biomass conversion to bio-based products

BIOMASS CONVERSION TO BIO-BASED PRODUCTS

innovative ● entrepreneurial ● global

Creative

Resourceful

Excellent

Prof. Ir. Dr. Nor Aishah Saidina Amin

Chemical Reaction Engineering Group (CREG),

Faculty of Chemical & Energy Engineering,

University Technology Malaysia, Johor Bahru,

Malaysia.

PRESENTATION OUTLINE

Introduction

Biomass Opportunity & Biobased Chemical Market

Building Block Chemical from Biomass

Lignin for Carbon Cryogel Production

Properties of Carbon Cryogel

Potential of Carbon Cryogel as Catalyst for Biodiesel Production

Lignocellulosic Biomass Pretreatment

Ozonolysis Pretreatment

Potential Uses from Ozonolysis Pretreated Biomass

Sugars Derived Holocellulose for Levulinic Acid Production

Acid Hydrolysis and Dehydration for LA Production

Modified HY Zeolite & Functionalized Ionic Liquid as Catalyst

Conclusions

Acknowledgement

Malaysia: ~11% gross national

income (GNI) from

agriculture sector

80 million

tonnes

(2010)

110 million

dry tonnes

(2020)

Oil palm Rubber Kenaf Paddy

Source: National Biomass Strategy 2020

BIOMASS OPPORTUNITY

BIO-BASED CHEMICAL MARKET

Werpy et al., 2004.innovative ● entrepreneurial ● global

BUILDING BLOCK CHEMICALS

FROM BIOMASS

Succinic acid

Fumaric acid

OMalic acid

2,5-furan dicarboxylic acid

3-hydroxy propionic acid

OH NH2

Aspartic acid

Itanoic acid

Levulinic acid

Glycerol

Xylitol

3-hydroxybutyrolactone

Glutamic acid

Glucaric acid

Sorbitol

Lignocellulosic Biomass

Pretreatment

BIOMASS TO WEALTH INDUSTRY

BIOMASS

• Consist of cellulose, hemicellulose, lignin

• Limitation: lignin compound

PRETREATMENT

• degrade lignin

• Improve physical properties

• Increase holocelluloseaccessibility

BIO-BASED PRODUCT

• Convert sugars to valuable added product

GAP!!!

BIOMASS PRETREATMENT METHODS

Method Advantages Disadvantages

Alkali • High glucose recovery

• High solubility of hemicellulose

• Technology maturity for commercialization

• Corrosive

• Non-environmental friendly

Acid • Lower temperature and pressure

• Substrate rich in cellulose and xylan

• Corrosive

• non-environmental friendly

Hydrothermal • Only uses water for reaction medium

• Solubilize hemicellulose

• operated at high pressure

and temperature

• Lignin is remained in

sample

Explosion

• Limited chemicals are used except water

• Avoid excessive degradation of

monosaccharides

• Minimum corrosion of equipment

• Economical problem (high

operating cost)

• Inhibitor generation and

complex downstream

process

BIOMASS PRETREATMENT METHODS

Method Advantages Disadvantages

Ionic Liquid • Tunability

• High thermal stability

• Low volatility

• Much effort needed to make

the method commercially viable

Microwave-

assisted

• Shorter time

• Increases pretreatment selectivity

• Decreases the pretreatment energy

output

• Enhances enzymatic efficiency

• Involve corrosive chemical

• Much effort to make the MW

pretreatment commercially

viable

• High cost

Ozonolysis • Ambient operating condition

• High lignin degradation without affecting

the cellulose component

• Substrate rich in cellulose and xylan

• No toxic waste produce

• High cost ozone production

Constituents Composition (wt%)

Cellulose 30-31

Hemicellulose 20-24

Lignin 18-25

Ash 3-5

OIL PALM FRONDS (OPF)

Physical Properties

Moisture content 10 wt.%

Crystalinity 28-34 %

Surface area 1.0029 m2/g

Pore volume 0.0029 cm3/g

Pore diameter 11.57 nm

OZONOLYSIS SYSTEM FOR

OPF PRETREATMENT

Water film

Lignin film

OPF Surface

Treated OPF surface

HOW THE OZONE WORKS?

