Professional Documents
Culture Documents
Benzene/Toluene
06/07-6
July 2007
This Report was prepared by Nexant, Inc. (“Nexant”) and is part of ChemSystems Process Evaluation/Research Planning
(PERP) Program. Except where specifically stated otherwise in this Report, the information contained herein is prepared on the
basis of information that is publicly available, and contains no confidential third party technical information to the best
knowledge of Nexant. The aforesaid information has not been independently verified or otherwise examined to determine its
accuracy, completeness, or feasibility.
Neither Nexant, Subscriber, nor any person acting on behalf of either assumes any liabilities with respect to the use of, or for
damages resulting from the use of, any information contained in this Report. Nexant does not represent or warrant that any
assumed conditions will come to pass.
The Report is submitted on the understanding that the Subscriber will maintain the contents confidential except for the
Subscriber’s internal use. The Report shall not be reproduced, distributed, or used outside Subscriber’s organization without
first obtaining prior written consent by Nexant. Each Subscriber agrees to use reasonable effort to protect the confidential nature
of the Report.
Contents
Section Page
Benzene/Toluene i
PERP 06/07-6
Q207_00101.0007.4106
Contents
2.4.1 Introduction........................................................................................ 37
2.4.2 BTX Extraction Processes ................................................................. 39
2.4.3 Single Aromatics Extraction Processes ............................................. 45
2.5 DEALKYLATION PROCESSES ................................................................. 48
2.5.1 Introduction........................................................................................ 48
2.5.2 Hydrodealkyation............................................................................... 48
2.5.3 Toluene Disproportionation ............................................................... 54
2.6 PRODUCTION FROM COKE OVEN LIGHT OIL..................................... 57
2.7 PRODUCTION OF AROMATICS VIA NONCONVENTIONAL ROUTES 58
2.7.1 Asahi Chemicals’ Alpha Process ....................................................... 58
2.7.2 BP/UOP’s Cyclar™ Process ............................................................... 59
2.7.3 CP Chem’s Aromax® Process............................................................ 64
™
2.7.4 UOP’s RZ Platforming .................................................................... 66
2.7.5 Summary of Non-conventional Routes.............................................. 68
3 Developing Technologies ......................................................................................... 70
3.1 METHANOL TO AROMATICS .................................................................. 70
3.2 METHANE TO BENZENE .......................................................................... 71
3.3 PATENTS OF INTEREST ............................................................................ 72
3.3.1 Axens (IFP) and SK Corporation....................................................... 72
3.3.2 Chevron Phillips Chemical Company (CPChem).............................. 75
3.3.3 China Petroleum and Chemical Corporation (CPCC) & Sinopec ..... 76
3.3.4 ExxonMobil ....................................................................................... 77
3.3.5 Fina Technology Inc. ......................................................................... 78
3.3.6 Institut Francais DuPetrole (IFP) ....................................................... 78
3.3.7 SABIC................................................................................................ 79
3.3.8 UOP.................................................................................................... 79
4 Economic Analysis ................................................................................................... 80
4.1 BASIS ............................................................................................................ 80
4.1.1 Pricing Basis ...................................................................................... 80
4.1.2 Investment Basis ................................................................................ 81
4.1.3 Cost of Production Basis.................................................................... 81
Benzene/Toluene ii
PERP 06/07-6
Q207_00101.0007.4106
Contents
Appendix Page
Benzene/Toluene iii
PERP 06/07-6
Q207_00101.0007.4106
Contents
Figure Page
Benzene/Toluene iv
PERP 06/07-6
Q207_00101.0007.4106
Contents
Table Page
Benzene/Toluene v
PERP 06/07-6
Q207_00101.0007.4106
Contents
Benzene/Toluene vi
PERP 06/07-6
Q207_00101.0007.4106
Contents
Benzene/Toluene vii
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
1.1 INTRODUCTION
Aromatics are produced as coproducts in refinery catalytic reformers, olefins plants, coal tar
processing, and toluene disproportionation (TDP) units. In addition, on-purpose supplies of
benzene are produced via toluene hydrodealkylation (THDA) units. THDA units are the swing
source and used when benzene supply is tight and prices get high enough to justify the
economics of those plants.
