identified as homologs of alkyl phe-

nyl phenol, based on available mass spectra of methyl and

ethyl or dimethyl phenyl phenols.

Figure 47 shows a chromatogram of the basic subfraction

of resins derived from sugarcane bagasse liquid products,

while Figure 48 shows the Total Ion Chromatogram "TIC" of

this same subfraction. Various single ions were monitored

throughout the run. At first ion 107 (m/z=107), which rep-

resents the base peak of many pyridines and anilines (c.f.

Table 34) was monitored; later ions 129 (alkyl quinolines),

155 (phenyl pyridines) and finally 179 (benzoquinolines)

were monitored. Identities of the numbered peaks in Figure

47, which are revealed in Table 36, indicate that the compo-

nents having ion 107 in the "SIM" chromatogram were phenols

rather than anilines or pyridines. However, as Table 36

confirms, this basic subfraction is rich in quinolines and

most prominently benzoquinolines. Some aklyl indoles are

present in this basic subfraction, a situation also encoun-

tered with model compounds, which reflects their weakly

basic nature. On the other hand, a neutral specie, like

carbazole, which is expected to be present only in the neu-

tral subfraction, based on the behaviour of model compounds

( c. f. Part-2), has been found in the acidic subfraction

11

L

J"' ~~~~~~~~~~~~~~~~~....,.~...--..,.~...--..,.~,-....,.~y---y~y---y~y---,-~y---,-~y---,-~y---,-~y---,-~.--,--,~~....,.~~~~~~

10 20 30 40 50 60 70 80 90 100

Figure 45: GC-FID chromatogram of "acidic subfraction" of the "resins fraction" derived from "Brazilian sugarcane bagasse" liquefaction products, as obtained on a carbowax 20 M column. Conditions as in Figure 37. Identities of numbered peaks are given in Table 35.

...... lI1 1')

S.I.M.

---, ---.--------. T.I.C.

de Ii l A /,_ 1 ooA l -~~ .. i

,--~-r

40

4

I 45 - I r r -

Minutes

11

12 10

50 55

Figure 46: Total ion chromatogram (T.I.C.) of acidic subfraction of resins derived from Brazilian "sugarcane bagasse" liquids. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric con-ditions are given in Tabl~ 6. Peak numbers same as Figure 45.

...... U1 w

'Tl

I-'·

lO c:: t-1 ro .::..

(j\ 0 0 ::i

rt"

I-'· ::i c:: ro 0..

t-3 . H

. "'

no

:;::

.....

::> c:. ,... ro "'

"' "' ...., 0 ...., "' co

0

r:n . H

::;::

I-" w

I-" .,,_

;>- r J I

)

t· f

i

f7S1

'Tj

f-'·

<.O c:: 11

([) ""' O"\ (') 0 ::i

rt

f-'· ::i c:: (1

) CL

""'3

H ~ C

X>

'-" ..... 0 0 .....

0 '-"

CJ)

H ::s::

l ~~ 1"

\_.,

.--ii

) -·

SS1

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

l-56

TABLE 35

COMPOUNDS IDENTIFIED IN THE ACIDIC SUBFRACTION OF THE "RESINS"

FRACTION DERIVED FROM SUGARCANE BAGASSE LIQUEFA~TION PRODUCTS, AS

STUDIED ON A CARBOWAX 20M CAPILLARY COLUMN

RETENTION RETENTION TIME INDEX (min)

40. 5 2 2032.4

42.32 2071. 3

42.89 2083.6

43.54 2097.6

45.47 2139.2

4 5. 80 214 6. 4

47.57 2184.6

47. 72 2187.8

49.84 2233.6

52.75 2296.4

54.39 2331. 8

55.15 2348.2

61.14 2477.5

61. 78 2491. 3

72. 54 2723.6

74.62 27 68. 5

POSSIBLE COMPOUND(S) OR COMPOUND

THREE MOST ABUNDANT CHARACTERISTIC MASSES(m/Z)

CONCENTRATION METHOD (wt%)** OF

107;122;70

121;136;91

152;151;76

107;122;77

107;122;121

121;135;136

121;.136;91

107;136;77

135;107;150

135;107;150

70;42;41

71;41;42

149;104;57

170;169;141

115;144;116

144;115;116

TYPE

c2-Alkyl-Phenol

c 3-Alkyl Phenol

Bephenylene

P-Ethyl Phenol

3,4-Xylenol

2,3,5-Trimethyl Phenol

m-Isopropyl Phenol

P-n-Propyl Phenol

c 4-Alkyl Phenol

c 4-Alkyl Phenol

Undecanoic Acid

c 11-carboxylic Acid

0.23

0.07

0. 25

0.75

0.07

0. 14

0. 14

0.19

0.05

0.08

1. 25

0.33

Phthalic Acid Dialkyl 1.39 Ester

Phenyl Phenol Isomer 0.42

1-Naphthol 0.04

2-Naphthol 0.24

IDENTIFI-CATION

C;MS

C;MS

C;MS;Rc

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C;MS

C; MS

C; MS

C;MS;R

C;MS;R

157

TABLE 35 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND(S) CONCENTRATION METHOD NO.* TIME INDEX ABUNDANT OR COMPOUND (wt%)** OF

(min) CHARACTERISTIC TYPE IDENTIFI-MASSES(m/Z) CATION

17 75. 32 2783.6 158;157;128 Methyl Naphthol 0.65 C;MS

18 77. 81 2837.4 158;157;128 Methyl Naphthol 0.17 C;MS

19 78.15 2844.7 158;157;128 Methyl Naphthol 0.03 C;MS

20 78.37 2849.5 172;171;157 c 2-Alkyl Naphthol 0.15 C;MS

21 7 8. 54 2853.l 172;157;171 c 2-Alkyl Naphthol 0.14 C;MS

22 79.95 2883.6 158;128;157 Methyl Naphthol 0.41 C;MS

23 80.65 2898.7 172;157;171 c 2-Alkyl Naphthol 0.16 C;MS

24 82.47 2937.5 170;141;115 m-Phenyl Phenol 1. 71 C; MS; R

25 83.46 2959.3 170;141;115 Phenyl Phenol Isomer 2.53 C;MS

26 84.23 2975.9 170;169;115 Phenyl Phenol Isomer 0.74 C;MS

27 85.22 2997.3 184;183;115 Methyl Phenyl Phenol 0.94 C;MS

28 85.60 3005.5 184;183;115 C#-Alkyl Phenyl 1.13 MS henol

29 85.93 3012.6 198;197;168 C#-Alkyl Phenyl 1.16 MS henol

30 8 6. 20 3018.5 16 7; 16 6; 8 3. 5 Carbazole 2. 56 C;MS;R

31 87.01 3036.0 184;183;185 Methyl Phenyl Phenol 1. 23 C;MS

32 87.34 3043.1 184;212;183 Cp-Alkyl Phenyl 0.77 MS henol

33 88. 96 3078.1 198;184;197 C~-Alkyl Phenyl 0.46 MS henol

158

TABLE 35 CONTINUED


(min) CHARACTERISTIC TYPE IDENTIFI-MASSES(m/Z) CATION

34 89.65 3093.0 198;197;169 C~-Alkyl Phenyl 1. 20 MS henol

35 90.31 310 7. 2 198;197;183 C~-Alkyl Phenyl 0.22 MS henol

36 90.79 3117.6 198;199;183 C~-Alkyl Phenyl 0.29 MS henol

37 91. 23 3127.1 198;183;41 C~-Alkyl Phenyl 0.04 MS henol

38 91. 99 314 3. 4 212;197;183 C~-Alkyl Phenyl 0.33 MS henol


40 93.37 3173.2 197;212;182 Cp-Alkyl Phenyl 0.12 MS henol


42 94.36 3194.6 19 7 ; 212 ; 18 4 C ~-Alkyl Phenyl 1. 97 MS henol

43 95.04 >3200 198;183;197 C rAlkyl Phenyl 1. 33 MS henol

44 95.56 >3200 198;183;197 C~-Alkyl Phenyl 0.51 MS henol

aC = Computer Match

bMS = Mass Spectral Studies

cR = Retention Time (Index) of Authentic Standard

*Peak numbers refer to CJ:-FID Chromatogram in Figure 45.

**Coocentrations determined by GC-FID and expressed as wt% of th: acidic subfraction.

159

(component 30, Table 35) and here in the basic subfraction

(component 38, Table 36), and in high concentrations rela-

tive to the respective subfractions. The contamination

level of carbazole in the acidic subfraction, however, is

negligible since this subfraction represents less than 8% of

the resins fraction, while over 60% of the resins fraction

is basic, as has been shown in Table 28.

Table 36 indicates that approximately 50% of the compo-

nents were identified using authentic standards, while the

rest were identified by computer match and mass spectral

investigation, due to limited number of model compounds.

Figure 49 shows a chromatogram of the neutral subfrac-

tion of resins derived from sugarcane bagasse liquefaction

products, while Figure 50 shows the Total Ion Chromatogram

"TIC" of this same subfraction. Two single ions were moni-

tared throughout the run: Ion. 107, to monitor phenols

(between 40 and 70 minutes, Figure 50) and ion 167 later on

to monitor carbazoles. These ions are the base peaks of

such chemical species, as Tables 33 and 32 indicate.

As the "SIM" chromatogram and the results in Table 37

indicate, components with ion 107 are really phenols, while

those having ion 167 are carbazoles, as expected. Note the

large concentration of carbazoles in the "SIM" chromatogram

and also in Table 3 7. This Table also indicates that the

JL 't l'l JO

1 '\ 10

-.-~....-.-,--..-......-.-,---.--.---.....-r-T~~~.--r-.---r-....--.--T-r--..-.....-r--1---r-..-.....-.--.-r-T"-.-,.-~.---.-~~-.---

ro ~ ~ ~ ~ M ro n ~

Figure 47: GC-FID chromatogram of basic subfraction of the "resins fraction" derived from brazilian sugarcane bagasse liquefaction products using a carbowax 20 M column. Conditions as in Figure 37. Identities of numbered peaks are revealed in Table 36.

!--'

°' 0

S.I.M.

25 T.I.C.

Figure 48:

~ ~ .. ' . ~

2

/\ a AL t. ~~t~ 11

8

Minutes

Total ion chromatogram (T.I.C.) of the basic subfraction of "resins" derived from Brazilian "sugarcane bagasse" liquids. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric conditions appear in Table 6. Peak numbers same as Figure 47.

t-'

°' t-'

S. I.M.

13 ""---......_.

T.I.C. 50 55

Figure 48: Continued

16 22

60

Minutes

~ fli·~ 26

27

' ~ 2a2l 30

.. _.LU~~ _ .... .A. ft

I --,--~....--~-,.~~~

65 70

I-' O"I N

"Ij

t-3

I F~~

Cf.)

r-·

l.Q

H

H

c ::;::

t-1

CJ

(1)

...., "'

~

co

n 0 ::i

rt

r-·

::i c (1) a.

