Aromatics Upgrading Technologies: Ihs Chemical

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IHS CHEMICAL
Aromatics Upgrading Technologies

Process Economics Program Report 25E
December 2016 ihs.com
PEP Report 25E

Aromatics Upgrading
Technologies
Rajesh Kumar Verma

Principal Analyst
Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC (Ellen.Blue@ihsmarkit.com)
IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies
PEP Report 25E

Aromatics Upgrading Technologies
Rajesh Kumar Verma, Principal Analyst
Abstract
Transalkylation, disproportionation, alkylation, and dealkylation are the most widely used processes in a
refinery complex for C7, C9, C10 aromatics upgrading, and xylene isomerization is used to increase the para-
xylene content of streams from low to high. Many licensors and technology developers provide process
technologies and proprietary catalysts for these processes, each with advantages and disadvantages over
other technologies. In this report, the technological advancements and production economics are updated
for the following three processes:
The UOP Tatoray process for upgrading toluene, C9, and C10 aromatics, by catalytic disproportionation
and transalkylation, to a commercial grade mix of xylene product (>98 wt% C8 content) and high-purity
benzene by-product (>99.9 wt% purity)
The UOP isomerization process for isomerizing xylenes in a para-xylene-lean stream to provide a para-
xylene-rich stream, by converting meta- and ortho-xylenes to an equilibrium mixture of xylenes, with
ethylbenzene either dealkylated to benzene or isomerized to xylenes.
The CB&I Detol process for converting a toluene-rich stream to high-purity benzene product.
This report also provides an industry review of p-xylene and benzene, including the market shares of various
licensors for the selected processes, process PFDs, patent summaries, and an upfront Summary section.
For the process analyses, we evaluate and discuss patent and other non-proprietary information, particularly
to extract key process conditions and parameters necessary to forming the design basis for each process.
An Aspen simulation model is developed and engineering judgement is applied to define the detailed
material and energy balances. Plant construction costs (CAPEX), including ISBL and OSBL costs, are
estimated for each processes by individual equipment sizing and costing with the aid of IHSs proprietary
software PEPCOST. Operating costs are calculated based on unit consumption of raw materials, utilities,
and direct costs as well as depreciation and return on investment.
Production economics presented in the report are based on cost data for the US Gulf Coast (USGC) region.
However, an Excel-based data module iPEP NavigatorAromaticsUpgrading is included as an attachment to
the electronic report, to allow our clients to convert the economics of the discussed upgrading processes to
the corresponding economics in five other regions (Canada, China, Germany, Japan, and the Middle East).
2016 IHS 1 December 2016
Contents
1 Introduction 10
2 Summary 13
Commercial aspects 13
Benzene 14
Xylenes 14
C7A and C9A upgrading to benzene and xylene 16
Process economics summary 16
UOPs transalkylation process 17
UOPs xylene isomerization process 18
CB&Is Detol process 18
Process summary 18
3 Industry status 20
Specifications of major streams in an aromatics complex 20
Naphtha reformate 20
Mixed xylenes 21
Benzene 22
para-Xylene 23
Supply and demand 24
Mixed xylenes 24
Benzene 26
Toluene 27
Toluene disproportionation and hydrodealkylation 27
List of producers and plant capacities 29
Price trends for feedstock and products 36
4 Technology review 38
Feedstock and products 38
Aromatics complex unit configurations 39
Aromatics complex process description 42
Benzene and toluene recovery unit 43
Toluene column 44
Xylene, ortho-xylene, and heavy aromatics columns 44
p-Xylene recovery unit 45
Xylene isomerization unit 48
Aromatics upgrading to xylene and benzene 50
Overview 50
Catalytic hydrodealkylation of toluene 50
Thermal hydrodealkylation of toluene 50
Toluene disproportionation and transalkylation of C7 and C9 aromatics 51
Selective toluene disproportionation 52
Toluene methylation 52
Transalkylation process 53
Chemistry 53
Alkylation 57
Hydrocracking 58
IHS CHEMICAL
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No portion of this report may be reproduced, reused, or otherwise distributed in any form without prior written consent, with the exception of any internal client distribution
as may be permitted in the license agreement between client and IHS. Content reproduced or redistributed with IHS permission must display IHS legal notices and
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incurred by reliance on information or any statement contained herein. In particular, please note that no representation or warranty is given as to the achievement or
reasonableness
2016 IHS of, and no reliance should be placed on, any projections, forecasts, estimates, or assumptions, and,2due to various risks and uncertainties, actual events December 2016
and results may differ materially from forecasts and statements of belief noted herein. This report is not to be construed as legal or financial advice, and use of or reliance
on any information in this publication is entirely at clients own risk. IHS and the IHS logo are trademarks of IHS.
Isomerization 58
Ring saturation 59
Coking 59
Process variables 59
Temperature and pressure dependency 59
Feed quality 60
Reaction severity 61
Temperature 61
H2 partial pressure 62
Space velocity 62
Methyl/phenyl or methyl/ring ratio in the feed 62
Process development 63
Major commercial processes 66
ExxonMobils TransPlusSM process 66
ExxonMobils toluene disproportionation process MTDP-3SM 67
UOP TAC9 process 68
GTC-Transalkylation process (GTC-TransAlkSM) 68
Catalyst development 69
Summary of technology development 76
Xylene isomerization 77
Chemistry 78
Xylene isomerization 78
Ethylbenzene conversion 79
Side reactions 79
Temperature 79
H2 partial pressure and reactor pressure 80
H2/HC ratio 80
Reaction severity 80
Space velocity 80
Process and catalyst development 80
Liquid phase xylene isomerization 81
Vapor phase xylene isomerization 81
Vapor phase isomerization without a hydrogen atmosphere 81
Vapor phase isomerization with a hydrogen atmosphere 81
Major commercial processes 86
ExxonMobils XyMaxSM process 86
Axens-Engelhard Octafining process 88
GTC GT-IsomPXSM technology 88
JSC SIE Neftehim process 89
Toluene hydrodealkylation 90
Catalytic hydrodealkylation versus thermal hydrodealkylation 91
Chemistry 91
Side reactions 92
Feed composition 94
Temperature 94
Pressure 95
Toluene conversion 95
H2/HC ratio 95
Process and catalyst development 95