About 70 percent of the global production of benzene is by extraction from either reformate or
pyrolysis gasoline (pygas). Reformate is formed in the catalytic reforming of naphtha, a
technology primarily directed at the production of high octane gasoline components. Pygas is a
liquid byproduct formed in the production of olefins by steam cracking liquid feeds, such as
naphtha or gas oil. Ethylene plants typically operate near full capacity, but the feedstock slate
may vary depending on market conditions. Extraction from reformate and pygas are the most
economical sources of benzene.
The composition of BTX (benzene, toluene and xylenes) depends on the source. Table 1.1
compares BTX from pygas and reformate. Pygas is typically rich in benzene, whereas xylenes
and toluene are the main components of reformate.
Table 1.1
Typical BTX Composition from Pygas and Reformate
(Weight Percent)
Typical
Demand
Pygas¹ Reformate Split
Standard Medium
Severity Severity CCR² SR³
BTX content 58 42 51 42
Benzene 48 44 17 14 49
Toluene 33 31 39 39 23
Xylenes 19 25 44 47 28
Table 1.1 also very roughly shows the global demand for BTX products. In general, benzene is
present in the main feedstocks in proportions lower than market demand, whereas toluene is in
considerable excess, as are xylenes. To some extent this imbalance is corrected by their relative
values as gasoline components because refiners have the option of extracting BTX as chemical
Benzene/Toluene 1
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
products or blending them in fuel. Xylenes and toluene are more valuable as blendstocks than
benzene, and the benzene content in gasoline is restricted for environmental reasons.
1.2.1 Conventional
Essentially all of the benzene, toluene and mixed xylenes (BTX) recovered in an oil refinery is
produced in the catalytic reforming unit (both continuous catalytic regenerative (CCR) and semi-
regenerative (SR) types). In a refinery which is not integrated into petrochemical production, the
reformate product, or C5+ stream, containing benzene and heavier aromatics, is utilized as a high
octane gasoline blendstock. In recent years, the utilization of benzene in the U.S. gasoline pool
has decreased as a result of the limits placed on benzene content in gasoline by environmental
regulations. Many U.S. refineries that are not integrated with aromatics production remove the
benzene precursors upstream of the reforming unit, which minimizes benzene levels in
reformate. The benzene precursors are typically utilized as isomerization unit feedstock for
incorporation into the gasoline pool. Conversely, refineries that are integrated with aromatics
production maximize the production of benzene in the reformer unit.
Benzene production can vary based on reformer operating rates and seasonal demand for
gasoline, feedstock slate and severity of the operations. Production from this source is expected
to grow tracking gasoline consumption growth. The only difference in operations for aromatics
production and motor fuel production is in the choice of operating parameters (especially
feedstock selection) to maximize the yields of BTX.
Benzene/Toluene 2
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
The reaction kinetics are such that naphthene dehydrogenation is the fastest and paraffin
dehydrocyclization is the slowest. While operating within these boundaries hydrocracking of
paraffins and naphthenes also occurs. However, for a given catalyst, lower operating pressures
will deemphasize hydrocracking, and thus make it possible to achieve better yields.
The maximum potential yields of aromatics that could be obtained from naphthenes and
paraffins if hydrocracking could be suppressed are determined by the thermodynamic equilibria
for aromatization reactions. These data show, first, that corresponding aromatic yields from the
various classes of compounds follow the order (from highest to lowest) alkylcyclohexanes,
alkylcyclopentanes, paraffins. Second, aromatic yields increase with the number of carbon
atoms per molecule; benzene from C6 paraffin has a lower yield than toluene from C7 paraffin.
Third, for a given reactant, the potential aromatics yield increases as the hydrogen partial
pressure is decreased.
As the catalyst ages, it is necessary to change the process operating conditions to maintain the
reaction severity and to suppress undesired reactions. The basic relationships are shown in
Table 1.2.