CX>

0

£91

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

164

TABLE 36

COMPOUNDS IDENTIFIED IN THE BASIC SUBFRACTION OF THE "RESINS" FRACTION

DERIVED FROM SUG~RCANE BAGASSE LIQUEFACTION PRODUCTS, AS STUDIED ON A

CARBOWAX 20M'CAPILLARY COLUMN


30.04

31. 51

32.56

33.34

35.03

37.51

38.87

39. 18

41. 70

4 2. 92

43.37

47.42

47.65

52.83

54.05

56.22

56.53

1806.2

1837.8

1860.5

1877.5

1914.0

1967.4

1996.8

200 3. 5

20 57. 9

2084.2

2093.9

2181. 3

2186.3

2 29 8 .1

23 24. 6

2371. 5

2378.0

POSSIBLE COMPOUND(S) CONCENTRATION METHOD THREE MOST ABUNDANT CHARACTERISTIC MASSES (rn/Z)

94;67;41

129;102;128

143; 142; 115

143; 115; 128

94; 6 6; 6 5

143; 142; 115

107;108;77

10 7; 12 2; 121

157; 115; 156

152; 151; 76

107;122;77

121;136;77

107; 136; 7 7

16 9; 14 0; 16 8

117;90;89

13 0; 13 1; 10 3

130;131;103

OR COMPOUND (wt%)** OF TYPE IDENTIFI-

2-Arnino Pyridine

Qui no line

8-Methyl Quinoline

2-Methyl Quinoline

Phenol

4-Methyl Quinoline

P-Cresol

2,4-Xylenol

2,4-Dirnethyl Qui no line

Unidentified

P-Ethyl Phenol

rn-Isopropyl Phenol

P-n-Propyl Phenol

4-Arnino Biphenyl

In dole

Methyl Indole

7-Methyl Indole

0.05

1. 51

0.05

0.26

0.14

0.46

0.27

0. 48

0.06

1. 25

0.06

0.26

0.04

0.39

0.25

0.10

CATION***

C;MS;R

C;MS;R

C;MS;R

C; MS

C;MS;R

C; MS

C;MS;R

C;MS;R

C;MS

C;MS;R

C; MS

C;MS

C;MS

C;MS;R

C; MS

C;MS;R

165

TABLE 36 CONTINUED


(min) CHARACTERISTIC TYPE IDENTIFI-MASSES (m/Z) CATION***

18 58.34 2417.l 130; 131; 77 Methyl Indole 0.09 C;MS

19 58.94 24 29. 9 167;166;139 4-Aza-Fluorene 0.21 C;MS;R

20 59.70 2446.4 144;145;130 2,3-Dimethyl Indole 0.09 C;MS;R

21 59.95 2451. 9 130;145;115 c2-Alkyl Indole 0.21 C;MS

22 61. 46 2484.5 17 0; 141; 115 Phenyl Phenol Isomer 0.30 C;MS

23 62.46 2506. 0 184;139;92 Dibenzothiophene 0.15 C;MS;R

24 63.32 2524.5 130;131;77 c 2-Alkyl Indole 0.03 C;MS

25 66.07 2583.9 180;152;151 Methyl Phenazine 0. 08 C;MS

26 67. 86 2622.5 179;178;151 7,8-Benzoqu:noline 1. 09 C;MS;R

27 69.20 2651. 6 179;178;151 Acridine 0.66 C;MS;R

28 71.17 26 94. 1 179;178;151 Benzoquinoline Isomer 0.20 C;MS

29 71. 42 2699.5 179;178;151 Benzoquinoline Isomer 0.47 C;MS

30 71. 96 2711. 2 179;178;151 5,6-Benzoquinoline 0.45 C;MS;R

31 72. 40 2720. 6 179;178;151 Benzoquinoline Isomer 0.23 C;MS

32 73.90 2752.9 193;178;165 Methyl Benzoquinoline 0.08 C;MS

33 74.23 2760.2 144;115;116 2-Naphthol 0.24 C;MS;R



36 82.04 2928.7 170;141;115 m-Phenyl Phenol 0.32 C;MS;R

37 83.00 2949.6 17 0; 115; 141 Phenyl Phenol Isomer 0.47 C;MS

38 86.15 3017.3 167;166;139 Carbazole 7.76 C;MS;R

PEAK NO.*

39

40


89.33 3086.0

90.65 3114.5

166

TABLE 36 CONTINUED

POSSIBLE COMPOUND(S) OR COMPOUND


TYPE

181;180;152 Methyl Carbazole

181;180;152 Methyl Carbazole



0.30

0.06

IDENTIFI-CATION***

C;MS

C;MS

**Concentrations determined by GC-FID and expressed as wt% of the basic subfraction.

***C. F. Table 35

4S l ~1 .. t.kt

I !>QI t·· t~'r i ··r, \~

w~~

Figure 49: GC-FID chromatogram of neutral subfraction of the "resins fraction" derived from "Brazilian sugarcane bagasse" liquefaction products as obtained on a carbowax 20 M capillary column. Conditions as in Figure 37. Identities of numbered peaks are given in Table 37.

I-' (jl .....J

S.I.M.

• , , , ., Y -. r --. .,. ~ ~~l~JU.~~

. .. ..... • +

I -.- --r---1

T. r.c: 30 35 40 45 Minutes

Figure 50: Total ion chromatogram (T.I.C.) of neutral subfraction of "resins" derived from Brazilian "sugarcane bagass~' liquids. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric conditions are given in Table 6. Peak numbers same as Figure 49.

I-' O"I CXl

'-"'.!

>-3

i:r.

i

H

f-'·

H

<.O

. ::;::

c

(')

"' 0 ~

. (1)

U1

.·~

0

N "'

0 0 ::i

('T

f-'· ::i c (1) °'

N '°

w

0

..,, ..... ::l

(=-

"' .... Ill rn

~~

°' ..,, r~

J

f ....

~~

0

r JO

k•1S

7.f

t~

t

11~

l 69

1

~~--c===-==-=====---~ _lf,:::::=:::=:::=:~-~_llJj_ S. I.M.

48 49

45

r-- -,--·-1--------.---, 75

T.l.C.

Figure 50:

80

Continued

47

I I

53

56

1 - ,-- ,-- r -,-- --, 85 90 95

Minutes

...... -...J 0

171

neutral subfraction is rich in indoles and naphthonitriles.

Some aromatic hydrocarbons have also been found in this sub-

fraction, however, aromatic hydrocarbons and phenols repre-

sent approximately 4% by weight and 12% by weight of the

identified portion of the neutral subfraction, while over

83% of it is represented by neutral species. Identification

of approximately 33% of the compounds in Table 37 was car-

ried out using authentic standards, while 50% of them were

identified based on computer match and mass spectral stud-

ies. In 17% of the cases, mass spectral inspection only was

implemented. Such components were tentatively identified as

highly aklylated phenols or carbazoles, whose mass spectra

were not available in the computer files. Compositional

assignments were therefore based on the mass spectral char-

acteristics of lower alkyl derivatives of such chemical

species.

The relative distribution of the total volatiles (vola-

tile to GC) present in the respective resins subfractions of

sugarcane bagasse and in unfractionated resins is demon-

strated in Table 38, while the distribution of the identi-

fied species, as specific compounds or compound types, in

unfractionated resins is summarized in Table 39. According

to Table 38, less than 37% of the resins fraction is vola-

tile; whereas the chemical species identified and quanti-

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

172

TABLE 37

COMPOUNDS IDENTIFIED IN THE NEUTRAL SUBFRACTION OF THE "RESINS"

FRACTION DERVIED FROM SUGARCANE BAGASSE LIQUEFACTION PRODUCTS, AS

STUDIED ON A CARBOWAX 20M CAPILLARY COLUMN


33.23

35.07

37.49

38.94

39.09

39.35

41. 36

42.36

42.53

43.53

43.87

4 4. 90

45.26

45.39

45.89

46.87

47.30

47.78

1875.0

1914.7

1967.0

1998.3

20 01. 5

2007.1

20 50. 5

2072.1

2075.8

2097.4

2104.7

2126.9

2134.7

2137.5

2148.3

2169.5

2178.8

218 9. 1

POSSIBLE COMPOUND($) OR COMPOUND


CONCENTRATION METHOD

121;136;91

10 8; 10 7 i 77

135;150;91

118;146;90

107;122;77

122;107;77

121;136;91

122; 107 i 77

121;136;91

107;121;122

121;136;91

135;150;91

121;136;91

121;150;135

121i13 6; 91

135;121;150

107;135;150

121; 13 6; 91

(wt%)** OF TYPE

c 3-Alkyl Phenol 0.02

0-Cresol 0.13

c4-Alkyl Phenol 0.08

Methyl Indanol 0 .14

2,5-Xylenol 0.08

2,4-Xylenol 0.14

c 4 -Al~yl Phenol 0.04

2,3-Xylenol 0.20

c3-Alkyl ~henol 0.11

P-Ethyl Phenol 0.46


2-t-Butyl Phenol 0.03



2,3,5-TrimethylPhenol 0.52



P-n-Propyl Phenol 0.08

IDENTIFI-CATION***

C;MS

C;MS;R

C;MS

C;MS

C;MS;R

C;MS;R

C;MS

C;MS;R

C;MS

C;MS;R

C;MS

C;MS;R

C;MS

C;MS

C; MS; R

C;MS

C;MS

C;MS

173

TABLE 37 CONTINUED



19 48.06 219 5. 2 135; 150;91 C 4-Alkyl Phenol 0.08 C;MS

20 48.68 2208.5 13 5; 15 0; 91 4-t-Butyl-Phenol 0. 14 C;MS;R

21 49.26 2221.1 121;136;91 c 3-Alkyl Phenol 0.02 C;MS

22 49.81 2232.9 16 6; 16 5; 83 Fluorene 0.17 C;MS;R

23 50. 5 5 2248.9 121;91;164 c 5-Alkyl Phenol 0.07 MS

24 51. 90 227 8 .1 107;121;91 3,4,5-TrimethylPhenol 0.06 C;MS;R

25 52. 6 6 2294.5 153; 126; 127 Naphthonitrile 2.06 C;MS

26 53.09 2303.7 135; 121; 164 C 5-Alkyl Phenol 0.08 MS

27 54.35 2330.9 117;90;89 Indole 0.09 C;MS;R

28 55. 0 2 2345.4 130;131;103 2-Methyl Indole 0.08 C;MS;R

29 55.64 2358.8 167;153;140 Methyl Naphthonitrile 0.82 C;MS

30 56.46 2376.5 130;131;103 7-Methyl Indole 0.52 C;MS;R

31 57.97 2409.1 167;166;140. Methyl Naphthonitrile 0.08 C;MS

32 59.87 2450.1 144;145;130 2,3-Dimethyl Indole 0.27 C;MS;R

33 60.20 2457.2 130;145;131 c 2-Alkyl Indole 0.39 C;MS

34 61. 71 2 48 9. 8 170; 14 1; 115 Phenyl Phenol Isomer 0.63 C;MS +5-Ethyl Indole