5 UOPs transalkylation process 99
Scope 99
Process description 109
Feed 109
Reaction 110
Product fractionation 110
Process discussion 111
Process scheme 111
Catalyst 111
Feed composition 112
Reactor 112
Recycle gas compressor 112
Make-up H2 112
Cost estimates 112
Fixed capital costs 113
Production costs 113
Economic discussion 113
6 UOPs xylene isomerization process 119
Scope 119
Feed section 126
Reaction section 127
Product fractionation section 127
Process scheme 128
Catalyst 128
Reactor 128
Make-up H2 129
Cost estimates 129
7 CB&Is Detol process 136
Scope 136
Feed section 144
Reaction section 145
Product fractionation section 146
Catalyst 147
Reactor 147
Make-up H2 147
Cost estimates 147
Appendix APatent summaries 153
Appendix BDesign and cost basis 181

Design conditions 182
Cost basis 182
Capital investment 182
Effect of operating level on production costs 184
Appendix CCited references 185
Appendix DPatent references by company 195
Appendix EProcess flow diagrams 199
Tables
Table 2.1 Economics summary for the studied processes 17
Table 2.2 Process summary for the studied processes 19
Table 3.1 Major properties and composition of naphtha reformate 21
Table 3.2 Major specifications for mixed xylenes product 22
Table 3.3 Major specifications for benzene product 23
Table 3.4 Major specifications for p-xylene product 24
Table 3.5 World supply and demand for mixed xylene by region 25
Table 3.6 World supply and demand for individual C8 products by region in 2015 (ktpy) 25
Table 3.7 Consumption of xylene isomers by end use for 2015 (ktpy) 26
Table 3.8 World supply and demand for benzene by region in 2014 (ktpy) 26
Table 3.9 World supply and demand for toluene by region in 2015 (ktpy) 27
Table 3.10 Current and forecasted world production of benzene and xylene using different
processes by region 28
Table 3.11 World mixed xylene production capacity of transalkylation/disproportionation
processes 29
Table 3.12 World benzene production by transalkylation/disproportionation/HDA processes 32
Table 4.1 Freezing points for xylene isomers and related compounds in the C6C9 range 47
Table 4.2 Reaction controlling functions in transalkylation and disproportionation chemistries 59
Table 4.3 Me/Ph ratios of transalkylation reaction mixture components 62
Table 4.4 Disproportionation of C7C11 methylbenzenes over an aluminosilicate catalyst (US
3350469) 70
Table 4.5 Results of C7C11 methylaromatics disproportionation over an aluminosilicate catalyst
containing Re, Sn, and Ge (EP 1882728) 73
Table 4.6 Results of C7C11 methylaromatics disproportionation over an aluminosilicate catalyst
containing Re, Sn, and Ge as a function of temperature (EP 1882728) 74
Table 4.7 Operating conditions for commercialized transalkylation processes 77
Table 4.8 Major operating conditions for some commercialized xylene isomerization processes 90
Table 5.1 Design basis for the transalkylation process 100
Table 5.2 Toluene and C9 aromatics upgrading to benzene and xylene by UOPs Tatoray
processMajor streams flows 101
processMajor equipment 107
processUtilities summary 109
processTotal capital investment 115
processProduction costs 116
Table 6.1 Design basis for the xylene isomerization process 120
Table 6.2 UOPs xylene isomerization process for upgrading p-xylene-lean feed to a p-xylene-rich
streamMajor streams flows 121
streamMajor equipment 125
streamUtilities summary 126
Table 6.5 UOPs xylene isomerization process for p-xylene-lean feed upgrading to p-xylene-rich
streamTotal capital investment 132
Table 6.6 UOPs xylene isomerization process for p-xylene-lean feed upgrading to p-xylene-rich
streamProduction costs 133
Table 7.1 Design basis for the toluene hydrodealkylation process 137
Table 7.2 CB&Is Detol process for upgrading toluene to benzeneMajor streams flows 138
Table 7.3 CB&Is Detol process for upgrading toluene to benzeneMajor equipment 143
Table 7.4 CB&Is Detol process for upgrading toluene to benzeneUtilities summary 144
