TOS, hr

Alk

ylat

eY

ield

,%

0 2 4 6 8 100

10

20

30

40

50

Egg ShellEgg WhiteEgg Yolk

Bronsted Site Distribution

TOS, hr

Alk

ylat

eY

ield

,%

0 3 6 9 12 150

15

30

45

60

75

P/ O = 5P/ O = 10P/ O = 20

TOS, hr

Alk

ylat

eY

ield

,%

0 2 4 6 8 100

10

20

30

40

50

60

70

410.25

22

24 /

TOS, hr

Alk

ylat

eY

ield

,%

0 9 18 27 36 450

10

20

30

40

50

Predicted YieldExperimental Yield

TOS, hr

Con

vers

ion,

%

0 9 18 27 36 450

20

40

60

80

100

Predicted ConversionExperimental Conversion

Table 1: Input parameters for model simulations

OSV 1, kg/ kgcat-hr Feed P/ O ratio 5 Si/ Al ratioa 15

catR 3 x 10-4, m

cat a 937, m3/ kgcat

liq a 450, m3/ kg

s b 1

cat 0.48

cat 2 2

1 900 22 12 23 1 24 46 25 2 26 2

a de Jong et al. (1996); b Sarsani (2007)

TOS, hr

Dim

ensi

onle

ssC

once

ntra

tion

0 2 4 6 8 100

0.035

0.07

0.105

0.14

0.175

n-buteneisooctanesisooctenes

C12H24S – C20H40S

C4H8 + S C4H8S

+ C4H8

C8H16S + i-C4H10

C8H18 Isomerized C8H18

TMP 100 RON

DMH 71 RON

+ nC4H8 + i-C4H10

C12H26 – C20H42 C5H12 – C7H14

60 – 93 RON

Cracked Products

Low Temperature

Minor

Minor

Minor

Low

Isobutane/ Olefin Ratio

High

90 RON

Contact Time Low High

High

Modeling of Key Reaction Pathways; Zeolite Catalyzed Alkylation Processes Subramanya V. Nayak, Palghat A. Ramachandran, Milorad P. Dudukovic Chemical Reaction Engineering Laboratory (CREL), Center for Environmentally Beneficial Catalysis (CEBC)

Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis

Solid acids (Zeolites) are heterogeneous catalysts that can replace conventional

liquid catalysts like HF and H2SO4

Examples: Butane to Octane (LPG to Gasoline) Synthetic Detergent (Linear alkyl benzene)Advantages: Non-corrosive and environmentally friendly Simple separation and recoveryChallenge:

Develop and demonstrate an environmentally friendly and competitive Solid Acid Catalyst (SAC) technology to conventional technologies

Introduction

Alkylation processes catalyzed by zeolites

Brønsted acid sites in a zeolite

Simplified alkylation mechanism (Roeseler, 2004)

ObjectiveTo model the key reaction pathways affecting the

performance of zeolite catalyzed alkylation of isobutane and n-butene.

Six lump Kinetic ModelModel assumptions:1.Protonation and addition of lighter olefins on the zeolite Brønsted acid site to form isooctenes can be treated as effectively the same reaction step.2.Hydride transfers between different isomers of isooctenes and isobutane and the direct alkylation between different lighter olefins and isobutane can be treated as effectively the same reaction step.3.C5 to C7 hydrocarbons formed by alkylation reactions are ignored.4.Alkylates formed are considered to collectively represent all the isomers of isooctanes.5.Once C12 carbocation is formed, the Brønsted acid site is irreversibly blocked, causing zeolite deactivation .6.Highly branched paraffinic hydrocarbons formed by addition of isooctanes and olefins causes further decrease in catalyst activity.7.Dimers formed by isomerization of isooctenes, irreversibly adsorb to the Brønsted acid site to further decrease the zeolite activity. 8.Cracking of the heavier hydrocarbon is ignored as it is not prevalent under alkylation conditions.

Key Reaction Pathways

SHCSHCHC k 16884841

SHCSHCHC k 188841043

SHCSHCHC k241284168

4

SHCSHCHC k261284188

5

SHCSHC k168168

6

SHCHCSHCHC k 841881041682

Alkylation Reactions

Deactivation Reactions

Transient Reactor and Zeolite Particle Models

E-1as Framework of Beta ZeoliteSi/ Al = 15

CSTR Zeolite Particle

Crystal

Remarks:• Transient reactor model considers residence time distribution.• Transient zeolite particle model considers reaction, diffusion and deactivation. • Reactor model and zeolite particle model are coupled using film transport.• Detail model equations and solution procedure is explained elsewhere (Nayak et al., 2008).

Results and Discussions

Protonation & Addition

Hydride Transfer

Direct Alkylation

Oligomerization

Alkylation

Isomerization

H

OSi Al+

Base Case

Predicted dimensionless concentration of n-butene, isooctane and isooctenes as a function of

TOS for the base case simulation (refer to Table 1 for input parameters).