Table 1.2
Basic Relationships in Catalytic Reforming
Naphthene
Reaction Hydrocracking Isomerization Dehydrocyclization Isomerization Dehydrogenation
Reaction rate Slowest Rapid Slow Rapid Fastest
Heat effect Exothermic Mildly Mildly Mildly Quite
Exothermic Endothermic Exothermic Endothermic
Effect of:
High pressure Aids None Hinders None Hinders
High temperature Aids Aids Aids Aids Aids
High space velocity Hinders Hinders Hinders Hinders Hinders
Effect on:
Hydrogen production Absorb None Evolves None Evolves
RVP Increase Increase Decrease Decrease Decrease
Density Decrease Decrease Increase Increase Increase
Volume yield Varies Increase Decrease Increase Decrease
Octane Increase Increase Increase Decrease Increase
Benzene/Toluene 3
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
Asahi Chemical’s Alpha Process, which has been operating at the company’s Mizushima
complex in Okayama, Japan, since 1993, employing an olefinic feed (licensed by Stone
& Webster).
The first commercial operation of BP/UOP’s CyclarTM Process was in 1999 at Saudi
Basic Industries Corporation (SABIC).
UOP’s RZ PlatformingTM process started up its first commercial unit in the second
quarter of 1998.
Each of the technologies is described briefly in the report that follows. The BTX distribution for
each of the non-conventional routes is compared with a conventional CCR reformate
(RON=102) distribution in Figure 1.1. As can be seen in the figure, benzene production from the
Aromax® process is significantly more than from the Alpha process (i.e. 65 percent versus 30
percent). The benzene production from the CyclarTM and RZ PlatformingTM processes is similar
and lower than these two processes. The CCR route produces the least amount of benzene at the
suggested conversion.
Figure 1.1
Aromatics Distribution in Non-Conventional Routes
100%
80%
60%
40%
20%
0%
CCR CYCLAR RZ AROMAX ALPHA
PLATFORMING
Benzene Toluene Mixed Xylenes C9+ Aromatics
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene 4
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
Pygas also contains significant quantities of diolefinic materials, which tend to form gum on
standing for any period of time, even at ambient conditions. These diolefinic materials are
removed (by reaction to olefins and paraffins) by a first stage hydrotreatment, which for this
analysis is assumed to be included in the olefins unit itself. A second stage of hydrotreatment is
necessary before the pygas is suitable for aromatics extraction; the costs of this downstream
processing are more properly borne by the produced aromatics.
Yields of pygas are determined by the severity of the cracking operation, and the composition of
the feedstocks. Both of these factors are themselves determined by the overall economics of the
plant with aromatics production of secondary importance. The effect of the various feeds on the
aromatics yields is shown in Figure 1.2. In general the heavier the feed, the more aromatics are
produced.
Figure 1.2
Effect of Steam Cracker Feedstock on Aromatics Yield
0.60
0.50
Ton Per Ton of Ethylene
0.40
0.30
0.20
0.10
0.00
ethane propane n-butane light full range light AGO HVGO
naphtha naphtha
BENZENE TOLUENE XYLENES OTHER
Q207_00101.0007.4106_char t s.xls
The effect of increasing severity of the cracker operation is to increase the yield of aromatics.
This is shown in Figure 1.3 for a full range naphtha (FRN) feedstock. The severity (defined by
the propylene to ethylene ratio) is varied from a high severity operation (P/E=0.48) to a medium
severity (P/E=0.59). The BTX content is lowered from 69 to 42 percent of the pygas and the
Benzene/Toluene 5
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
benzene drops from 39 to 19 percent. As the yield of ethylene is also increasing, the ratio of
aromatics to ethylene falls and then rises.
Figure 1.3
Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed
1.2
P/E=0.590
1.0
Ton Per Ton of Ethylene
P/E=0.540
0.8 P/E=0.516
P/E=0.478
0.6
0.4
0.2
0.0
HIGH STANDARD INTERMEDIATE MEDIUM
BENZENE TOLUENE XYLENES OTHER
Q207_00101.0007.4106_char t s.xls
Azeotropic distillation, which uses a low boiling point solvent with an affinity for
nonaromatics. The solvent is distilled overhead with the nonaromatic raffinate.