35 63.60 2530.6 130;131;159 C 3-Alkyl Indole 0.21 C;MS

36 64.58 2551. 8 130; 158; 172 c 4-Alkyl Indole 0.02 MS

37 6 5. 21 256 5. 4 178;176;89 Phenanthrene 0. 27 C;MS;R

174

TABLE 37 CONTINUED


(min) CHARACTERISTIC TYPE IDENTIFI-MASSES(m/Z) CATION***

38 6 5. 39 2569.3 178;176;89 Anthracene 0.22 C;MS;R

39 67. 93 26 24. 1 130;131;173 c5-Alkyl Indole 0.21 MS

40 6 8. 38 2633.8 131; 130; 201 c 6-Alkyl Indole 0.15 MS

41 70.48 267 9. 1 130;145;215 c 7-Alkyl Indole 0.20 MS

42 73 .11 2735.9 130; 131; 173 C 5-Alkyl Indole 0.12 MS

43 73.70 2748.6 192;191;189 9-Methyl Anthracene 0. 10 C;MS;R

44 81. 02 2906.6 152;180;208 Anthraquinone 0.72 C;MS;R

45 81. 78 2923.1 202;200;101 Fluoranthene 0.49 C;MS;R

46 82.48 2938.2 202;216;215 Methyl Fluoranthene 0.08 C;MS Pyrene

47 85.52 3003.8 167;139;83.5 Carbazole 0.05 C;MS

48 86.49 3024.7 167;139;83.5 Carbazole 7.04 C;MS;R

49 86.89 3033.4 167;139;83.5 Carbazole 8.41 C;MS

50 88.69 3072. 2 216;215;108 Methyl Pyrene 0.17 C;MS

51 89. 9 5 3099.4 181;180;152 Methyl Carbazole 2.91 C;MS

52 91.14 312 5. 1 195;194;180 C 2-Alkyl Carbazole 0.05 C;MS

53 91. 82 3139.8 181;180;152 Methyl Carbazole 0.56 C;MS

54 93. 3 3 3172.4 195;194;180 c 2-Alkyl Carbazole 0.15 C;MS

55 93.76 3181. 7 180;195;209 C 4-Alkyl Carbazole 0.28 MS

56 94.71 >3200 195;194;180 C 2-Alkyl Carbazole 0.41 MS

175

TABLE 37 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND(S} CONCENTRATION METHOD NO.* TIME INDEX ABUNDANT OR COMPOUND (wt%)** OF

(min} CHARACTERISTIC TYPE IDENTIFI-MASSES(m/Z} CATION***

57 95.50 >3200 19 5 ; 2 0 9 ; 18 0 c 3-Alkyl Carbazole 0.06 MS

58 96. 10 >3200 195;194;180 c 3-Alkyl Carbazole 0.15 MS

59 97.62 >3200 167;209;252 c 6-Alkyl Carbazole 0.07 MS


**Concentrations determined by GC-FID and expressed as wt% of the neutral subfraction.

***C. F. Table 35

176

tated in Table 39 represent approximately 26% of the whole

resins fraction, which amounts to 70% of the total volatiles

in this fraction.

As for resins derived from Brazilian "Mina do Leao"

Solvent Refined Coal (SRC), its acidic, basic and neutral

subfractions (c.f. Table 28) were analyzed by HRGC/MS in a

similar manner, and under identical experimental conditions

to those employed for sugarcane bagasse.

Figures Sl, S3 and SS

acidic, basic and neutral

show gas chromatograms of the

subfractions, respectively of

resins derived from the Brazilian SRC, while Figures S2, S4

and 56 show the total ion chromatograms of the re spec ti ve

subfractions. Identities of the numbered peaks in Figures

Sl, 53 and S5 are shown in Tables 40, 41 and 42, respec-

tively. As shown in Table 40, the acidic subfraction is

composed exclusively of the acidic species phenols, inda-

nols, naphthols and long chain carboxylic acids. A negligi-

ble contamination from the weaker base 2,5-dichloro aniline

(component 23) has occurred. The major basic species iden-

tified in the basic subfraction are anilines, quinolines and

benzoquinolines as indicated in Table 41. The contamination

of this subfraction with some phenols, indanols or tetral-

ones, was inevitable. Tetralones, however, represent a

major chemical class in the neutral subfraction, as Table 42

177

TABLE 38

Percent Volatiles in the Resins Fraction of Sugarcane Bagasse and its Respective Acidic, Basic and Neutral

Subfractions

SUBFRACTION

Acidic

Basic

Neutral

* wt% VOLATILES IN SUBFRACTION

54.97%

31. 37%

42.01%

Total % Volatiles in Unfractionated "Resins"

* As determined by GC-FID

** Calculated using the results of-Table 28

% OF RESINS ** FRACTION

4.33%

19.88%

12.08

36.29%

178

TABLE 39

Percent Distribution of Identified Compounds in the Acidic, Basic and Neutral Subfractions of Bagasse-Derived Resins


Phenol

P-Cresol

0-Cresol

2,4-Xylenol

2,5-Xylenol

3,4-Xylenol

P-Ethyl Phenol

c2 -Alkyl Phenol Isomers

m-Isopropyl Phenol

P-n-Propyl Phenol



c3-Alkyl Phenol Isomers

c4 -Alkyl Phenol Isomers

c5-Alkyl Phenol Isomers

2-t-Butyl Phenol

4-t-Butyl Phenol

Methyl Indanol

Undecanoic Acid

* CONCENTRATION (wt%)

0.09

0.18

0.04

0.37

0.02

0.01

1.05

0.02

0.05

0.22

0.17

0.02

0.09

0.18

0.05

0.01

0.05

0.04

0.12

179

TABLE 39 Continued


c 11-carboxylic Acid


m-Phenyl Phenol

Phenyl Phenol Isomers

Methyl Phenyl Phenols

c 2 -Aklyl Phenyl Phenols

c 3-Alkyl Phenyl Phenols



c 6 -Alkyl Phenyl Phenols


c 8 -Alkyl Phenyl Phenols

1-Naphthol

2-Naphthol

Methyl Naphthol

c 2 -Alkyl Naphthol

2-Amino Pyridine

Qui no line

8-Methyl Quinoline

2-Methyl Quinoline

4-Methyl Quinoline


0.03

0.12

0.36

1.02

0.18

0.22

0.32

0.25

0.02

0.03

0.01

0.02

<0.01

0.18

0.11

0.04

0.03

1. 02

0.03

0.18

0.31

180

TABLE 39 Continued



4-Amino Biphenyl

4-Aza Fluorene

Methyl Phenazine

7,8-Benzoquinoline

Acridine

5,6-Benzoquinoline

Other Benzoquinolines

Methyl Benzoquinolines

Bephenylene

Dibenzothiophene

Phenanthrene

Anthracene

9-Me-Anthracene

Fluoranthene

Methyl Fluoranthene/Pyrene

Anthraquinone

Indole

7-Methyl Indole

Methyl Indole Isomers

2,3-Dimethyl Indole


0.04

0.03

0.14

0.05

0.74

0.45

0.30

0.61

0.26

0.07

0.10

0.08

0.07

0.03

0.15

0.08

0.22

0.29

0.23

0.25

0.14

181

TABLE 39 Continued

* COMPOUND OR COMPOUND TYPE CONCENTRATION (wt%)

c2 -Aklyl Indoles 0.28

c3-Alkyl Indoles 0.06


c5 -Alkyl Indoles 0.10



Naphthonitrile 0.63

Methyl Naphthonitrile 0.26

Carbazole 8.03

Methyl Carbazole 1. 31

c2 -Alkyl Carbazoles 0.17

c3-Alkyl Carbazoles 0.06



* Concentrations determined by GC-FID and expressed as wt% of unfractionated resins.

182

demonstrates. The contamination of this subfraction with

acidic (phenols, indanols), and weakly basic (anilines) com-

pounds was also inevitable, however, such species represent

less than 14% by weight of the identified components. The

contribution of aromatic hydrocarbons to this neutral sub-

fraction is negligible, as Table 42 confirms.

The relative distribution of the total volatiles pres-

ent in the respective resins subfractions of the Brazilian

SRC and in unfractionated resins is displayed in Table 43,

while the distribution of the identified species, as spe-

cific compounds or compound types, in unfractionated resins

is summarized in Table 44. According to Table 43, less than

28% of the resins fraction is volatile, whereas the chemical

species, identified and quantitated, in Table 44 represent

approximately 24% of the whole resins fraction, which

amounts to 86% of the total volatiles in this fraction.

HRGC/MS has been implemented, so far, for the analysis

of the resins subfractions in various liquid fuels, utiliz-

ing a single capillary column. The information obtained

from the gas chromatograph, when combined with that of the

mass spectrometer proved to be sufficient for the identifi-

cation and quantitation of the numerous components in such

complex mixtures. In the absence of a mass spectrometer,

however, identification by High Resolution GC alone is pos-

10 22

4L1J 7 I 25 33

11 13

1i I U I~· 38

~n I 47

S0...-1 l+-51

.\.lJ_,_ L 618 ~ h)

---, r--.-----T -- r---r-- T

10 20 30- -, 1 - ,-- - ,-- 40-- ,---, ,-- I 50 -- , 1 ' 1 60 1 1 ,- -,---.,b_____,--,---,---, eb I I I l

Figure 51: GC-FID chromatogram of derived from "Brazilian tions as in Figure 37. Table 40.

"acidic subfraction" of the "resins fraction" Mina do Leao solvent refined coal". Condi-Identities of numbered peaks are given in

I-' ex:> w

~ ~ J~ - ,,,. ' A J._., t. c-A.. l_ ""' ~ _,_ ~~L ll_. ~- __ ~-LL_ S.I.M.

42

10 _Jlj2 33 3LJJ40

4ll 22 23 34

30 31 P\i;. 3 39

-..J'"--"-1'--,. ...... -.J·~29 ~"' l~v ~ • • .... 4 +· .~. • d.. •'

40 45 50 55 T. I. C. 60 Hinutrs

Figure 52: Total ion chromatogram of the acidic subfraction of "resins~ derived from Brazilian "Mina do Leao" SRC. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric conditons appear in Table 6. Peak numbers same as Figure 51.

I-' CX)

"'"

~....../ ./''-' J, {, => '·

S.I.M. ,

51

43 ~~J.!'):/\__Jv

lo 7 50 l ~~~0 ~

,---1----,---r I I 70 75 80 85

Ninutes


I-' 00 lJl

10

L 20

24 r.1.7 38

9 L.

3

41

I I 20 I I I I 3b I 1 I 1 40 I I j I sQ I I I I 60 1 I 1 1 7b 1 I 1 1 80 I I I I 90 r·

Figure 53: GC-FID chromatogram of derived from Brazilian tions as in Figure 37. Table 41.

"basic subfraction" of the "resins fraction" "Mina do Leao" solvent refined coal. Condi-Identities of numbered peaks are given in

I-' 00

°'

~ __ _____f:,,_t, ______,,,__ /\..._JM_ L JA;~ S.1.M.

10 l 9 Jl 13

3 I 111

I I - T I I r----,--,- --,- I I I I - T---1 I I I T I I 30 35 40 45

T.I.C. Minutes

Figure 54: Total ion chromatogram (T.I.C.) of the basic subfraction of "resins" derived from Brazilian "Mina do ~ao" SRC. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric conditions appear in Table 6. Peak numbers same as Figure 53.

I-' co -....J

1 S.I.M.

21

r 1-· -.- --,--- ,- -,---r- -, .--- -.-- ,-- r 50

T.I.C.


55 60 65 Minutes

.- -1 ·--i

70

I-' 00 00

"Ij

f-'·

<..Q c 'i

(])

U1 .e:. n 0 ::i

rt

f-'· ::i c (]) °'

~ ..... " c ... ro U

l >-'3

H

(")

...., V>

00

0 00 "' "" 0

I

~ C/

l I

H

L 3:

w

"'

w

a- w

( ....,

w ""

.i:- -

l"N

J

6/.

