gounder research laboratory: chemistry and catalysis of … · 2017. 5. 3. · gounder research...

Gounder Research Laboratory: Chemistry and Catalysis of Nanoscale Materials

Si Si O O

Si

~1 nm

10 µm!

Nanoscale catalysts with tunable site and structural properties

~1 nm

Rajamani Gounder [email protected]

Larry and Virginia Faith Assistant Professor of Chemical Engineering, Purdue University

Purdue Process Safety and Assurance Center (P2SAC) Meeting May 3, 2017 – West Lafayette, IN

SYNTHESIS

CHARACTERIZATION hν

*

CATALYSIS A

A* B* B

THEORY

Published: September 14, 2011

r 2011 American Chemical Society 21785 dx.doi.org/10.1021/jp2062018 | J. Phys. Chem. C 2011, 115, 21785–21790

ARTICLE

pubs.acs.org/JPCC

Adsorption and Diffusion of Fructose in Zeolite HZSM-5: Selection ofModels and Methods for Computational StudiesLei Cheng,† Larry A. Curtiss,*,†,‡ Rajeev Surendran Assary,†,§ Jeffrey Greeley,‡ Torsten Kerber,^ andJoachim Sauer^

†Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States‡Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States§Chemical & Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States^Institut f€ur Chemie, Humboldt-Universit€at zu Berlin, D-10099 Berlin, Germany

1. INTRODUCTION

Biomass has the potential to serve as a renewable energy sourceand to produce industrially important chemicals. However, achiev-ing controlled, energy-efficient conversion of cellulose to poten-tially useful chemicals poses a great challenge in catalysis science.Conversion of biomass to fuels and value-added chemicals is a verycomplex process.1 It involves, first, the hydrolysis of cellulose tocarbohydrates, followed by targeted dehydration, hydrogenolysis,dehydrogenation, hydrogenation, oxidation, etc. In a recent com-putational study2 of the conversion of glucose to 5-hydroxymethylfurfural (HMF), levulinic acid, and formic acid in a homogeneousenvironment, the thermochemical data were computed for theisomerization of glucose tomore active fructose species and for thesubsequent three targeted dehydration steps that complete theconversion to HMF. However, no computational studies of fruc-tose activation in solid acid catalysts have been reported. Experi-mentally, mineral acids in solution and acid sites on solid Brønstedcatalysts are commonly used to dehydrate hexoses.3,4 Severalresearch groups have used zeolites or acid ion-exchange resins toprepare HMF from fructose dehydration.5!9 Zeolite HZSM-5 isa very versatile catalyst and can be used as a solid acid for a rangeof reactions, such as alcohol dehydration, hydrocarbon isomer-ization, and alkylation. It has also been used previously in cat-alytic fast pyrolysis for biofuel production.10,11

Computational studies can help understand reaction mechan-isms and predict the thermodynamics, kinetics, and pore selectivities

of the reactions catalyzed by zeolites, such as those involvingfructose. Applying appropriate theoretical treatments to thesestudies of zeolites is crucial. Density functional theory (DFT) iscomputationally cost-efficient and has been routinely used in thecomputational catalysis community. However, the method suf-fers from the disadvantage of not accounting for long-rangedispersion interactions properly, and this limits its application inmany reactions catalyzed by zeolites. Tuma and Sauer applied ahybrid MP2:DFT scheme12 to add the MP2 corrections toreaction energies in the full periodic limit. The scheme canaccurately calculate bond rearrangement and dispersion interac-tions at the same time and yields reaction barriers comparable withthe experimental data.13,14 However, such an approach requiresmany expensive MP2 calculations of cluster models for theextrapolation of the final reaction energy to the periodic limit.Alternatively, a computationally less expensive scheme with anadded damped C6 dispersion term parametrized by Grimme15 tothe full periodic PBE energies16 (PBE+D) was found to yield reac-tion energies comparable to those predicted by the hybrid methodfor the methylation of alkenes13 and the alkylation of benzene inHZSM-5.17 In comparison to the DFT calculations, the PBE+Dreaction potential energy profile was shifted downward significantly