OPF surface

Exposure

cellulose surface

Kraft Lignin

Break AIL to ASL

Bio-based chemical

derived sugars

OBSERVATION FROM OZONOLYSIS

0 min (15-20) min (30-40)min

>50min End of reaction

Washing with NaOH

Before treatment

After washing and filtration

After Drying

PROTOTYPE FOR

OZONOLYSIS PRETREATMENT

innovative ● entrepreneurial ● global4/3/2020 14

Electrical

Outlet

OF OPF

LignocellulosicBiomass

Cellulose Hemicellulose Lignin

Ozonolysis

Sample CodedMoisture

content (wt.%)

Particle

size (mm)

Reaction time

Ozone flowrate

(mL/min)

concentration

(wt.%)

Untreated

(UTP)10 0.8 - - -

R3 30 0.8 1 30 40

R4 70 0.8 1 60 20

R5 30 0.3 2 60 20

R6 70 0.3 2 30 40

PRETREATED OPF

UntreatedLignin degrade

highly

fibrillar,

intact

morphology

structure

structure is

totally

disrupted

Lignin degrade:

medium

Lignin degrade:

structure is

slightly

disrupted

structure is

slightly

disrupted

FESEM - Morphology

PRETREATED OPF

Plasma cell wall

Microfibril Strand

Cellulose Rosette

UNTREATED OPF

PRETREATED OPF

Breakage of

cell wall

PRETREATED OPF

10 15 20 25 30 35 40 45 50

2-Theta

Lignin

Degradation

Crytalinity

Index (CrI)

BET Surface

(m2/g)

Diameter

Volume

(x 10-3 cm3/g)

n/a 36.1 1.03 11.40 2.93

90.15 51.9 0.74 11.10 2.05

39.02 52.1 1.07 98.74 2.65

1.83 50.1 1.00 11.01 2.76

treated sample increased the

intensity of crystal structure

higher lignin degradation (R4)

showed the highest intensity but

not CrI

POTENTIAL USES FROM

PRETREATED OPF

Cellulose Untreated OPF Treated OPF

feedsto

Sugars Derived

Holocellulose for

Levulinic Acid (LA)

Production

PRODUCTS FROM BIOMASS

PRETREATMENT – POTENTIAL USES

Ozonolysis

Sugars

5-hydroxymethyl furfural (5-HMF)

Levulinic Acid (LA)

LEVULINIC ACID – BUILDING BLOCK

CHEMICAL

Fuels additives

Flavoring & fragrance

Pharmaceutical agentsResins

Polymers

OHOH2C CHO

H3C COOH

+ HCOOH

levulinic acid

glucose

formic acid

OH OHHOH2C

fructose

isomerization

rehydration

dehydrationHMF

BIOMASS CONVERSION TO LA

Cellulose Glucose

Biomass

dissolution /

pretreatement

Cellulose

hydrolysis

Bronsted Acid

Bronsted AcidLewis Acid

ACID CATALYSTS FOR LEVULINIC ACID

PRODUCTION

Iron Modified HY Zeolite

(Fe/HY) catalyst

Functionalized Ionic

Liquid (FIL) catalysts

Catalysts preparation

Catalysts

characterization

Optimization

Catalyst screening

Levulinic acid production

from glucose

Levulinic acid production

from OPF

Kinetic study

Fe/HY ZEOLITE – XRD, FTIR

5 10 15 20 25 30 35 40 45 50

2 theta (o)

5% Fe/HY

10% Fe/HY

15% Fe/HY

HY zeolite

XRD patterns of HY zeolite and Fe/HY zeolite

catalysts.