Remarks:• It is observed that ultimately complete n-butene breakthrough is reached with TOS, due to complete deactivation of the zeolite catalyst.

Validation of kinetic and reactor models

Comparison of TOS dependent olefin conversion predicted by the model and that observed under experimental conditions

(OSV = 0.11 kg/ kgcat-hr, P/ O = 5;Sarsani, 2007).

Remarks: The steep decrease in olefin conversion predicted by model is because of following:• It is assumed that once C12 carbocation is formed the Brønsted acid site is irreversibly blocked, causing zeolite catalyst deactivation. However under experimental conditions it seems that the C12 carbocation further oligomerizes with butene, causing the slower decline of olefin conversion with TOS observed in the experimental data.

..............87843416842412 kk HCSHCHCSHC

• The beta zeolite used in the experiment contains both Brønsted and Lewis acid sites (Sarsani, 2007). Lewis acid sites do not catalyze the alkylation reaction, but the presence of strong Lewis acid sites promotes the formation of unsaturated compounds by butene reactions.• The model did not account for the additional reactions promoted by the catalyst that did not lead to the desired product as these reactions should be suppressed on the well designed catalyst.

Remarks:• Good agreement of model predictions with the experimental data is not obtained, with less than 5 % absolute error between predicted yield and experimental data.•This can be taken as proof that the model indeed captured the key reactions responsible for the production of alkylate and for the catalyst deactivation.•The slow drop in the alkylate yield is caused by intraparticle diffusion limitation in the zeolite pores.

Comparison of TOS dependent alkylate yield predicted by the model and that observed under

experimental conditions. (OSV = 0.11 kg/ kgcat-hr, P/ O = 5; Sarsani, 2007)

Influence of Design and Operating Parameters Hydride Transfer and Oligomerization

Remarks:• The hydride transfer step between isooctenes and isobutane is sterically more hindered than olefin oligomerization.• Steric effect can be mitigated to a certain extent by attaching the acid group to a tether and extending it away from the support surface.• By adding an efficient hydride donor to the zeolite, the intrinsic rate of hydride transfer can be increased.

Simulated alkylate yield as a function of TOS for various values of 2

224 /

Isobutane/ n-butene ratio (P/ O)Remarks:• A high feed P/ O ratio is beneficial for performance of zeolite catalyzed alkylation processes.• To maintain a high P/ O ratio in the reactor bulk, a back mixed reactor (slurry reactor) is more beneficial than a plug flow reactor (packed bed reactor). • However with an increase in P/ O ratio, the cost associated with separation and recycling the unreacted isobutane also increases.

Simulated alkylate yield as a function of TOS for various P/ O ratios

Optimal Brønsted Acid Site Distribution

Egg Shell Egg White Egg Yolk

Remarks:• In egg shell type of distribution, butene diffuses through a finite intraparticle space to reach the Brønsted acid sites. As a result, the P/ O ratio in the intraparticle space is much higher than in the bulk.• Alkylates formed in this thin shell can easily diffuse out to the bulk.

Simulated alkylate yield as a function of TOS for different types of Brønsted acid site distributions

Silicon/ Alumina RatioRemarks:• The decrease in Si/ Al ratio increases the initial Brønsted acid site concentration. As a result, the alkylate yield and zeolite catalyst life increase with a decrease in the Si/ Al ratio.

Summary1. Hydride transfer between isooctenes and isobutane and

oligomerization of isooctenes with olefins are the key reactions affecting the overall performance of zeolite catalyzed alkylation processes.

2. A slow rate of hydride transfer compared to oligomerization is the major cause of the low alkylates yield and shorter zeolite activity with time on stream (TOS).

3. To further enhance the science of zeolite catalyzed alkylation processes, we need to examine the consequences of zeolite morphology on the diffusion and reaction pathways of the organic molecules.

References:• de Jong, K.P., Mesters, C.M.A.M., Peferoen, D.G.R., van Brugge, P.T.M. and de Groote, C., (1996). Paraffin alkylation using zeolitie catalysts in a slurry reactor: Chemical engineering principles to extend catalyst lifetime. Chem. Eng. Sci. 51, 2053.• Nayak S.V., Ramachandran P. A., Dudukovic M. P., (2008) “Modeling of Key Reaction Pathways; Zeolite Catalyzed Alkylation Processes” submitted Chem. Eng. Sci. • Roeseler, C., (2004). UOP Alkylene™ Process for motor fuel alkylation. 3rd ed., Handbook of Petroleum Refining Processes, • Sarsani, V.S.R., (2007). Solid acid catalysis in liquid, gas-expanded liquid and near critical reaction media: Investigation of isobutane/ butene alkylation and aromatic acylation reactions. Ph D. Dissertation, University of Kansas.

Acknowledgements:This work is made possible by the support of the National Science Foundation (Grant EEC-0310689) and the Center for Environmentally Beneficial Catalysis (CEBC). Fruitful discussions with R.C. Ramaswamy, CREL, and S. Sarsani, U of Kansas were most appreciated.