Received: June 30, 2011Revised: September 8, 2011

ABSTRACT:The adsorption and protonation of fructose in HZSM-5 have been studiedfor the assessment of models for accurate reaction energy calculations and the evaluationof molecular diffusivity. The adsorption and protonation were calculated using 2T, 5T,and 46T clusters as well as a periodic model. The results indicate that the reactionthermodynamics cannot be predicted correctly using small cluster models, such as 2T or5T, because these small cluster models fail to represent the electrostatic effect of a zeolitecage, which provides additional stabilization to the ion pair formed upon the protonationof fructose. Structural parameters optimized using the 46T cluster model agree well withthose of the full periodic model; however, the calculated reaction energies are insignificant error due to the poor account of dispersion effects by density functionaltheory. The dispersion effects contribute !30.5 kcal/mol to the binding energy of fructose in the zeolite pore based on periodicmodel calculations that include dispersion interactions. The protonation of the fructose ternary carbon hydroxyl group wascalculated to be exothermic by 5.5 kcal/mol with a reaction barrier of 2.9 kcal/mol using the periodic model with dispersion effects.Our results suggest that the internal diffusion of fructose in HZSM-5 is very likely to be energetically limited and only occurs at hightemperature due to the large size of the molecule.

§  Topics in Catalysis, 58 (2015) 424-434 §  Catalysis Science & Technology, 4 (2014) 2877-2886 §  J. Physical Chemistry C, 118 (2014) 22815-22833 §  ACS Catalysis, 4 (2014) 2288-2297 §  Journal of Catalysis, 308 (2013) 176-188 §  ACS Catalysis, 3 (2013) 1469-1476 §  AIChE Journal, 59 (2014) 3349-3358 §  ACS Catalysis, 2 (2012) 2705-2713 Raj Gounder

Fabio Ribeiro

§  Journal of Catalysis, 313 (2014) 104-112 §  Journal of Catalysis, 308 (2013) 98-113 §  Journal of Catalysis, 296 (2012) 31-42 §  Journal of Catalysis, 287 (2012) 178-189

§  … and 12 more (with W. N. Delgass)

Jeff Greeley

§  ACS Catalysis, 4 (2014) 1091-1098 §  J. Physical Chemistry C, 115 (2011) 21785-21790

§  … and more in preparation

LONG-TERM GOAL: A collaborative project that can leverage the expertise of more than 1 faculty in Purdue ChE

P2SAC Project: Prevention through catalyst design for applications in the petrochemical industry (PI: Raj Gounder)


VISION: Prevention through catalyst design. Design catalysts to allow practicing safer industrial processes, and eliminating safety/occupational hazards.

CHEMICALS: Synthesis of solid Lewis acids for safer catalytic oxidation reactions

Example: Propylene oxide (PO) monomers §  7.7 million tons/yr produced

worldwide in 2012 (9.5/yr in 2016) §  BASF/Dow Chemical make PO

using Ti-zeolites (HPPO process)

Propylene epoxidation occurs on isolated Lewis

acidic Ti centers in zeolites Unwanted H2O2 decomposition to O2 occurs on non-framework TiO2 sites, potential overpressures / explosions

TiO2

SnO2

TiO2

SnO2

Ti

Ti

Ti

framework Ti desired non-framework TiO2 undesired

P2SAC Project: Development of Catalysts for Safer Oxidation Reactions

Technical Achievements (Years 1-2)

“Controlled Insertion of Tin Atoms into Zeolite Framework Vacancies and Consequences for Glucose Isomerization Catalysis”

J. C. Vega-Vila, J. W. Harris, R. Gounder Journal of Catalysis, 344 (2016) 108-120

“Methods to Synthesize Stannosilicate Materials with Controlled Tin Coordination” R. Gounder, J. C. Vega-Vila, J. Harris