4000 3600 3200 2800 2400 2000 1600 1200 800 400

15% Fe/HY

10% Fe/HY

5% Fe/HY

HY zeolite

Wavenumber (cm-1)

FTIR spectra of HY zeolite and Fe/HY zeolite

catalysts

• XRD patterns of Fe/HY zeolite matched

with parent HY zeolite.

• Modification has no obvious effect

• HY zeolite structure remained intact

• No significant band shift from Fe/HY

zeolites spectra

Ramli et al., App Cat B, 2015;163:487-498

Fe/HY ZEOLITE – N2 PHYSISORPTION

Catalysts SBET a

(m2/g)

Smeso b

(m2/g)

Smicroc

(m2/g)

Vporesd

(cm3/g)

Vmesoe

(cm3/g)

Vmicro f

(cm3/g)

Dmeang

Dmesoh

Dmicroi

HY zeolite 829.5 76.4 753.1 0.369 0.082 0.287 1.78 5.86 0.54 0.0716

5% Fe/HY 598.9 122.5 476.5 0.279 0.092 0.187 1.83 4.33 0.53 0.1371

10% Fe/HY 549.3 133.6 415.8 0.265 0.098 0.167 1.89 3.77 0.52 0.1532

15% Fe/HY 522.1 145.0 377.1 0.263 0.109 0.154 1.98 3.62 0.52 0.1626

Surface area and porosity of HY zeolite and Fe/HY zeolite catalysts

• Impregnation - decreased surface area and pore

volume

• Presence of Iron oxide blocked some of the pores

• Type I isotherm – microporosity of

samples

Fe/HY ZEOLITE – TPD, FTIR PYRIDINE

0 200 400 600 800

Temperature (oC)

Fe/HY 5%

HY zeolite

Fe/HY 10%

Fe/HY 15%

1560 1540 1520 1500 1480 1460 1440 1420

Wavenumber (cm-1)

15% Fe/HY

5% Fe/HY

10% Fe/HY

HY zeolite

NH3-TPD profiles of catalysts FTIR spectra of pyridine absorbed on catalysts

• Impregnation of FeCl3 increase the

acidity

Catalysts Total acidity

(mmol/g)

Number of acid

sites (µmol/m2)

HY zeolite 1.58 1.91

5% Fe/HY 2.81 4.69

10% Fe/HY 2.68 4.88

15% Fe/HY 2.12 4.06

• Fe/HY zeolites has higher Lewis acid

Fe/HY ZEOLITE – GLUCOSE TO

LEVULINIC ACID

120 140 160 180 2000

Reaction temperature (oC)

Levulinic acid

Formic acid

120 140 160 180 2000

Reaction temperature (oC)

Levulinic acid

Formic acid

120 140 160 180 2000

Reaction temperature (%)

Levulinic acid

Formic acid

Product yields versus reaction temperature at 3 h of reaction time for

5% Fe/HY zeolite (a), 10% Fe/HY zeolite (b), and 15% Fe/HY

zeolite (c) catalysts.

• Highest LA yield at 180 C

• 10% Fe/HY zeolite - highest catalytic performance

10% Fe/HY

• High performance – high no of acid sites,

appropriate ratio of Bronsted to Lewis acid

5% Fe/HY

15% Fe/HY

FUNCTIONALIZED IONIC LIQUID

Cation

Drying

1-butyl-3-methyl imidazolium

tetrachloroferrate

[BMIM][FeCl4]

1-sulfonic acid-3-methyl imidazoliumchloride [SMIM][Cl]

1-sulfonic acid-3-methyl imidazoliumtetrachloroferrate

[SMIM][FeCl4]

Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121.

FIL - ACIDITY

Pyridine-FTIR spectra of FIL catalysts.

