PEP Review 2012-06

HIGH-PURITY ISOBUTYLENE PRODUCTION BY MTBE CRACKING

By
Sumod Kalakkunnath
(December 2012)

ABSTRACT
This Review presents a technoeconomic evaluation of an isobutylene from methyl tertiary
butyl ether (MTBE) production process based upon the technical information and data available in
patents assigned to Evonik Oxeno GmbH on the subject. The design presented herein may differ
from an exact construct of an actual commercial Evonik Oxeno process. However, we firmly
believe that the process design and economics presented herein are a reasonably accurate
representation of the actual process, and should be within the marginal boundary of errors.
The process primarily consists of vapor-phase cracking of MTBE-rich feed in a fixed-bed,
shell-and-tube-type reactor over a proprietary magnesium aluminosilicate catalyst doped with an
alkali metal oxide. The reaction is endothermic and reaction heat is supplied through the shell
side via heating medium. The Evonik Oxeno process is carried out preferably at about 568°F
(298°C) and 109–124 psia with a 98.3 wt% purity MTBE feedstock assumed to be available from
an adjacent MTBE synthesis plant (analyzed in PEP Review 2012-07). Optimal weight hourly
space velocity is equal to 1–3 hr-1. MTBE cracking is a reversible reaction with isobutylene
production favored at higher temperatures and lower pressures. The catalyst and reaction
conditions selected provide a 94% MTBE conversion to isobutylene with methanol being the
major by-product. Side reactions, including dehydration of methanol and dimerization of
isobutylene have been accounted for in the process design.
The cracking reaction is followed by a series of product purification steps, including
distillation towers, water wash column, and molecular sieve-based dehydration to achieve a 99.95
wt% isobutylene purity. The excess MTBE-methanol stream is recycled back to the MTBE
synthesis plant while the heavies and inerts are purged to avoid build up. Methanol tends to form
azeotropes with several of the feed components such as: C4/C5 hydrocarbons, MTBE, 2-methoxy
butane, and diisobutene, which complicates the separation procedure.
Our cost analysis is based on a plant producing 150,000 metric t/yr of high-purity isobutylene
(HPI) at a 0.9 stream factor (equal to an installed capacity of 167,000 metric t/yr). The required
installed capacity of an MTBE synthesis plant for the above isobutylene capacity is approximately
284,000 metric t/yr (at a 0.9 stream factor). Cost estimates, details thereof and relevant
assumptions are provided in this Review.
The economics of an integrated MTBE-isobutylene plant (i.e., MTBE synthesis-dissociation-
isobutylene production) are also provided (see Tables 9, 10, and 11).

© 2012 IHS PEP Review 2012-06

 A private report by the

Process Economics
Program
Review No. 2012-06

HIGH-PURITY ISOBUTYLENE PRODUCTION

BY MTBE CRACKING

by Sumod Kalakkunnath

December 2012

Santa Clara, California 95054

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 CONTENTS

REVIEW SUMMARY .................................................................................................. 1

INTRODUCTION ........................................................................................................ 4
COMMERCIAL OVERVIEW ....................................................................................... 4
TECHNOLOGY OVERVIEW ...................................................................................... 5
Technical Review ....................................................................................................... 6
Reactors and Reaction System .................................................................................. 6
Catalyst and Catalyst Support .................................................................................... 6
Catalyst Life ................................................................................................................ 7
Process Description.................................................................................................... 8
Section 100—Isobutylene Production Section ........................................................... 9
PROCESS DISCUSSION........................................................................................... 15
Feedstock ................................................................................................................... 15
Catalyst System .......................................................................................................... 15
MTBE Cracking Reactor ............................................................................................. 15
Product Recovery ....................................................................................................... 16
By-Product Recovery.................................................................................................. 16
Process Waste Effluents ............................................................................................ 16
Materials of Construction ............................................................................................ 16
Process Design Optimization ..................................................................................... 17
COST ESTIMATES .................................................................................................... 21
Fixed-Capital Costs .................................................................................................... 21
Production Costs ........................................................................................................ 21
Integrated Plant Economics........................................................................................ 22
REFERENCES ........................................................................................................... 31

© 2012 IHS iii PEP Review 2012-06

 FIGURES

1 High-Purity Isobutylene Production by MTBE Cracking

Process Flow Diagram .......................................................................................... 33
2 High-Purity Isobutylene Production by MTBE Cracking
Net Production Cost and Product Value of Isobutylene as a Function of MTBE
Price (for Base-Capacity Plant) ............................................................................. 3
3 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Net Production Cost and Product Value of Isobutylene as a Function of C4
Stream (Raffinate-1) Price (for Base-Capacity Plant) ........................................... 3
4 High-Purity Isobutylene Production by MTBE Cracking
Net Production Cost and Product Value of Isobutylene as a Function of MTBE
Price (for Base-Capacity Plant) ............................................................................. 29
5 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Net Production Cost and Product Value of Isobutylene as a Function of C4
Stream (Raffinate-1) Price (for Base-Capacity Plant) ........................................... 29
6 High-Purity Isobutylene Production by MTBE Cracking
Product Value of Isobutylene as a Function of Plant Operating Level and Plant
Capacity ................................................................................................................. 30
7 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Product Value of Isobutylene as a Function of Plant Operating Level and Plant
Capacity ................................................................................................................. 30

© 2012 IHS iv PEP Review 2012-06

 TABLES

1 Comparison of Process Economics ...................................................................... 2

2 MTBE Cracking Process Comparison ................................................................... 8
3 High-Purity Isobutylene Production by MTBE Cracking
Design Bases......................................................................................................... 12
4 High-Purity Isobutylene Production by MTBE Cracking
Stream Flows ......................................................................................................... 13
5 High-Purity Isobutylene Production by MTBE Cracking
Major Equipment ................................................................................................... 18
6 High-Purity Isobutylene Production by MTBE Cracking
Utilities Summary ................................................................................................... 20
7 High-Purity Isobutylene Production by MTBE Cracking
Total Capital Investment ........................................................................................ 23
8 High-Purity Isobutylene Production by MTBE Cracking
Production Costs ................................................................................................... 24
9 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Utilities Summary ................................................................................................... 26
10 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Total Capital Investment ........................................................................................ 27
11 High-Purity Isobutylene Production from Steam Cracker C4 Stream
Production Costs ................................................................................................... 28

© 2012 IHS v PEP Review 2012-06