U.S. Provisional Application, Filed Aug. 29, 2016

Avoid HF-assisted synthesis of hydrophobic

zeolites


Counting Lewis acidic Sn sites in zeolites using four Lewis base titrants

“Titration and Quantification of Open and Closed Lewis Acid Sites in Sn-Beta Zeolites that Catalyze Glucose Isomerization”

J. W. Harris, M. J. Cordon, J. R. Di Iorio, J. C. Vega-Vila, F. H. Ribeiro, R. Gounder Journal of Catalysis 335 (2016) 141-154



“A Transmission Infrared Cell Design for Temperature-Controlled Adsorption and Reactivity Studies on Heterogeneous Catalysts”

V. J. Cybulskis, J. W. Harris, Y. Zvinevich, F. H. Ribeiro, R. Gounder Review of Scientific Instruments 87 (2016) 103101

Lab Safety Achievements (Years 1-2)

IR

LN2 inlet LN2 inlet

Gas inlet Gas outlet

(isolation valve) Over T thermocouple

Safer handling of liquid cryogens



Glucose-Fructose Isomerization (a model reaction)

“Titration and Quantification of Open and Closed Lewis Acid Sites in Sn-Beta Zeolites that Catalyze Glucose Isomerization”

J. W. Harris, M. J. Cordon, J. R. Di Iorio, J. C. Vega-Vila, F. H. Ribeiro, R. Gounder* Journal of Catalysis 335 (2016) 141-154

“Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites” P. Wolf, J. Harris, R. Gounder, C. Coperet, et al. (ETH-Zurich)

Helvetica Chimica Acta 99 (2016) 916-927


VISION: Prevention through catalyst design. Design catalysts to allow practicing safer industrial processes, and eliminating safety/occupational hazards.

REFINING: Synthesis of solid Brønsted acids to practice carbon chain growth chemistry

Example: Alkylation for high-octane gasoline §  2 million barrels/day produced

worldwide in 2016 §  Several refiners make alkylate

using H2SO4 or HF liquid acids §  Last major refinery/petrochemical

process using strong liquid acids

§  Technical challenges with solid catalysts: §  Catalyst lifetime (deactivation and fouling) and regeneration

§  Goal of this project: Basic research to enable solid acid alternatives

§  Some potential alternatives are emerging: §  Solid Lewis-Brønsted superacids §  AlkyClean® (Albermarle, CB&I, Neste Oil): 2700 barrels/day §  ISOALKY (Chevron): ionic liquids

(new project)

Alkylation catalysis: Background and Motivation

§  Mechanism (simplified):

§  Reaction: §  Alkylation of isobutane with light (C3-C5) olefins to make multiply-branched

C7-C9 alkanes with high octane number (gasoline)

§  Refinery Motivation: §  Worldwide capacity: 1.6 million BBL/day §  Total gasoline demand shrinking, but high octane (and clean) demand increasing §  Current alkylation units have reached capacity §  Butanes and pentanes (lighter HCs) are being excluded from the gasoline pool

due to Reid Vapor Pressure (RVP) limits §  New opportunities from increasing supply of light hydrocarbons in shale oil,

heavier hydrocarbons are attractive energy carriers

!"# $%&'( )*!*&+$!, (-# !% !"# &%. %&#/0 )%0)#0!1*!'%0#2#1+."#1# '0 !"'$ 1#*)!%13

4! '$ 2#1+ ('5/)-&! *0( 61%7*7&+ !%% #*1&+ !% 5%1#)*$!'5 8*0( ."#09 !"# 61%)#$$ (#2#&%6:#0!$ '0 ;*7&# < .'&&7# ':6&#:#0!#( %0 * )%::#1)'*& $)*&#3

!" #$%&'(& )'* +,$ -$%.+/0%+/'( %(- &$1$.+/0/+21'&& ') &'1/- %1321%+/'( .%+%12&+&