Q

-l ~

1or.i1~.o

I c t

I I

I . \ (

I N

681

4-7 18 29 30 34 1s I 26 I fl 32

~~ 12 I I

3 I I 10 I · 11.71 ... 'l4 I I.. I II 1131 '--\ I

. • ol II • W I I II 1111 o I II o I I II I e ·~

2

t~ 1 1 , ____ ,J ~_;"---- "-· /\,.__~._/---.;_,.._.,._.,,

,--. • I I I lb I I I I 20 I I I I 30 I I I I 40 I I I I SQ I I I I eO I I I I 70 I I I I 80 I I I I

Figure 55: GC-FID chromatogram of "neutral subfraction" of the "resins fraction" derived from Brazilian "Mina do Leao" solvent refined coal. Condi-tions as in Figure 37. Identities of numbered peaks are revealed in Table 42.

I-' \0 0

//] / '

/ .. S.I.M.

4-711 _____ - - - ----,,

12

,---,----r--...--~--~--~--...---.---,..-----y----.,---,----y----.,--~--~--~-~---.---~-~--~--~

T. I. C. 25 30 35 40 45 Minutes

Figure 56: Total ion chromatogram (T.I.C.) of the neutral subfraction of "resins" derived from Brazilian "Mina do Leao" SRC. Upper trace is for single ion monitoring (S.I.M.). Mass spectrometric conditions appear in Table 6. Peak numbers same as Figure 55.

I-' ID I-'

U1 O'I ..

Z6T

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

193

'rADLE 4 0


FRACTION DERIVED FROM "MINA DE LEAO" SRC.


32.04 1849.3

35.30 1919.7

35.51 1924.2

38.37 1986.0

3 9. 11 2002.0

39.43 2008.9

40.23 2026.1

4 0. 40 2029.8

41. 52 2054.0

42.36 2072.1

43.56 2098.0

44.66 2121. 8

45.36 2136.9

4 5. 49 2139.7

45.81 2146.6

46.61 2163.9

46.78 216 7. 5

4 7. 18 2176.2

POSSIBLE COMPOUNDS(S) CONCENTRATION METHOD THREE MOST ABUNDANT CHARACTERISTIC MASSES (m/Z)

OR COMPOUND (wt%)** OF TYPE IDENTIFI-

CATION***

205;57;41 Di-t-Butyl Phenol 0.19 C;MS

94;66;65 Phenol 0.04 C;MS;R

108;107;77 0-Cresol 0.03 C;MS;R

118;146;90 Tetralone(Any Isomer) 0.11 C;MS

107;108;77 P-Cresol 0.14 C;MS;R

12 2; 12 1; 10 7 2,5-Xylenol 0.15 C;MS;R

130; 129; :is Indenol 0.47 C;MS

12 2; 10 7; 71 c 2-Alkyl Phenol 0.06 C;MS

108;93;71 c 2-Alkyl Phenol 0.02 C;MS

130;129;115 Indenol 0.61 C; MS

107;122;77 P-Ethyl Phenol 0.41 C;MS;R

130;115;148 Methyl Indanol 0.23 C;MS

71; 135; 150 c4-Alkyl Phenol 0.01 C;MS

107; 122;77 3,4-Xylenol 0.09 C;MS;R

121;136;77 2,3,5-Tri-Me-Phenol 0.07 C;MS;R

10 7; 15 0; 77 c 4-Alkyl-Phenol 0.05 C;MS

107;91;77 c 4-Alkyl-Phenol 0.10 C;MS

107;77;91 0-n-Propyl Phenol 0.06 C;MS

194

'l'AUL.b: 4 U CON'l' l NU.b:IJ

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUNDS(S) CONCENTRATION METHOD NO.* TIME INDEX ABUNDANT OR COMPOUND (wt%)** OF


19 47. 56 2184.4 121;136;77 m-Isopropyl Phenol 0.14 C;MS

20 47.73 218 8. 0 107;136;77 P-n-Propyl Phenol 0. 20 C;MS


22 48.35 2201.4 130;148;104 Methyl Indanol 0.40 C;MS

23 48. 6 9 2208.8 161;163;126 2,5-Di-Chloro-Aniline 0.28 C;MS

24 49.16 2218.9 121; 13 6; 91 c 3-Alkyl Phenol 0.22 C;MS

25 49.66 2229.7 12 1 ; 15 0 ; 13 5 c 4-Alkyl Phenol 0.06 C;MS

26 5 0. 78 2253.9 130;115;148 Methyl Ind anol 0.04 C;MS

27 51.19 2262.7 121;135;150 c 4-Alkyl Phenol 0. 11 C;MS

28 51. 83 2276.6 13 4; 10 5; 11 7 Methyl Indanol 0.14 C; MS

29 52.53 2291. 7 71;122;164 c 5-Alkyl Phenol 0.05 MS

30 52.74 2296.2 107;108;150 C~-Alkyl Phenol or 0.21 C;MS 133; 148; 115 ethy~ Indanol

31 53.76 2318. 2 71; 130; 148 Methyl Indanol 0.12 C;MS

32 54.25 2328.8 70;148;162 C 2-Alkyl Indanol 0.40 C;MS

33 5 5. 16 2 34 8. 4 133;148;162 C 2-Alkyl Indanol 0.65 C;MS

34 56.15 2 36 9. 8 133;148;105 C 2-Alkyl Indanol 0.36 C;MS


36 56.75 2382.8 147;162;133 c 3-Alkyl Indanol 0.03 MS


38 58.46 2419.7 120;148;133 c 3-Alkyl Indanol 0.41 MS

195

TABLE 40 CONTINUED


(min) CHARACTERISTIC TYPE MASSES(m/Z)

39 59.82 2449.0 133;148;105 c3-Alkyl Indanol 0.30

40 60.94 2473.2 14 9; 10 4; 5 7 Phthalic Acid Dialkyl 0.88 Ester

41 61. 97 2495.4 135;164;136 c 5-Alkyl Phenol 1.10

42 62.31 2502.8 120;148;147 c 2-Alkyl Indanol 0.80

43 63.00 2517.7 13 3; 16 2; 10 5 c 4-Alkyl Indanol 0.06

44 69.14 2650.2 133; 176; 120 c 3-Alkyl Indanol 0.17

45 72. 73 2727.7 115;144;116 1-Naphthol 0.31

46 74.56 27 67. 2 144;115;116 2-Naphthol 0.24

47 75.61 2 78 9. 9 43;41;127 Hexadecanoic Acid 0.76

48 77. 77 2836.5 158;157;128 Methyl Naphthol 0.10

49 79.83 2881. 0 158;151;128 Methyl Naphthol 0. 29

50 83.47 2959.5 41;43;129 Octanoic Acid 1. 52

51 85.12 2995.2 14 9; 16 7; 5 7 Phthalic Acid Dialkyl 1.15 Ester


**Concentrations determined by GC-FID and expressed as wt% of the acidic subf rac tion.

***C. F. Table 35.

IDENTIFI-CATION***

MS

C;MS

MS

C;MS

MS

MS

C;MS;R

C;MS;R

C;MS;R

C;MS

C;MS

C;MS;R

C;MS

196

'1'1\IH,F. 4 1


DERVIED FROM "MINA DE LEAO" SRC.


(min) CHARACTERISTIC TYPE IDENTIFI-MASSES(rn/Z) CATION***

1 22.77 1649.2 93;66;65 Aniline 0.06 C;MS;R

2 3 0. 08 1807.0 94;67;41 2-Arnino Pyridine 0.02 C;MS;R

3 31. 38 1835.1 12 9 ; 1 28 ; 102 Quinoline 0.35 C;MS;R

4 31. 64 184 0. 7 127;92;65 2-Chloro Aniline 0. 14 C;MS

5 33.31 1876.7 143; 128; 115 Quinaldine 0.03 C;MS

6 3 4. 97 1912.6 94;65;66 Phenol 0 .11 C;MS;R

7 35.21 1917.8 108;107;90 0-Cresol 0.08 C;MS;R

8 37.86 1975.0 13 2; 13 3; 11 7 Isoquinoline,1,2,3,4- 0.09 C;MS Tetra-Hydro

9 38.68 1992. 7 118;146;77 Tetra lone 0.31 C;MS

10 38.87 1996.8 83;118;146 Tetra lone 1. 34 C;MS

11 39.16 2003.0 107;122;77 P-Cresol 0. 28 C;MS;R

12 42.16 2067.8 107;136;77 2-n-Propyl Phenol 0.11 C;MS

13 4 3. 26 2091.6 127;129;92 4-Chloro Aniline 0.47 C;MS

14 43.64 2099.8 107;122;77 P-Ethyl Phenol 0.12 C;MS;R

15 44.69 212 2. 4 130;148;120 Methyl I ndanol 0.16 C;MS



18 47.39 2180.7 121; 13 6; 91 rn-Isopropyl Phenol 0.02 C;MS

197

TABLE 41 CONTINUED

PEAK RETENTION RETENTION TliREE MOST POSSIBLE COMPOUNDS(S) CONCENTRATION METliOD NO.* TIME INDEX ABUNDANT OR COMPOUND (wt%)** OF


19 47. 67 2186.7 107; 136; 77 P-n-Propyl Phenol 0.17 C;MS

20 48.46 2203.8 161;163;126 2,5-Di-Chloro-Aniline 2.48 C;MS

21 51. 64 2272.4 133;134;105 Methyl Indanol 0.05 C;MS

22 54.19 2327.5 117;90;89 Indole 0.01 C;MS;R

23 54.95 2343.9 133;134;105 Methyl Indanol 0.22 C;MS

24 55.93 2 36 5. 1 133;148;105 C 2-Alkyl Indanol 0.18 C;MS


26 56.49 2377.2 130;131;77 7-Methyl Indole 0.02 C;MS;R

27 57. 7 9 2405.2 133;148;105 c 2-Alkyl Indanol 0.03 C;MS

28 58.41 2418.6 120;148;133 c 3-Alkyl Indanol 0 .11 MS

29 59.64 244 5. 2 133;148;162 c 3-Alkyl Indanol 0.03 MS

30 60.42 2462.0 149;57;41 Phthalic Acid-Dialkyl 0.07 C;MS Ester

31 60.73 246 0. 7 93;135;66 c 5-Alkyl Aniline 0.07 MS

32 61. 99 2495.8 120;148;107 c 3-Alkyl Indanol 0 .11 MS

33 67.64 2617.9 179;178;151 7,8-Benzoquinoline 0.04 C;MS;R

34 69.73 2663.0 179;178;151 Acridine 0.07 C;MS;R

35 72. 40 2720.5 115;144;116 1-Naphthol 0.23 C;MS;R

36 74.24 27 60. 2 144; 115; 116 2-Naphthol 0.16 C;MS;R

37 74.79 2772.1 127;129;169 c 6-Alkyl Chloro- 0.06 MS Aniline

198

TABLE 41 CONTINUED

PEAK NO.*

RETENTION RETENTION THREE MOST POSSIBLE COMPOUNDS(S) OR COMPOUND

CONCENTRATION METHOD TIME INDEX ABUNDANT (wt%)** OF (min) CHARACTERISTIC TYPE

MASSES (m/Z)