• [SMIM][FeCl4] consisted of both Lewis and

Bronsted acid sites

• Bronsted – sulfonic acid group in cation

• Lewis – FeCl4 in anion

Acidity of FIL

[SMIM][FeCl4]

[SMIM][Cl]

[BMIM][FeCl4]

FeCl3.6H2O

N N+ 6H2O

N N+ SO3HCl

+ FeCl3.6H2O

CH2Cl2

FeCl3.6H2O

N N+ 6H2O

N N+ SO3HCl

+ FeCl3.6H2O

CH2Cl2

FeCl3.6H2O

N N+ 6H2O

N N+ SO3HCl

+ FeCl3.6H2O

CH2Cl2

1-butyl-3-methyl imidazolium tetrachloro ferrate

1-sulfonic acid-3-methyl imidazolium chloride

1-sulfonic acid-3-methyl imidazolium

tetrachloro ferrate

[BMIM][FeCl4]

[SMIM][Cl]

[SMIM][FeCl4]

Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121

FIL – GLUCOSE TO LEVULINIC ACID

1 2 3 4 50

Levulin

Reaction time (h)

1 2 3 4 50

Reaction time (h)

1 2 3 4 50

Reaction time (h)

LA yield using [BMIM][FeCl4], [SMIM][Cl], [SMIM][FeCl4] as a

catalyst ■ 170 °C, ▲150 °C, ●130 °C, ×110 °C. 10g FIL, 10 ml H2O

[BMIM][FeCl4]

[SMIM][Cl]

• [SMIM][FeCl4] - highest catalytic performance

• High activity – high acidity comprised of both

Bronsted and Lewis acid sites [SMIM][FeCl4]

Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121

Fe/HY – GLUCOSE TO LEVULINIC ACIDGlucose

(G) Levulinic acid

Humins and unidentified soluble products

k35-hydroxymethyl furfural (H)

Reaction scheme for glucose conversion to LA

Key Steps Reaction

1. Glucose conversion to 5-HMF

2. Glucose decomposition to

humins

3. 5-HMF conversion to LA

4. 5-HMF decomposition to

humins

(Eq. 1)

(Eq. 2)

𝑅𝐺 = (𝑘1 + 𝑘2)𝐶𝐺

𝑅𝐻 = 𝑘3 + 𝑘4 𝐶𝐻

−𝑑𝐶𝐺

𝑑𝑡= 𝑘1 + 𝑘2 𝐶𝐺

𝑑𝐶𝐻

𝑑𝑡= 𝑘1𝐶𝐺 − 𝑘3 + 𝑘4 𝐶𝐻

𝑑𝐶𝐿𝐴

𝑑𝑡= 𝑘3𝐶𝐻

(Eq. 3)

(Eq. 4)

(Eq. 5)

Ramli et al., Chem. Eng. J. 283, 150-159.

Fe/HY – GLUCOSE TO LEVULINIC ACID

0 50 100 150 200 250

6.0 Glucose conversion

Reaction time (min)

0 50 100 150 200 250

Reaction time (min)

5-HMF conversion

-ln(1-X) versus time for (a) glucose conversion and (b)

5-HMF conversion using 10% Fe/HY zeolite. ■ 120

°C, ▲ 140 °C, ● 160 °C, * 180 °C, ○ 200 °C.

- 10% Fe/HY zeolite

- 120 to 200 °C from 0 to 240 min

-Linearity of -ln(1-X) versus time

- 1st order reaction

FIL – GLUCOSE TO LEVULINIC ACID

0 50 100 150 200 250 300

6.0 Glucose conversion

Time (min)

0 50 100 150 200 250 300

Time (min)

5-HMF conversion

Effect -ln(1-X) versus time for glucose conversion and 5-

HMF conversion using [SMIM][FeCl4].

■ 110 °C, ▲ 130 °C, ● 150 °C, * 170 °C.