;"# $':6&#$! :#)"*0'$: %0# )*0 '02%=# 5%1 !"#*)'(>)*!*&+?#( 8#3@3, ?#%&'!#>)*!*&+?#(9 *&=+&*!'%0 %5'$%7-!*0# .'!" A>7-!#0# '$ (#6')!#( '0 B'@3 C3 ;"#(%-7&# 7%0( %5 !"# *&=#0# *(($ !% !"# 6%$'!'2#&+)"*1@#( )*17%0 *!%: %5 !"# !#1!'*1+>7-!+& )*!'%0 )"#>

:'$%17#( %0 *0 *)'( $'!# 8!"'$ %&#/0 *(('!'%0, '3#3, $!#644 '0 B'@3 C, '$ $%:#!':#$ 1#5#11#( !% *$ !"# *&=+&*!'%0$!#6 '0 !"# 0*11%.#1 $#0$#93 4! )*0 #*$'&+ 7# $##0 !"*! *"'@"&+ 71*0)"#(, $#)%0(*1+ %)!+& )*!'%0 .'!" !"#$=#&#!%0 %5 A,A,C>!1':#!"+&6#0!*0# #:#1@#$ 51%: !"'$%&#/0 *(('!'%03 D#E!, *0 !"#$%:%&#)-&*1 "+(1'(# !1*0$>5#1 8$!#6 4449 )*0 7# #02'$*@#( ."')" @'2#$ !"# !#1!'*1+)*!'%0 .'!" !"# $*:# )*17%0 $=#&#!%03 F-)" !#1!'*1+)*17#0'-: '%0$ )*0 -0(#1@% *)'(>)*!*&+?#( !"#&$:%>&#)-&*1 "+(1'(# !1*0$5#1 8$!#6 G '0 B'@3 C9, #3@3, 51%: *0'$%7-!*0# :%&#)-&#, ."')" &'7#1*!#$ !"# 61%(-)! :%&#>)-&# A,A,C>!1':#!"+&6#0!*0#, *0( *! !"# $*:# !':#,)&%$#$ !"# )*!*&+!') )+)&#3

4! '$ 7#+%0( !"# $)%6# %5 !"'$ *))%-0! !% ('$)-$$, '05-&& (#6!", !"# 2*&'('!+ %5 !"'$ :#)"*0'$: 5%1 '$%7->!*0#HA>7-!#0# *&=+&*!'%0 %0 $%&'( *)'($3 4! '$ %72'%-$,"%.#2#1, !"*! '! $-55#1$ 51%: *! &#*$! !.% $#2#1# $"%1!>)%:'0@$I 8'9 '! 5*'&$ !% #E6&*'0 !"# 5%1:*!'%0 %5 !"#%!"#1 !1':#!"+&6#0!*0#$, '3#3, A,A,J>, A,C,C> *0( A,C,J>!1':#!"+&6#0!*0#, %5 !"# ('71*0)"#( *0( :%0%>71*0)"#( '$%%)!*0#$, *0( %5 !"# '$%*&=*0#$ .'!" &#$$*0( :%1# !"*0 #'@"! )*17%0 *!%:$ 8&'@"! *0( "#*2+#0($93 ;% *))%-0! 5%1 !"# 5%1:*!'%0 %5 !"# %!"#1!1':#!"+&6#0!*0#$, *)'(>)*!*&+?#( 1#*11*0@#:#0!$ %5!"# )*17%0 $=#&#!%0 *! !"# &#2#& %5 !"# )"#:'$%17#('$%%)!+& )*!'%0$ *1# -$-*&&+ '02%=#( 8#2#0 '5 !"'$ '$*))#6!#(, '! 1#:*'0$ %6#0 ."+ $% &'!!&# A,A,C>!1'>:#!"+&6#0!*0# '$ 5%1:#( '0 '$%7-!*0#HA>7-!#0# *&=+>&*!'%093 ;"#1# '$ 0% .*+, "%.#2#1, !% '0!#161#! !"#