Table 7.5 CB&Is Detol process for upgrading toluene to benzeneTotal capital investment 149
Table 7.6 CB&Is Detol process for upgrading toluene to benzeneProduction costs 150
Figures
Figure 1.1 Simplified block flow diagram of an aromatics complex simulated to derive the xylene
isomerization and transalkylation unit's feed 12
Figure 2.1 World consumption of benzene by end use in 2014 14
Figure 2.2 World producers of mixed xylenes by region in 2015 15
Figure 3.1 Price trends for aromatics 37
Figure 4.1 Typical aromatics complex with a simple configuration 40
Figure 4.2 Typical aromatics complex with a complex configuration 41
Figure 4.3 Product slate flexibility for benzene and p-xylene 42
Figure 4.4 Typical bock diagram for BTX recovery unit 43
Figure 4.5 Block flow diagram of a typical p-xylene recovery unit (adsorption process) 46
Figure 4.6 Block flow diagram of a typical p-xylene recovery unit (crystallization process) 48
Figure 4.7 Block diagram of a typical xylene isomerization unit (UOP design) 50
Figure 4.8 Block flow diagram of a typical hydrodealkylation unit 51
Figure 4.9 Block flow diagram of a typical thermal hydrodealkylation unit (UOP design) 52
Figure 4.10 Block flow diagram of a typical toluene methylation process (GTC process) 53
Figure 4.11 Effect of C9 aromatics on overall product yield 61
Figure 4.12 Dependency of product selectivity on methyl/phenyl ratio in feed for transalkylation at
equilibrium at 427C 63
Figure 4.13 Two stage transalkylation process (US 6958425) 64
Figure 4.14 Transalkylation run results with and without a catalyst guard bed (US 7154014) 65
Figure 4.15 Effect of temperature on toluene conversion (US 6383967) 71
Figure 4.16 Effect of toluene conversion on para-xylene selectivity (US 6383967) 71
Figure 4.17 Effect of catalyst pretreatment on activity (US 7273828) 74
Figure 4.18 Effect of catalyst pretreatment on light ends yield (US 7273828) 75
Figure 4.19 Effect of C9A in feed on product yield (BE 716016) 76
Figure 4.20 Integrated aromatics complex, including naphtha hydrotreating unit, reformer, xylene
fractionation, transalkylation, xylene isomerization, ED unit, and p-xylene recovery
unit (US 7405335) 82
Figure 4.21 Effect of EB conversion on p-xylene equilibrium conversion (US 20080146859, US
20100125160) 85
Figure 4.22 Effect of system pressure on xylene loss (US 20080146859, US 20100125160) 86
Figure 4.23 ExxonMobils dual-bed xylene isomerization process configuration 87
Figure 4.24 Overall heat of reaction for hydrodealkylation 93
Figure 4.25 Effect of temperature on the major reactions in hydrodealkylation processes 94

Figure 4.26 Effect of Pt and Mo contents in hydrodealkylation catalyst on overall feed conversion
and BTE selectivity (WO 2008015027) 97
Figure 5.1 Effect of plant capacity on investment costs 118
Figure 5.2 Net production cost of mixed xyleness product as a function of operating level and
plant capacity 118
Figure 6.2 Net production cost of deheptanizer bottoms product as a function of operating level
and plant capacity 135
Figure 7.2 Net production cost of benzene product as a function of operating level and plant
capacity 152
Figure 8.1 C7A and C9A to xylene by UOPs Tatoray process (1 of 2) 200
Figure 8.1 C7A and C9A to xylene by UOPs Tatoray process (2 of 2) 201
Figure 8.2 UOPs xylene isomerization process 202
Figure 8.3 Toluene to benzene by CB&Is Detol process (1 of 2) 203
Figure 8.3 Toluene to benzene by CB&Is Detol process (2 of 2) 204
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Aromatics Upgrading Technologies

December 2016 ihs.com

PEP Report 25E

Rajesh Kumar Verma

PEP Report 25E

2016 IHS 1 December 2016

2016 IHS 3 December 2016

Summary of technology development 98

2016 IHS 4 December 2016

Appendix BDesign and cost basis 181

2016 IHS 5 December 2016

2016 IHS 6 December 2016

Figure 4.25 Effect of temperature on the major reactions in hydrodealkylation processes 94

2016 IHS 7 December 2016

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