- [SMIM][FeCl4]

-110 to 170 °C from 0 to 300

-Linearity of -ln(1-X) versus

- 1st order reaction

PRESENTATION OUTLINE

Presentation OutlineProposed model Reaction conditions Ea (kJ.mol-1) Reference

120 – 200 °C10% Fe/HY zeolite

Ea1 = 66

Ea2 = 76

Ea3 = 68

Ea4 = 67

This study

110 – 170 °C[SMIM][FeCl4]

Ea1 = 50

Ea2 = 34

Ea3 = 26

Ea4 = 44

This study

180 – 280 °CNon catalyzed

Ea1 = 108

Ea2 = 136

Ea3 = 89

Ea4 = 109

Ea5 = 131

(Jing and LÜ, 2008)

170 – 210 °CH2SO4

Ea1 = 86

Ea2 = 57

Ea3 = 209

(Chang et al., 2006)

140 – 180 °CHCl

Ea1 = 160

Ea2 = 51

Ea3 = 95

Ea4 = 142

(Weingarten et al.,

140 – 180 °C[C2OHMIM][BF4]

Ea1 = 56 (Qu et al., 2012)

80 – 120 °CCrCl3 in [AMIM][Cl]

Ea1 =135 (Zhang et al., 2014)

Glucose 5-HMF LA

Humins Humins

Glucose 5-HMF LA

Humins Humins

Glucose 5-HMF LA

Humins Humins

Decomposition

product

Glucose 5-HMF LA1

Humins

Glucose 5-HMF LA

Humins Humins

Glucose 5-HMF1

Introduction of catalyst (Fe/HY @

[SMIM][FeCl4]) has accelerated the

reaction, consequently lowering the Ea

LEVULINIC ACID PRODUCTION

FROM BIOMASS FEEDSTOCKS

BiomassCellulose

content (%)Catalyst

LA yield (%) Efficiency

(%)Biomass Theoretical

Oil palm fronds 45.2 Fe/HY zeolite 19.6 32.1 61.1

Oil palm fronds 45.2 [SMIM][FeCl4] 24.8 32.1 77.3

Water hyacinth [1] 26.3 H2SO4 9.0 18.7 48.2

Wheat straw [5] 40.4 H2SO4 19.9 28.7 68.8

Rice straw [18] 46.1 S2O82-/ZrO2-SiO2-Sm2O3 22.8 32.7 70.0

Empty fruit bunch

41.1 Cr/HY zeolite 15.5 29.2 53.2

Sorghum grain [19] 73.8 H2SO4 32.6 52.4 62.2

Fe/HY AND FIL REUSABILITY FOR

LEVULINIC ACID PRODUCTION

1 2 3 4 5

cose (

Glucose (Fe/HY) Glucose ([SMIM][FeCl])

OPF (Fe/HY) OPF ([SMIM][FeCl4])

ld fro

Lignin for

Carbon Cryogel Production

PRODUCTS FROM BIOMASS

PRETREATMENT – POTENTIAL USES

Carbon Cryogel

Ozonolysis

Sugars

5-hydroxymethyl furfural (5-HMF)

Levulinic Acid (LA)

CARBON CRYOGEL

Phenol / Resorcinol

Catalyst /

catalyst support

Carbon

gels Formaldehyde

Aerogel Cryogel Xerogel

Substituted phenol and formaldehyde derivatives can be used to

produce organic gels

Synthesis

from toxic

chemicals

Expensive

drying

process

CARBON CRYOGEL

Mix with furfural, EtOH,

acid sulfuric, distilled water

• Heat treatment at 90˚C

(silicone oil temp.), 0.5 h

• Solvent exchange with t-butanol

• Pre-frozen 24 h (refrigerator),

• dried at -60 ˚C, 8 h (condenser temp.)