;*7&# <4$%7-!*0#H*&=#0# *&=+&*!'%0 %0 $%&'( )*!*&+$!$3 K-11#0! 61%)#$$ (#2#&%6:#0!$ *! !"# 6'&%! 6&*0! $!*@#

D%3 L#2#&%6#1H&')#0$#1 K*!*&+$! M#*)!%1 !+6# N&=+&*!#)*6*)'!+8=@H(9

M#5#1#0)#$

< O*&(%1 ;%6$P# NHF ;1'5&-%1%:#!"*0#$-&5%0') *)'(%0 * 6%1%-$ $-66%1!

B'E#( 7#(, *)'( :%2#$ *&%0@7#(, 61%61'#!*1+ 61%)#$$ 5%1*)'( 1#@#0#1*!'%0

QQ R<S,<TU

A K*!*&+!')*, D#$!# V+,K%0%)%

W1%61'#!*1+ X0=0%.0, .'!" 1#)+)&# *0()*!*&+$! 1#@#0#1*!'%0

TYZ R<Y,<[U

C K"#:')*& M#$#*1)" \]')#0$'0@, K"#21%0

N0!':%0+6#0!*5&-%1'(# %0*)'(>.*$"#( $'&')*

F&-11+ 1#*)!%1 <<<Z R<Y,<[U

J XVW W1%61'#!*1+, 1#$#:7&#$ !1*('!'%0*&"+(1%)*17%0 )%02#1$'%0 )*!*&+$!$

X0=0%.0, .'!" )%0!'0-%-$ )*!*&+$!1#@#0#1*!'%0 -$'0@ "+(1%@#0

X0=0%.0 R<Y,<[U

B'@3 C3 F':6&#$! )*!*&+!') )+)&# 5%1 !"# *&=+&*!'%0 %5 '$%7-!*0# .'!"A>7-!#0#3

<[S '( )&!#*%+,- .( /$%% 0 1%#%234!4 /56%3 78 9:888; :8<=:88

Weitkamp and Traa, Catal. Today 49 (1999) 193-199

Intermolecular hydride transfer

reactions are critical

Promoted by stronger acids and

higher acid site densities


§  Several process safety and hazard issues with liquid acid catalysts:

§  Catalyst consumption (H2SO4) is high §  Catalyst aftertreatment: spent acid contains tarry hydrocarbons and water §  Alkylate quality is lower from H2SO4 catalysts than HF §  HF is toxic and corrosive, safety hazards with handling and operation §  1960s-1986: HF plants >> H2SO4 plants

§  Liquid acid catalysts for alkylation:

§  1932: Vladimir Ipatieff (UOP): Aluminum Chloride (AlCl3/HCl, BF3/HF) §  1930s (late): Sulfuric acid (H2SO4) §  1942: Hydrofluoric acid (HF) plants built by Phillips

§  Demand for high-octane aviation gasoline for World War II (5M gallons/day) §  1952: Demand increased again during Korean War (14M gallons/day) §  1980s: Demand increase due to phase-out of leaded gasoline (50M gallons/day)



§  Catalyst consumption (H2SO4) is high §  Catalyst aftertreatment: spent acid contains tarry hydrocarbons and water §  Alkylate quality is lower from H2SO4 catalysts than HF §  HF is toxic and corrosive, safety hazards with handling and operation §  1960s-1986: HF plants >> H2SO4 plants




Marathon Refinery, Texas City, TX October 31, 1987

“On the fateful Friday, October 31, 1987, according to Marathon spokesman William

Ryder, refinery workers were using a crane to lift a 40-ton heat exchanger convection section from a hydrofluoric acid heater. At about 5:20 PM, the crane

failed and the piece fell. As it fell, and severed a 4″ loading line containing hot acid and a 2″ pressure relief line to an HF alkylation reactor settler drum. Hydrogen

fluoride vapors were emitted under pressure for about two hours and the vessel was plugged and drained approximately 44 hours later.