38 75.20 2781.0 127;129;155 c6-Alkyl Chloro- 0.02 Aniline

39 77. 50 2830.6 158;157;128 Methyl Naphthol <0.01

40 79.82 2880.8 158;157;128 Methyl Naphthol 0.02

41 85. 72 3008.1 16 7; 16 6; 8 3. 5 Carbazole 0. 16

42 89.59 3091. 7 219;217;218 N-Phenyl, 1-Naphthyl 0. 27 Amine



***C. F. Table 35

IDENTIFI-CATION***

MS

C;MS

C;MS

C;MS;R

C;MS;R

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

199

TABLE 42


FRACTION DERIVED FROM "MINA DE LEAO" SRC


12. 3 5 14 24. 3

21. 50 1621.8

32.92 1868.3

39.62 2013.0

40. 06 2022.5

40. 29 2027.4

40.54 2032.8

41. 30 2049.2

42.38 2072. 6

42.74 2080.3

43.84 210 4. 1

45.25 213 4. 5

45.70 2144.2

46.86 216 9. 3

47.22 2177.0

47.53 2183.7

47.89 2191. 5

48.98 2215.0

POSSIBLE COMPOUND($) OR COMPOUND

THREE MOST ABUNDANT CHARACTERISTIC MASSES (m/Z)


104;132;91

128;127;129

205;41;57

118; 146; 90

117;118;146

90; 118; 146

118;146;90

153;154;152

108;93;91

107;136;77

127;129;91 107;122;121

130;115;148

130;115;148

107;91;77

10 7; 15 0; 77

121; 13 6; 77

121;136;77

161;163;126

TYPE

Tetralin <0.01

Naphthalene <0.01

Di-t-Butyl Phenol 2.00

Tetralone 11.26

Tetralone 12.66

Tetralone 8.70

Tetralone 13.04

Acenaphthene <0.01

c 2-Alkyl Phenol <0.01


4-Chloro Aniline 0.38 + P-Ethyl Phenol

Methyl Indanol 0.93

Methyl Indanol 0.10



m-Isopropyl Phenol 0.93


2,5-Dichloro Aniline 1.36

IDENTIFI-CATION***

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C;MS;R

C;MS

C;MS

C;MS C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C;MS

C; MS

200

TABLE 42 CONTINUED

PEAK NO.*

RETENTION RETENTION POSSIBLE COMPOUNDS(S) OR COMPOUND


CONCENTRATION METHOD TIME INDEX (wt%)** OF (min)

19 49.48 222S.8

20 Sl. 76 227S.O

21 S2.20 2241. 4

22 S2. 77 2296.8

23 S4.00 2323.4

24 S4. 24 2328.6

2S s s. 17 2348.6

26 S6.31 2373.2

27 S6.S3 2378.0

28 S7.90 2407.6

29 S9.24 2436.S

30 61. 78 2491. 3

31 62.48 2 so 6. 4

32 63.23 2S22.6

33 64.22 2S44.0

34 86.41 3023.0

130;11S;l48

107;136;164; 133;148;10S

121;149;178

10 7 i 121; l 78 133;148;10S

10 7 i 121 i l 78

107;77;178

13 3 i 14 8 ; 16 2

13';148;10S

133; 148; 162

147;162;176

13 3 i 14 7 i 16 2

149;S7;41

120;148;162

133;162;176

149;S7;41

167;143;83.S

TYPE

Methyl Indanol

C c;-Alkyl Phenol -fMethyl Indanol

c6-Alkyl

Cl\-Alkyl -fMethyl

Phenol

Phenol Indanol

0.06

0.03

0.11

0.04

CS-Alkyl Phenol 0.09

CS-Alkyl Phenol 0.04

c 2-Alkyl Indanol 0.20

C 2-Alkyl Indanol 0.43








Carbazole 5.74



IDENTIFI-CATION***

C;MS

MS

MS

MS

MS

MS

MS

C;MS

C;MS

MS

MS

C;MS

C;MS

MS

C;MS

C;MS;R

201

TABLE 43

Percent Volatiles in the Resins Fraction of Brazilian SRC and its Respective Acidic, Basic and Neutral Subfractions

SUBFRACTION

Acidic

Basic

Neutral

Total % Volatiles in Unfractionated Resins

*

wt% VOLATILES* IN SUBFRACTION

21.59%

11. 46%

80.40%

As determined by GC-FID ** Calculated using the results of Table 28.

% OF RESINS** FRACTION

2. 30%

7.70%

17.32%

27.32%

202

TABLE 44

Percent Distr. of Identified Compounds in the Acidic, Basic and Neutral Subfractions of Brazilian SRC-Derived Resins


Phenol

0-Cresol

P-Cresol

2,5-Xylenol

3,4-Xylenol

P-Ethyl Phenol


m-Isopropyl Phenol

0-n-Propyl Phenol

P-n-Propyl Phenol

c2 -Alkyl Phenols

c3 -Alkyl Phenols

Di-t-Butyl Phenol

c4-Alkyl Phenols

c5-Alkyl Phenols

c6-Alkyl Phenols

Indenols

Methyl Indanols


0.08

0.06

0.22

0.02

0.01

0.13

0.01

0.25

0.01

0.15

0.07

0.11

0.49

0.13

0.17

0.04

0.12

0.64

203

TABLE 44 Continued


c2 -Alkyl Indanols

c3-Alkyl Indanols

c4-Alkyl Indanols

Phthalic Acid Dialkyl Esters

Hexadecanoic Acid

Octadecanoic Acid

1-Naphthol

2-Naphthol

Methyl Naphthol

Tetralones

Indole

7-Methyl Indole

Carbazole

Aniline

2-Amino Pyridine

Quinoline

Tetra-Hydro-Isoquinoline

Quinaldine

2-Chloro-Aniline


0.85

0.41

0.05

1. 62

0.09

0.17

0.20

0.14

0.07

12.00

0.01

0.01

1. 47

0.04

0.01

0.25

0.06

0.02

0.10

204

TABLE 44 Continued


4-Chloro-Aniline

2,5-Dichloro-Aniline

c5-Alkyl Aniline

c6-Alkyl Aniline

7,8-Benzoquinoline

Acridine

N-Phenyl, 1-Naphthyl Amine

*


0. 34

2.14

0.05

0.06

0.03

0.05

0.19

Concentrations determined by GC-FID and expressed as wt% of unfractionated resins.

205

sible only if two capillary columns of different polarities

are employed, to compare Kovats retention indexes for real

samples, and as many relevant authentic standards, as possi-

ble.

This "two capillary column" approach was investigated

in this work, and applied to study the resins subfractions

of sugarcane bagasse. A slightly polar fused silica capil-

lary column, liquid phase SE-54, was selected as a second

column. Retention behaviour of all previously used model

compounds on this particular column were determined. Figure

57 shows a chromatogram of the neutral standards, identities

of which are revealed in Table 45. Figures 58, 59 and 60

display chromatograms of basic standards whose identifica-

tion is given in Table 46, while Figures 61 and 62 show

chromatograms of acidic standards which are identified in

Table 47.

Acidic, basic and neutral subfractions of resins from

sugarcane bagasse, which have been already analyzed on the

Carbowax capillary column, were then studied on the SE-54

column. The purpose of this investigation was to compare

the retention indexes information from the SE-54 column with

that from Carbowax 20 M. The MS, however, was still coupled

to the GC during this part of the study. Figures 63, 64 and

65 show chromatograms of the acidic, basic and neutral sub-

3

2

f--r----,-

5

4

-, 10

6

10 11 14

15

8

13

9 7 12

r-20 I I I I r- I I I I I I 30 40


16 17 18

19 20

I --1 - - I I I- - -,---, 50

Figure 57: GC-FID chromatogram of neutral standards. Conditions: 54 m x 0.32 mm i.d. fused silica capillary column temperature programmed from 60°C to 280°C at 2°C/min with 5 min initial hold. Other conditions are dis-played in Table 7. Peak identities are given in Table 45.

N 0 0\

207

TABLE 45

RETENTION CHARACTERISTICS OF NEUTRAL STANDARDS ON SE-54 CAPILLARY

PEAK RETENTION NO.* TIME

(min)

1 4.82

2 7.19

3 9. 4 4

4 10.42

5 11.34

6 12.95

7 25.10

8 29.92

9 31. 50

10 32.07

11 35.09

12 37.75

13 38.08

14 38.68

15 38.97

16 42.18

17 43.49

18 52.45

19 55.59

20 57.40

RETENTION INDEX ** (RSD)

N.D.+

N .D.

1003.8±0.7(0.07%)

1021.4±0.7(0.07%)

1037.6±0.8(0.08%)

1006.3±0.5(0.05%)

1282.5±1.2(0.09%)

1368.6±1.0(0.07%)

1396.6±1.1(0.08%)

1406.0±0.9(0.06%)

14 6 0 • 1± 0 • 7 ( 0 • 0 5 % )

1507.4±0.8(0.05%)

1513.5±0.7(0.05%)

1524.1±0.6(0.04%)

15 3 0. 2± 1. 1 ( 0 . 0 7 % )

1586.6±0.5(0.03%)

1610.0± 0.5 (0.03%)

1770.5±0.5(0.03%)

1826.9±0.6(0.03%)

1858.6±0. 7 (0.04%)

COLUMN

MODEL COMPOUND

Anisole

Phenetole

Cyclohexyl Acetate

Benzyl-Ethyl-Ether

2,3-Dihydro-Benzofuran

2,3-Dihydro,2-Methyl-Benzofuran

Indole

2-Methyl Indole

7-Methyl Indole

Diphenyl Ether

2-Methoxy Naphthalene

5-Ethyl Indole

2, 3-Dime thyl Indole

m-Phenoxy Toluene

Dibenzofuran

O Methoxy Biphenyl

Diphenyl Sulphide

Dibenzothiophene

1,2,3,4-Tetrahydro Carbazole

Carbazole

*Peak Numbers Correspond To Chromatogram In Figure 57

** 3 Determinations

+N.D.: Not Determined (Below 1000)

fr

2 1

I I

5, 7

r--. 10

10 .. 11

8

12 16.

.13 17 26 15 14

22 25

~· -\.--1 '---J \..... I\. _____ _,\....

I 1- -- o ,- ---. 20 30


Figure 58: GC-FID chromatogram of basic standards on SE-54 column. Conditions as in Figure 57. Peak identities are revealed in Table 46.

N 0 00

29 26

24

221 I 29 . 36 33

191 II I ~ II ~ j n

.. .. .. _J ______ ....

I \_J \j ~ .'-v-_ I'----- - ~ ''---- --- --- - - - - __ J \....

r-1-·---.-2h I I I I 3'o I I r I 4b I I I I sb I I I I s'o I I I I 16 I


Figure 59: GC-FID chromatogram of basic standards on SE-54 column. Conditions as in Figure 57. Peak identities are revealed in Table 46.

f\) 0 I.Cl '

3. 4 9

21 30

23 32

31 25

34

6 28 29 18 35 16 27

I I I I I I 1b I I I I 20 I I I I 30 I I I


I - - T ---,------,-----,------,-,-1 I I I 40 50

Figure 60: GC-FID chromatogram of basic standards on SE-54 column. Conditions as in Figure 57. Peak identities are given in Table 46.

l\J I-' 0

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

211

TABLE 46

RETENTION CHARACTERISTICS OF BASIC STANDARDS ON SE-54 CAPILLARY COLUMN


3.64

4.02

4. 3 2

6.48

7. 72

7.82

8.69

10.70

10. 7 8

11. 93

12.34

15.84

16.50

18. 87

20.80

25.79

26. 72

31. 61

32.38

32.87

RETENTION INDEX ** (RSD)

N.D.+

N.D.

N.D.

N. D.

N.D.

N.D.

N.D.