Lignin

Solvent exchange and Freeze dried

Cryogel Characterization TGA

surface area, TPD, TGA,

FESEM Characterization

• Under nitrogen flow: 500˚C,5 h

Carbon Cryogel

Carbonization

CARBON CRYOGEL

300 400 500 600 700

ity (m

Temperature (oC)

High total surface area and acidity

Optimum surface area and acidity

The optimum

temperature

EFFECT OF CARBONIZATION

TEMPERATURE ON CRYOGEL

CARBON CRYOGEL

TIME ON CRYOGEL

High total surface area of 214 m2/g and total

acidity of 11.29 mmol/gSelected as optimum condition at 500 ˚C and 4 h

ity (m

1 2 3 4 50

Time (h)

The optimum time

CARBON CRYOGEL

Thermal stability: Carbon cryogel > cryogel

100 Weig

sses ra

in–1)

Temperature (C)

200 400 600 8000

Cryogel

Carbon Cryogel

Volatilization

of moisture

Decomposition of SO3

& organic compound

Decomposition of lignin

CARBON CRYOGEL

TEMPERATURE ON CRYOGEL

Carbon CryogelCryogel

500X 500X

50m 50m

• Size reduction after carbonization

Decomposition of organic compound during carbonization

Reduction & reconstructuring of functional group & carbon bonding

Surface area increased

CARBON CRYOGEL AS CATALYST

FOR LEVULINIC ACID ESTERIFICATION

EtOH H2O+ +

Levulinic Acid Ethyl Levulinate

Levulinic Acid Esterification with Ethanol to Ethyl Levulinate

Carbon

cryogel

CARBON CRYOGEL AS CATALYST

FOR LEVULINIC ACID ESTERIFICATION

innovative ● entrepreneurial ● globalRef.: [1,2] Fernandes et. al, App. Cat. A, 2012. 425: p. 199-204; [3] Nandiwale et. al, App. Cat. A, 2013. 460: p. 90-98; [4] Cirujano et. al,

Chem. Eng. Sci., 2015. 124: p. 52-60; [5] Yan et. al, Cat. Comm., 2013. 34: p. 58-63; [6] Pasquale et. al, Cat. Comm., 2012. 18: p. 115-120.

CatalystTime

Temperature

Catalyst

loading (wt.%)

Molar ratio

(EtOH to LA)

(mol.%)Ref.

Amberlyst-15 5.0 70.0 2.5 5.0 55.0 [1]

SO4/SnO2 5.0 70.0 2.5 5.0 40.0 [2]

DPTA/DH-ZSM-5 4.0 78.0 25.0 6.0 82.0 [3]

UiO-66 8.0 78.0 1.82 15.0 94.0 [4]

H4SiW12O40/SiO2 6.0 75.0 51.0 18.0 67.0 [5]

40WD-S 10.0 78.0 107.7 (0.52) 64.0 76.0 [6]

Carbon Cryogel 3.0 150 25.0 20.0 84.0 This study

1 the data in wt.%2 the data in mol.%

CONCLUSIONS

o High lignin degradation without affecting cellulose & hemicellulose component

o High sugar recovery

o High levulinic acid production from the ozonolysis pretreated biomass

SUGARS DERIVED HOLOCELLULOSE FOR LEVULINIC ACID PRODUCTION

o Fe/HY zeolite and functionalized ionic liquid as catalyst

o Bronsted and Lewis acids play roles in levulinic acid production

o Both catalyst can be reused for glucose and OPF conversion

o Glucose conversion to levulinic acid –1st order reaction, Ea lower and

comparable with other catalysts

LIGNIN FOR CARBON CRYOGEL PRODUCTIONo Lignin and furfural was used to produce carbon cryogel

o Carbon cryogel - high thermal stability, acidity, and surface area

o As catalyst for ethyl levulinate production from levulinic acid - 87.7 wt% yield

ACKNOWLEDGEMENT

Universiti Teknologi Malaysia for supporting the

project under the Research University Grant

Vote No. 03H48 and 07H14

Chemical Reaction Engineering Group (CREG),

Universiti Teknologi Malaysia

www.fche.utm.my/staf/noraishah

Tel: +6075535579, +60127165490

Email: noraishah@cheme.utm.my

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