An extensive analysis was conducted to determine the total inventory loss and to

model the blowdown process and the concentrations of HF in the plume. Since the discharge rate was decreasing with time, a peak concentration of HF in the

emitted vapors occurred just before the water spray mitigation system became fully operative. Consequently, the mitigation efforts were more effective

late in the response when concentrations were already low.”

3000 people evacuated from homes (52-block area)

1000 people treated



§  Catalyst consumption (H2SO4) is high §  Catalyst aftertreatment: spent acid contains tarry hydrocarbons and water §  Alkylate quality is lower from H2SO4 catalysts than HF §  HF is toxic and corrosive, safety hazards with handling and operation §  1960s-1986: HF plants >> H2SO4 plants §  1987: Marathon Texas City accidental HF release, (3000 evacuated, 1000 treated) §  Extensive mitigation systems required for HF §  New installations are not even commissioned for HF

§  Can solid acids be developed to avoid the use of liquid acids?

... a brief history





§  Solid acid catalysts for alkylation:

§  1960s: Rare earth-exchanged FAU zeolites (Mobil, Sun Oil)

§  1974: Pt incorporation into zeolites for regeneration (Union Carbide)

§  1970s (late): Solid acids and zeolites (J. Weitkamp)

§  Supported liquid acids (triflic acid) on porous solids (Haldor-Topsoe)

§  Sulfated zirconia, heteropolyacids, organic resins §  Some catalysts themselves also

exhibit environmental and health hazards

Alkylation catalysis: Main Challenges with Solid Acid Alkylation

§  Technical challenges with solid catalysts:

§  Catalyst lifetime (deactivation and fouling) §  Catalyst regeneration §  Loss in conversion + loss of selectivity to alkylate (and formation of oligomers)


!""# $% &'()*$+,-.+ /*0.%1234)"5 !"6# 7.%. 8$9:+4$ ;<4<12=. ,3$094<:.>094.:. <1?21<4,$: <3 7.11@ /+.4<,1.+ <;;$9:4 $: 4A. 3.<%;A 8$% 3$1,+ <1?21<4,$:;<4<12343 A<3 0..: B901,3A.+ %.;.:412 !"#@

!" #$%&'() *'$)+,'- .* &-./+)$(' $%01%$)&.( .(-.%&2 $3&2-

C: 4A. 1<4. "DEF3G H.,4?<*B +.I.1$B.+ 3B.;,<11<0$%<4$%2 4.;A:,J9.3 4<,1$%.+ 8$% < 4,*.)%.3$1I.+,:I.34,K<4,$: $8 ,3$094<:.><1?.:. <1?21<4,$: $: 3$1,+;<4<12343@ LA. *<,: 8.<49%.3 $8 4A.3. 4.;A:,J9.3 7.%.B%$+9;4 3<*B1,:K ,: 3A$%4 ,:4.%I<13 MNN,:34<:4<:.$93OO$% NN+,88.%.:4,<1OO 3<*B1,:KP ;$*0,:.+ 7,4A A,KA)%.3$)194,$: <:<123,3 $8 4A. ;$*B1.Q B%$+9;4 *,Q49%.3 02;<B,11<%2 K<3 ;A%$*<4$K%<BA2@ L2B,;<1 %.39143$04<,:.+ $: <: <;,+ 8$%* $8 =.$1,4. R <%. +.B,;4.+,: ',K@ 6@