1026.3±0.3(0.03%)

1029.0±0.7(0.07%)

1048.1±0.4(0.04%)

1055.6±0.2(0.02%)

1118.1±0.5(0.05%)

1129.9±0.2(0.02%)

1173.7±0.8(0.07%)

1206.8±0.5(0.04%)

1296.0±0.6(0.05%)

1313.4±0.3(0.02%)

1398.2±0.7(0.05%)

1412.0±0.6(0.04%)

MODEL COMPOUND

3-Methyl Pyridine

2,6-Dimethyl Pyridine

2-Ethyl Pyridine

Aniline

3,4-Dimethyl Pyridine

2-Amino Pyridine

5-Ethyl, 2-Methyl Pyridine

~!-Methyl Aniline

m-Toluidine

N,N-Dimethyl Aniline

4-Ethyl,3-Methyl Pyridine

0-Ethyl Aniline

2,4-Dimethyl Aniline

Quinoxaline

Qui no line

8-Methyl Quinoline

1,2,3,4-Tetrahydro Quinoline

2,3 Dimethyl Quinoxaline

0-Nitro Aniline


212

TABLE 4 6 CONTINUED

PEAK RETENTION RETENTION INDEX ** NO.* TIME (RSD) MODEL COMPOUND

(min)

21 32.88 1421.2±0.6(0.04%) 2,6-Dimethyl Quinoline

22 34.99 1460.5±0.7(0.05%) 2-Phenyl Pyridine

23 35.52 1468.7±0.6(0.04%) 3-Phenyl Pyridine

24 35.93 1476.0±0.7(0.05%) 4-Phenyl Pyridine

25 36.36 1484.5±0.2(0.01%) 2-Benzyl Pyridine

26 39.90 1492.6±0.5(0.03%) 1-Amino Tetralin

27 37.89 1510.7±1.1(0.07%) m-Nitro Aniline

28 39.76 1544.2±0.9(0.06%) 1-Naphthyl Amine

29 4 5 .14 1640.8±0.7(0.04%) Azobenzene

30 45.82 1652.3±0.8(0.05%) Diphenyl Amine

31 46.31 1660.2±0.6(0.04%) 4-Aza-Fuorene

32 51. 36 1752.3±1.1(0.06%) Phenazine

33 54.03 1798.3±0.5(0.03%) 7,8-Benzo~uinoline

34 54.87 1813.4±0.5(0.03%) 5,6-Benzoquinoline

35 56.00 1834.5±0.7(0.04%) Acridine

36 71. 79 2114.7±0.9(0.04%) N-Phenyl,1-Naphthyl Amine

* Peak Numbers Correspond To Chromatograms In Fiugres 58-60

** 3 Determinations (Retention Indices Calcualted By Interpolation Between n-Alkanes)

+N.D.: Not Determined (Below 1000)

JJ 12

9

7

--r·---,- 10

11

12 +-

14. 15

18

19

21 22

,--,---,-- I I I I I I I I I I I j I I I ~ ~ ~ ~


Figure 61: GC-FID chromatogram of acidic standards on SE-54 capillary column. Conditions as in Figure 57. Peak identities are revealed in Table 47.

N I-' w

16

·- 20

17 ..___ 5 8

23

10

.--! I I I I 1b I I I I 20 30 40 I I I I Sb I I


Figure 62: GC-FID chromatogram of acidic standards on SE~54 capillary column. Conditions as in Figure 57. Peak identities are revealed in Table 47.

"' I-' ~

215

TABLE 47

RETENTION CHARACTERISTICS OF ACIDIC STANDARDS ON SE-54 CAPILLARY COLUMN

PEAK RETENTION RETENTION INDEX NO.* TIME (min) (RSD)

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

4.24

7.21

9.39

10.48

11.60

13.14

16.03

17.13

17.75

20.67

21. 21

21. 46

24.01

24.51

25.62

25.64

25.73

29.58

34. 72

39.79

40.00

50.91

52.33

N.D.

N.D.

1002.7±0.9(0.09%)

1021.1±0.7(0.07%)

1042.1±0.5(0.05%)

1069.7±0.4(0.04%)

1121.2±0.5(0.05%)

1141.2±0.4(0.04%)

1151.1±0.6(0.05%)

1202.9±0.8(0.07%)

1213.2±1.0(0.08%)

1217.6±0.8(0.07%)

1263.4±0.4(0.03%)

1272.1±0.5(0.04%)

1291.1±0.7(0.05%)

1292.5±0.5(0.04%)

1294.1±0.5(0.04%)

1362.6±0.4(0.03%)

1454.2±0.3(0.02%)

1544.6±0.5(0.03%)

1548.0±1.0(0.06%)

1742.5±1.1(0.06%)

1767.8±0.8(0.05%)

** MODEL COMPOUND

Cyclohexanol

Phenol

Benzyl Al coho 1

0-Cresol

P-Cresol

2,6-Xylenol

2,5-Xylenol

4-Ethyl Phenol

2,3-Xylenol

P-Methoxy Phenol

1-Indanol

m-Methoxy Phenol

2-t-Butyl Phenol

2-Sec-Butyl Phenol

4-t-Butyl Phenol

3-t-Butyl Phenol

2-t-Butyl, 6-Methyl Phenol

2-t-Butyl, 4-Methyl Phenol

2,6-Di-t-Butyl Phenol

2,4-Di-t-Butyl Phenol

2-Naphthol

m-Phenyl Phenol

9-Hydroxy Fluorene

* Peak numbers correspond to chromatograms in Figures 61 And 62

**3 Determinations

N.D.: Not Determined (Below 1000)

216

fraction of resins from sugarcane bagasse. Iden ti ties of

the numbered peaks in these chromatograms are given in

Tables 48, 49 and 50 for the respective fractions. It is

clear from Figure 64 that the SE-54 is not the optimum liq-

uid phase for the basic subfraction of resins, although the

acidic and neutral subfractions behaved well. The correla-

tion between retention indexes of standards (Tables 45, 46

and 47) and the relevant components identified in the resins

subfractions (Tables 48, 49 and 50) is very good.

Good correlation was also obtained on the Carbowax col-

umn (c.f. Tables 31 to 34 and 35 to 37). Such results, on

both capillary columns, are summarized in Table 51.

l 41 19

l

I I 1 1 20 J 30,.-.- I I 4li I I I I s'o I I I I 60 I I I I 70 I I I I ab I I I I s'o I I ' I


Figure 63: GC-FID chromatogram of the "acidic subfraction" of the "resins fraction'' derived from "Brazilian" sugarcane bagasse_ liquefaction products using an SE-54 capillary column. Conditions: As in Figure 57. Identities of numbered peaks are given in Table 48.

N I-' -..J

I I I 1--- -T l 1- -,-- r-- -,------.--I l I I I ,--,---, I -, ----, I -, ---,- --1 20 30 40 50 60


Figure 64: GC-FID chromatogram of the basic subfraction of the "resins" fraction derived from "Brazilian'' sugarcane bagasse liquefaction products as obtained on an SE-54 colu~n. Conditions: As in Figure 57. Identi-ties of numbered peaks are given in Table 49.

N ...... 00

70

3

,-----,-- -T----,---,---,,--,--,------,--,----,,-,.---,----r---.~,--.----r--.~.----.---r-,-~.----.-----.---.---,,---,.---,---,---,~,--,----,---,---,,----r---,

~ ~ ~ W ~ M M 00


Figure 65: GC-FID chromatogram of the neutral subfraction of the "resins fraction" derived from "Brazilian" sugarcane bagasse liquefaction products as obtained on an SE-54 column. Conditions as in Figure 57. Identities of numbered peaks are given in Table 50.

N ...... l.O

PEAK NO.*

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

220

TABLE 48


FRACTION DERIVED FROM ''.BR~~l;.J1IAN SUGARCANE B~GASS~ LIQUEFACTION

PRODUCTS STUDIED ON AN SE-54 CAPILLA~Y COLUMN


17.18

17.70

18.32

19.91

21.13

34.56

39.95

41.04

42. 56

43.30

44.74

46.08

46.60

47.77

48.09

50.67

51. 04

RETENTION THREE MOST INDEX** ABUNDANT

CHARACTERISTIC MASSES (m/Z)

1141. 7

1151.0

1162.1

1190. 3

1212.1

1451.5

1547.6

1567.0

1594.0

1607.3

1632. 9

1656.8

1666.0

1686.9

1692.6

1738.6

174 5 .1

107;122;77

107;122;77

71;41;43

71;41;43

71;41; 87

152;151;76

144;115;116

133; 120 ;71

71;43;41

71;41;42

164;163;42

158;157;129

15 8; 15 7; 77

158;157;128

71;41;55

71;41;70

170; 141; 115

POSSIBLE COMPOUND(S) OR .COMPOUND TYPE

P-Ethyl Phenol

2, 3-Xylenol

Solvent Impurity

Solvent Impurity

Solvent Impurity

Unidentified

2-Naphthol

Unidentified

Solvent Impurity

Solvent Impurity

Unident:ified

Methyl Naphthol

Methyl Naphthol

Methyl Naphthol

Alkyl Carboxylic Acid

Alkyl Carboxylic Acid

m-Phenyl Phenol

METHOD OF

IDENTIFICATION

C;MS;R

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C;MS;R

221

TABLE 48 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND{S) METHOD NO.* TIME INDEX** ABUNDANT OR COMPOUND OF

{min) CHARACTERISTIC TYPE IDENTIFICATION MASSES {m/Z)

18 51.41 1751. 7 l 7 0; 141; 115 Phenyl Phenol Isomer C;MS

19 51. 93 1761.0 l 7 0; 141; 115 Phenyl Phenol Isomer C;MS

20 54.06 l 798. 9 184;128;127 Methyl Phenyl Phenol C;MS

21 54.55 1807.7 178;89;76 Unidentified

22 55 .14 1818.2 17 0 • 16 9 • 13 9 Methyl Phenyl Phenol C;MS

23 55. 8 9 1831.6 184;183;77 Methyl Phenyl Phenol C;MS

24 56.66 184 5. 2 184;185;115 Methyl Phenyl Phenol C;MS

25 56.91 1850.6 184;185;115 Methyl Phenyl Phenol C;MS



28 57.56 1861. 2 184;183;165 Methyl Phenyl Phenol C;MS


30 58.69 1881. 5 198;197;184 c 2-Alkyl Phenyl Phenol C;MS

31 59.25 1891. 4 198;197;115 C 2-Alkyl Phenyl Ph'"'nol C;MS

32 60.52 1914.0 184;183;197 c 2-Alkyl Phenyl Phenol C;MS

33 61. 02 1923.0 184;183;165 Methyl Phenyl Phenol C;MS

34 61. 27 1927.4 198;197;184 c 2-Alkyl Phenyl Phenol C;MS

35 61. 71 1935.3 198;183; 197 c 3-Alkyl Phenyl Phenol MS

36 62.60 1951.2 198;197;168 C 2-Alkyl Phenyl Phenol C;MS

37 63.01 1958.3 152;182;76 Unidentified

222

TABLE 48 CONTINUED

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND(S) METHOD NO.* TIME INDEX** ABUNDANT OR COMPOUND OF

(min) CHARACTERISTIC TYPE IDENTIFICATION MASSES(m/Z)