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

Y9<1,4<4,I.12G 4A. 9:3<4,38<;4$%2 4,*.)$:)34%.<*0.A<I,$% 3A$7: ,: ',K@ 6 ,3 42B,;<1 8$% <11 3$1,+ <;,+33;%94,:,=.+ <3 ;<4<12343 8$% ,3$094<:. <1?21<4,$:G <:+4A,3 A<3 3$ 8<% B%.I.:4.+ 3$1,+ ;<4<12343 8%$* 0.,:K.*B1$2.+ ,: ;$**.%;,<1 ,3$094<:.>094.:. <1?21<4,$:B%$;.33.3@ LA.%. A<3G A$7.I.%G 0..: 3$*. B%$K%.33 ,:<:<12=,:K 4A. %.<3$:3 8$% 4A. B$$% 4,*.)$:)34%.<*0.A<I,$% $8 3$1,+ <1?21<4,$: ;<4<12343@ / 1,*,4.+ :9*)0.% $8 B%$;.33 +.I.1$B*.:43 A<I. .I.: 0..: +%,I.: 4,114A. B,1$4 B1<:4 34<K.@

4" 5,.3'-- 2'6'%.78'()- $) )9' 7&%.) 7%$() -)$:'

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

C4 ,3 ,:4.%.34,:K 4$ :$4,;. 4A<4 < 319%%2 %.<;4$% ,3.*B1$2.+ ,: <4 1.<34 $:. $8 4A. B%$;.33 +.I.1$B*.:431,34.+ ,: L<01. "@ / 319%%2 %.<;4$% B%$0<012 A.1B3 4$31$7 +$7: 4A. +.<;4,I<4,$: <:+ NN+.3.1.;4,I<4,$:OO $8

',K@ 6@ V$:I.%3,$: $8 < 1,J9,+ ,3$094<:.>")094.:. *,Q49%. $: <V.R)DW =.$1,4. ,: < 8,Q.+)0.+ %.<;4$% M(!WF!VG )!(" 0<%G 1,J9,+8..+ %<4.!E@5 ;*(>AG *<33 $8 ;<4<1234!"@_ KG !',3$094<:.! !'""094.:. !"" " "PG <84.% !"(`"5#@

*+ ,-"$.&/)0 1+ (%&& 2 3&$&45#"# (67&5 89 :;999< ;9=>;99 "D5

Alkylation catalysis: Main Challenges with Solid Acid Alkylation

§  Requirements for any solid acid (zeolite) catalyst:

§  At least as durable as liquid acids §  Low sensitivity to feedstock composition, impurities §  Higher quality (octane) alkylate than liquid acids (very evolved/optimized processes) §  (Regulation / legislation) away from liquid acids §  One Breakthrough: More than 1 paraffin activated per olefin (… or no olefins)


T. F. Degnan, Curr. Opin. In ChE 9 (2015) 75-82

§  Shell strategy (K. P. de Jong), 1990s:

§  Beta zeolite shows optimal shape selectivity §  Want lower Si/Al (higher concentrations of acid sites)

§  Gives higher alkylate quality, longer lifetime §  Novel synthesis techniques needed

§  No halogens or other additives

§  Albermarle strategy (AlkyStar®), 1990s-present

Alkylation catalysis: Main Challenges with Solid Acid Alkylation -1

-

AlkyClean!!!!

Solid Acid Alkylation

October 6, 2006

Development of a Solid Acid Catalyst Alkylation Process

http://crelon-web.eec.wustl.edu/files/CRELMEETINGS/2006/AlkyClean.pdf

§  1994: ABB Lummus (now CB&I) starts research effort to displace HF and H2SO4 using zeolite-catalyzed alkylation

§  1996: Akzo Nobel (now Albemarle) joins effort to develop catalyst

§  2001: Neste Oil joins venture to test this

§  2002: 10 BBL/day demonstration in Neste’s Porvoo refinery in Finland

§  ……

§  2013: Shandong Wonfull Petrochemical Group Ltd. (China) licenses this technology

§  2015: Zibo Haiyi Fine Chemical Co. (a subsidiary of Wonfull) constructs a unit (2700 BBL/day) and starts up §  RON: 96-98

T. F. Degnan, Focus on Catalysts, April 2016

gounder research laboratory: chemistry and catalysis of … · 2017. 5. 3. · gounder research...

Documents