38 63.34 1964.4 184;183;212 c 3-Alkyl Phenyl Phenol MS

39 63.53 196 7. 7 198;197;169 c 3-Alkyl Phenyl Phenol MS

40 64.66 1987.8 198;197;212 C 3-Alkyl Phenyl Phenol MS

41 64.88 1991.7 198;197;212 c 3-Alkyl Phenyl Ph nol MS

42 6 5. 90 2009.9 197;198;212 c 3-Alkyl Phenyl Phenol MS

43 66.06 2012.7 197;198;212 c 3-Alkyl Phenyl Ph.:nol MS

44 68.82 2061. 9 212;197;181 c 4-Alkyl Phenyl Phenol MS

45 70.07 2084.3 149;212;115 C 4-Alkyl Phenyl Phenol MS

46 70 .11 2085.0 149;212;211 c 4-Alkyl Phenyl Phenol MS

47 71. 40 210 7. 9 220;219;165 Unidentified

48 73.49 2145. 2 194;165;97 c5-Alkyl Phenyl Phenol MS

49 74.80 216 8. 5 198;197;183 C 5-Alkyl Phenyl Phenol MS

50 83.81 2329.1 189;218;94.5 Un id en tif ied

51 84.00 233 2. 4 189;218;94.5 Unidentified

52 84. 32 2 338. 2 94;218;189 Unidentified

53 90.20 >2400 149;167;57 Phthalic Acid Dialkyl Ester C;MS


**Retention indices calculated by interpolation between n-alkanes.

223

TABLE 49


DERIVED FROM "BRAZILIAN SUGARCANE BAGASSE LIQUEFACTION PRODUCTS,

STUDIED ON AN SE-54 CAPILLARY COLUMN

PEAK RETENTION RETENTION THREE MOST POSSIBLE COMPOUND(S) METHOD NO.* TIME INDEX ABUNDANT OR COMPOUND OF

(min) CHARACTERISTIC TYPE IDENTIFICATION MASSES (m/Z)

1 18. 20 1160.0 107; 122; 77 c2-Alkyl Phenol C;MS

2 18.52 116 5. 7 107;122;77 c2-Alkyl Phenol C;MS

3 19.33 1180 .1 107;122;77 c2-Alkyl Phenol C;MS

4 19.57 1184.4 107; 122; 77 c2-Alkyl Phenol C;MS

5 19.76 1187. 8 107; 122; 77 c2-Alkyl Phenol C;MS

6 20.06 1201.1 121; 136; 77 c3-Alkyl Phenol C;MS

7 20.85 1207.2 129; 102; 128 Quinoline C;MS;R

8 21.44 1217.7 129; 102; 128 Isoquinoline C;MS

9 25.15 1283.8 117;90;89 Indole C;MS;R

10 26.90 1317. 8 143;142;115 Methyl Quinoline C;MS

11 29.08 1353.9 143;142;115 Quinaldine C; MS

12 29.40 1359.6 143;142;115 Lepidine C;MS

13 31. 56 1398.4 130; 131; 103 7-Methyl Indole C;MS;R

14 34.28 1446.5 152;151;76 Unidentified

15 35.28 1464.3 154; Unidentified

16 35.49 1468.0 155; Unidentified

17 37.48 150 3. 4 13 0 ; 14 4 ; 14 5 c2-Alkyl Indole C;MS

224

TABLE 49 CONTINUED



18 38.75 1526.2 174; Un identified

19 39.39 1537.6 170;141;115 Phenyl Phenol Isomer C;MS

20 52.46 1770. 3 184;139;92 Dibenzothiophene C;MS;R

.21 53.41 17 87. 4 178; Unidentified

22 54.03 179 8. 5 179;178;151 7,8-Benzoquinoline C;MS;R

23 56.04 1834.3 179;178;151 Acridine C;MS;R

24 57.29 1856.5 179; 178; 151 Benzoquinoline Isomer C;MS

25 57. 3 8 1858.1 167; 166; 139 Carbazole C;MS

26 58.54 1878.8 16 7; 16 6; 13 9 Carbazole C;MS;R

27 58.58 1879.6 167;166;139 Carbazole C;MS

28 58.69 1881.5 167;166;139 Carbazole C;MS

29 58 '7 9 1883.2 167; 166; 139 Carbazole C;MS

30 61. 62 1933.6 181;180;152 Methyl Carbazole C;MS

31 62.35 1946.7 181;180;152 Methyl Carbazole C;MS


33 64.25 1980.7 193;178;165 Methyl Benzoquinoline C;MS


PEAK NO.*

l

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

225

TABLE 50


FRACTION OF "BRAZILIAN SUGARCANE BAGASSE" LIQUEFACTION PRODUCTS,

STUDIED ON AN SE-54 CAPILLARY COLUMN

RETENTION RETENTION THREE MOST ABUNDANT CHARACTERISTIC MASSES ( m/Z)

TIME INDEX (min)

16.03

17.19

17. 86

21.18

21.40

21. 83

23.38

24.04

24.25

25.14

25. 72

26.83

27.37

28.75

30.13

3 0. 26

31.33

1121.4 107;122;77

1142.0 107;122;77

1154.0 107;122;77

1213.0. 121;136;91

1217.0 121;136;91

1224.6 121;136;91

1252.3 121;150;135

1264.l 121;136;91

1267.8

1283.7

1293.9

1313.8

132 3. 3

134 7. 9

1372. 6

137 4. 9

1393.9

132;104;103

117;90;89

135;150;121

135;150;121

121; 13 6; 91

130;131;103

130;131;103

121; 135; 150

130;131;103

POSSIBLE COMPOUND(S) OR COMPOUND TYPE

2,5-Xylenol

P-Ethyl Phenol

2,3-Xylenol

c3-Alkyl Phenol

c 3-Alkyl Phenol

C 3-Alkyl Phenol

C 4-Alkyl Phenol

c 3-Alkyl Phenol

Unidentified

Indole

4-t-Butyl Phenol

Butyl-Phenol

c 3-Alkyl Phenol

Methyl Indole

2-Methyl Indole

c 4-Alkyl Phenol

7-Methyl Indole

METHOD OF

IDENTIFICATION

C;MS;R

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS

C;MS

C;MS;R

C;MS;R

C;MS

C;MS

C;MS

C;MS;R

C;MS

C;MS;R

226

TABLE SO CONTINUED

PEAK ~TENTidN RETENTION THREE MOST POSSIBLE COMPOUND(S) METHOD NO.* TIME INDEX ABUNDANT OR COMPOUND OF


18 32.06. . 1406. 9 121;13S;lSO c 4-Alkyl Phenol C;MS

19 33.07 142 4. 9 121; 13 s; 91 c 4-Alkyl Phenol C;MS

20 33.S2 1433. 0 121;91;164 cs-Alkyl Phenol MS

21 34.37 1448.2 121;91;164 cs-Alkyl Phenol MS

22 34.62 14S2.S 1S2; 1Sl;76 Unidentified

23 36.90 1493.2 1S3;126;127 Cyano Naphthalene C;MS

24 37.63 1S06. 2 130;14S;llS S-Ethyl Indole C;MS;R

2S 38.S6 1S22.7 l S 3 ; l 26 ; l 27 . Cy a no Naphthalene C;MS

26 38.63 1S24.0 1S3;126;127 Cy a no Naphthalene C; MS

27 39.10 1S32.4 168;139;127 Dibenzofuran C;MS;R

28 39.64 1S4 2. 0 170;141;11S Phenyl Phenol Isomer C ;MS

29 40.03 1S49.0 167;1S3;140 Methyl Naphthontirle C;MS

30 40.16 lSS l. 3 144;11S;ll6 2-Naphthol, C;MS;R

31 41. 37 1S72. 9 144;14S;l30 c 2-Alkyl Indole C;MS

32 43.lS 1604.S 166;16S;83 Fluorene C;MS;R

33 43.60 1612.S 127; Unidentified

34 44.24 1623.9 167;1S3;140 Methyl Naphthonitrile C; MS

3S 44.77 1633.S 167; 1S3; 140 Methyl Naphthoni tri le C;MS

36 4 4. 94 1636.4 167;1S3;140 Methyl Naphthonitrile C; MS

37 4S.Sl 1646.6 184;183;16S Methyl Phenyl Phenol C;MS

227

TABLE 50 CONTINUED


(min) CHARACTERISTIC TYPE IDENTIFICATION MASSES(m/Z)


39 46.63 16 66. 6 130;131;159 c3-Alkyl Indole MS

40 46.79 166 9. 4 167; 166; 140 c 2-Alkyl Naphthonitrile MS

41 47.21 1676.8 12 7 ; 15 5 ; 115 Unidentified

42 47.81 1687.6 179;178;89.5 Unidentified

43 48.37 1697.6 17 0; Unidentified

44 48.56 1701.0 152; Unidentified

45 48.82 1705. 5 179;178;165 Methyl Fluorene C;MS

46 49. 45 1716.9 130;131;173 c4-Alkyl Indole MS

47 49.94 1725. 6 115; Unidentified

48 50.33 1732.4 167;166;140 c2-Alkyl Naphthonitrile MS

49 52.50 1771.2 180;179;165 Methyl Fluorene C;MS

50 52.60 1773.0 184;139;92 Dibenzothiophene C;MS;R

51 54.04 1798.6 178; 176; 89 Phenanthrene C;MS;R

52 54.62 1808.8 178;176;89 Anthrecene C;MS;R

53 56.70 1845.9 16 7 ; 16 6; 14 0 C 2-Alkyl Naphthonitrile MS

54 57.49 1860.l 16 7; 13 9 i 8 3 • 5 Carbazole C ;MS; R

55 58.24 1873.4 167;139;83.5 Carbazole C;MS

56 58.43 1876.9 16 7 ; 13 9 ; 8 3 • 5 Carbazole C;MS

57 59.67 1899.0 167;139;83.5 Carbazole C;MS

58 61. 67 1934.6 16 7 ; 13 9 ; 8 3 • 5 Carbazole C;MS

228

TABLE 50 CONTINUED





61 62.96 195 7. 5 195;194;180 c 3-Alkyl Carbazole MS

62 63.99 197 5. 9 195;194;180 c 3-Alkyl Carbazole MS

63 64.70 1988.6 195;209;180 C 3-Alkyl Carbazole MS

64 6 5. 16 1996.7 195;194;180 C 2-Alkyl Carbazole MS

65 6 5. 38 2 00 0. 7 149 Unidentified

66 65.56 2003.9 195;194;180 c3-Alkyl Carbazole MS

67 65.92 2010.2 180;195;209 c 4-Alkyl Fluorene MS

68 66.50 2020.6 57; Unidentified

69 67. 5 4 2039.2 195;194;180 c3-Alkyl Carbazole MS

70 68.23 2051. 4 202;200;101 Fluoranthene C;MS;R

71 68.53 2056.7 202;200;101 Fluoranthene C;MS

72 69.58 2 07 5. 5 195;180;209 c 3-Alkyl Carbazole MS

73 71. 06 2101.9 216;215;108 Methyl Fluoranthene C,MS

74 71. 52 2110 .1 101;218;204 Ethyl or Dimethly Cl6Hl2 MS

75 73 .11 2138.3 218;204;101 Ethyl or Dimethyl Cl6Hl2 MS

*Peak numbers refer to GC-FID Chcomatogram in Figure 65

229

TABLE 51

COMPONENTS IDENTIFIED IN THE RESINS SUBFRACTIONS OF SUGARCANE BAGASSE,

BASED ON KOVATS RETENTION INDEXES OF MODEL COMPOUNDS ON SE-54 AND

CARBOWAX AND 20M CAPILLARY COLUMNS

IDENTIFIED RETENTION RETENTION INDEX RETENTION INDEX RETENTION INDEX

COMPONENT INDEX OF MODEL ON CARBOWAX OF MODEL

ON SE-54 COMPOUND COMPOUND

2,5-Xylenol 1121.4 1121. 2 2001. 5 2001. 0

P-Ethyl Phenol 1141. 7 1141. 2 2093.9 2093.4

2,3-Xylenol 1151.0 1151.1 2072.1 2070.6

Quinoline 1207.2 120 6. 8 1837.8 1831. 3

Indole 1283.7 1282.5 2330.9 2329.5

4-t-Butyl Phenol 1293.1 1291. 9 2208.5 2214. 7

2-Methyl Indole 1372.6 1368. 6 23 45. 4 2342.7

7-Methyl Indole 139 8. 4 1396.6 2378 2381. 6

5-Ethyl Indole 1506.2 15 07. 4 2489.8 2493.6

2-Naphthol 1547.6 1548.0 2760.2 2763.7

Fluorene 1604.5 16 04. 5 2232.9 2230.4

m-Phenyl Phenol 1745.1 1742.5 2937.5 2 93 3. 4

Dibenzothiophene 1770.3 1770.5 2506.0 2512.4

7,8~Benzoquinoline 1798. 5 1798. 3 2622.5 2617.7

Phenanthrene 1798.6 1800.4 2565.4 2560.4

Anthracene 1808.8 1808.5 2569.3 2 56 5. 4

Acridine 1834.3 1834.5 26 51. 6 26 48. 5

Carbazole 1860.1 1858.6 3018.5 3021. 4

Fluoranthene 2051. 4 2048.2 2923.1 2918.5

CONCLUSIONS

Two important issues were addressed in this thesis:

The development of a reasonably rapid, single step, reprodu-

cible liquid chromatographic method for the efficient frac-

tionation of alternative fuels, and the detailed characteri-

zation of the "resins" fraction, as defined by this method,

by HRGC/MS.

When compared to other methods in the literature (c.f.

Table 52), this LC method provides a complete fractionation

of the liquid fuels, in a single step, and yields the actual

group type distribution of the various chemical classes

(oils, resins, asphaltenes and asphaltols) in a discrete

form that other methods have failed to accomplish. Total

time of the developed method is 5 hours. Reproducibility of

the method is good (<2% R.S.D. for polar fraction), and

recoveries of 88% or better have been achieved in most

cases. The method confirms that the various fractions gen-

erated by solubility methods (oils, asphaltenes and asphal-

tols) are highly impure and strongly overlapping (Figure 5,

p. 47 and Figure 6, p. 49), while the resins fraction

derived from Attapulgus clay columns is pure (Figure 4, p.

230

231

46). The minimum overlap among the resin, asphal tene and

asphaltol fractions, as obtained by this LC method, and the

excellent repeatability associated with their production

(R.S.D. of 1.3%, 2.1% and 1.9%, respectively, Table 8, p.

51), emphasizes the reliability of the chromatographic defi-

ni ti on of such classes. Since these fractions do differ

chemically from those obtained by other separation schemes,

it appears necessary to propose new definitions of such

fractions.

The use of volatile eluents (except for pyridine)

throughout this study was essential to guarantee complete

and quantitative recovery of the different components during

the solvent evaporation step.

The time it takes to generate the eight fractions by

the LC method is about five hours. For routine applica-

tions, this is rather long. However the analysis time could

be reduced to about two hours if one employed several pres-

surized solvent reservoirs to achieve higher flow rates.

The detection system can still be gravimetry, or the column

effluent could be passed through two detectors in series: a

refractive index (R.I.), to monitor the separation between

the saturates and the aromatics, and an ultra violet (U.V.)

photometer for the aromatic fractions. Gravimetry, although

tedious, proved useful in determining percent recovery and

TABLE 52

Comparison of Fractionation Methods8

Solvent SESCb SARAC SARA SARA PONA TLC RSMCe Hellgeth This Extraction (ref.34) Phillips Jewell et al. llPLC & (Poirier et al. (Mobil et al. Work

(ref. 74) (ref. 24) (ref. 53) (ref. 28) SOAPd ref. 116) ref. 241) (ref. 44)

Basis Class Function- Class Class Class Class Class Class Polarityh

Class for typef ality type type type type typeg type & type Separation function-

ality

Purity Strong Some Some Some Some Some k Minor Some N.A.e Minor of overlap overlap 1 overlapj overlapj overlapj overlap overlap overlap overlap Fractions

Reproduci- Fair N.R.m Bad Good (resin Good N.R. N.A. Good <2% bility (ref. 96) (ref. 96) fraction Good Good (<2% R.S.D.) R.S.D. polar

ref. 214) fraction N (,..)

-Many steps -One step -2 Steps -Many steps -2 Steps -One step -2 Steps -One step -2 Steps -One step N Ease -3 fractions -10 fractions -4 fractions -4 fractions -4 fractions -4 fractions -3 fractions -6 fractions -5 fractions -8 fractions

Analysis Days Hours 2 Days 2 Days 2 Days 1 !lour 1 Hour !lours !lours Hours timen

Sample 0 5-10 5-10 Size gms gms gms gms mgs mgs0 mgs gms gms gms

Basis Gravimetry for Grav!- Grav!- Gravi- Gravi- + R. I. F.I.D. Gravi- Gravi- Gravi-Quant it a- me try me try me try me try R.I./U.V. me try me try me try ti on

Model Compounds No Yes No Yes Yes Yes No Yes Yesp Yes Used

TABLE 52 CONTINUED

aSpecifically for coal-derived liquids

bSESC: 3'_equential flution by 3'_olvent fhromatography

cSARA: ~aturate, Aromatic, _!!.esin & ~sphaltene

dPONA: !araffin, Q_lefin, !!aphthene & Aromatic

SOAP: ~aturate, Qlefin, Aromatic & Polar

eRSMC: ~ecycle 3'_olvent !:f.ultiple Characterization

fOils, asphaltenes & asphaltols

gMaltenes, asphaltenes & asphaltols

hBased on !!_ildebrand solubility parameter

1considerable overl~p among compound classes (ref. 165}, some overlap among class types (ref. 34}

jDue to maltenes precipitation in n-alkanes

kAll polar compounds are eluted as a single peak

1Not available, method not published in detail

~ot reported

nTime required for determination of % distribution of classes in liquid fuel

0 sample size for HPLC analysis

PModcl compounds employed afterwards to monitor separation and characterization of the respective fractions by HPLC/FTIR

N VJ VJ

234

degree of overlap between fractions. High resolution gas

chromatographic and mass spectroscopic techniques were

employed to analyze the various fractions generated, first

using model mixtures, and later on using liquid fuels.

Work with model compounds has confirmed that the non-

polar fractions of the liquid fuel (saturate and aromatic

hydrocarbons) can be obtained with minimal overlap among the

compound classes, and that silica gel effectively divides

the aromatics by ring number into monoaromatic, diaromatic,

triaromatic, and polynuclear aromatic fractions that are

free of nitrogen-containing compounds. Contamination of the

aromatic fractions with arylethers, dibenzofurans and diben-

zothiophenes was observed and reflects the highly non-polar

nature of such compounds. The majority of the acidic (phe-

nols), basic (amines, pyridines and quinolines) and neutral

(benzofurans, indoles and carbazoles) model compounds, how-

ever, eluted from silica gel columns with the resins frac-

tion. This indicates that if such monofunctional compounds

exist in liquid fuels, then one would find them in this

fraction. Difunctional compounds, such as 2-aminopyridine,

eluted as "asphaltenes" which is not unusual considering the

acidic nature of the silica substrate. Polyfunctional com-

pounds are expected to be strongly retained on the silica

surface, and, depending on their molecular weights, some are

235

expected to elute as asphaltols, while a small number may be

irreversibly adsorbed. These expectations are in accordance

with the literature (34,94,240). None of the monofunctional

or difunctional polar model compounds eluted as asphaltols.

GC/MS analysis of liquefaction products of Brazilian

sugarcane bagasse served two purposes: first, the actual

chemical composition of the aromatic, resin and asphal tene

fractions of this important fuel was determined, and second,

the efficiency of the LC fractionation method was proven by

GC/MS results. The high aromatic content of sugarcane

bagasse should be of considerable interest to the fine chem-

ical industry of Brazil.

LC separation of bagasse liquids

tions, based on chemical class, is

into discrete frac-

achieved. Non-polar

fractions are mainly hydrocarbons, with little contamination

from neutral-oxygen and sulfur heterocyclic compounds

( dibenzofuran and dibenzothiophenes), while virtually free

of neutral-nitrogen containing species (carbazoles, indoles,

etc.). The aromatics themselves are fractionated by ring

number, into minimally overlapping classes, as has been con-

firmed by GC-FID quantitation of all identifiable species in

these fractions.

The "resins" fraction is essentially composed of mono-

functional neutral-nitrogen (indoles, carbazoles and

236

nitriles), basic-nitrogen (quinolines, benzoquinolines) and

weakly acidic aromatic species (phenols), with little con-

tamination from polyaromatic hydrocarbons; while basic-ni-

trogen (particularly quinolines), strong acidic species

(carboxylic acids) and high molecular weight nitrogen PAH's

compose the "asphaltenes". The major difference between the

"resin" and the "asphaltene" fractions is therefore polarity

and complexity of the chemical species. The "asphaltols"

fraction, however, must be composed of highly non-volatile

species that are not amenable to analysis by GC. Analytical

techniques such as pyrolysis GC and pyrolysis GC/MS may be

necessary for their analysis.

Direct GC/MS analysis of tne crude "resins" fraction,

as defined by the LC method, indicated that such a fraction

was too complex for identification of individual compounds.

Fractionation of "resins" into acidic, basic and neutral

concentrates before GC/MS was essential.

The acid-base-neutral separation scheme, developed

using model compounds, and later applied to "resins frac-

tions" from different fuel sources, provided minimally over-

lapping subfractions which are enriched with specific com-

pound classes. Analysis of the "resins" acidic, basic and

neutral concentrates by GC/MS demonstrated an enhancement of

gas chromatographic resolution among the individual compo-

237

nents, resulting in more accurate identification and better

quantitation.

A large number of compounds were identified, and their

concentrations determined, in the resins subfractions of

Brazilian sugarcane bagasse liquefaction products and Bra-

zilian "Mina do Leao" SRC. The major components found in

the resins subfractions of the SRC are phenols, indanols and

naphthols (acidic subfraction); anilines and quinolines

(basic subfraction); and tetralones and carbazoles (neutral

subfraction). The respective subfractions of the sugarcane

bagasse are rich in alkyl phenols, phenyl phenols and

naphthols; quinolines and benzoquinolines; and indoles,

nitriles and carbazoles.

Despite the intermediate polarity nature of the

"resins" fraction, approximately 37% of bagasse-derived

resins and 27% of SRC-derived resins were volatile and could

be analyzed by GC/MS. Other techniques, such as field ioni-

zation (FI) or field desorption (FD) mass spectrometry would

be necessary for a better analysis of the non-volatiles in

these fractions.

The use of the GC/MS technique throughout this work

proved to be highly valuable. Many specific compounds were

positively identified by the combined use of chromatographic

retention indices and mass spectral data of authentic stan-

238

dards. Identification only as compound types, rather than

specific compounds, was arrived at in other cases. This was

due to the limited number of model compounds available.

This type of identification, however, satisfies the purpose

of this study.

The utilization of a chromatographic retention index

system, developed on two fused silica capillary columns, for

peak identification of components in "resins" subfractions

is a very useful approach. For future studies the use of

more standard compounds would be helpful.

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