Extractive distillation (ED), which employs a high boiling point solvent with an affinity
for aromatics. The influence that a solvent has on the boiling temperature of the various
components is significant. For benzene the boiling temperature increases by almost
100°F, whereas for cyclohexane the delta is about 13°F. Thus, the nonaromatics can be
distilled overhead, whereas the bottoms product will consist of solvent loaded with
aromatics. The aromatics can then be separated from the solvent by distillation. In the
ED step, the light nonaromatics are preferentially removed because of their lower boiling
point, although this can be partly compensated for by a high light/heavy selectivity of the
solvent. As a result, the aromatics product contains relatively small quantities of light
nonaromatics. This means that a benzene of reasonable quality may be obtained from C6-
Benzene/Toluene 6
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
C8 cut, but the toluene and xylenes would be poorer quality. For this reason, ED is
normally used when the feed is a heart cut of the appropriate boiling range.
Liquid/liquid solvent extraction (LLE), which uses solvents that form a separate liquid
phase. Aromatics are considerably more soluble than nonaromatics in the solvents
employed. The aromatics are extracted from the feed stream in a liquid/liquid contactor,
and the extract stream is stripped to recover the aromatic product and the solvent. In this
case, the aromatic product would tend to be more contaminated by the light nonaromatics
that are preferentially stripped off in the second stage. For liquid/liquid extraction, a low
light/heavy selectivity is required (i.e. fewer light nonaromatics pass into the solvent).
Within each type, there are a number of solvents available. However, for a given process design
the solvent type is not replaceable. LLE is usually employed where recovery of benzene and
toluene are important with respect to yield and quality. ED is usually employed where the key
product is benzene and/or the yield is not so critical.
The complementary features of the ED and the liquid/liquid extraction systems are often
combined when extraction of the full BTX range is required. In this case, the extract from the
liquid/liquid stage passes to an ED column, where nonaromatics and some aromatics are
removed as overheads product, which recycles to the liquid/liquid extraction stage. The bottoms
product from the ED column passes to a stripper to separate the purified aromatics and the
solvent.
In general LLE processes are more capital intense and have higher utility requirements, but
produce a higher product yield and are suitable for BTX separation. ED processes have lower
capital requirements and lower utility requirements. The ED processes tend to give a lower
product yield and are suitable for benzene separation. LLE is normally selected where there is a
need for high quality, high yield of toluene, particularly for subsequent conversion (e.g. TDP).
1.5 DEALKYLATION
The market demand for benzene, as a proportion of total BTX, is higher than the proportion of
benzene in typical BTX products. Conversion of toluene and, to a lesser extent, xylenes, is
practiced by two basic techniques:
Although not purely dealkylation, the topic of toluene disproportionation is also included
under this heading as a discretionary method of producing benzene. The toluene is
converted to benzene and xylenes in this process.
Benzene/Toluene 7
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
1.6 ECONOMICS
1.6.1 Reformate
The costs of production for the various technologies for producing reformate have been
developed at a world scale plant capacity of 500 kta. Of the five types of technologies reviewed
herein, we have shown that the economics can vary widely. This range of economic
performance is clearly seen in Figure 1.4, where all five processes are viewed on a side-by-side
basis. Aromax® is the low cost process which is consistent with previous PERP reports (02/03-
5). CCRTM and RZ PlatformingTM have essentially the same low cost of production. CyclarTM is
the highest cost route to reformate, which confirms the results from Nexant’s previous PERP
report (02/03-5). If a 30 percent discount is applied to the LPG feedstock price (pricing one
might find in the Middle East), the CyclarTM economics are competitive with the low cost
technologies.
It is important to note that the economics presented herein are in essence a “snapshot” in time.
In Figure 1.4 we have tried to mitigate this by comparing the fourth quarter 2006 costs with the
five-year historical averages for feed and product prices. In each analysis the results show
similar, but lower costs of production when using the 5-year average.
Figure 1.4
Cost of Production of Reformate
(500 kta USGC)
3.00
2.50
2.00
Dollars Per Gallon
1.50
1.00
0.50
0.00
AROMAX CCR RZ ALPHA CYCLAR
PLATFORMING
4Q2006 5 Yr Avg
Q207_00101.0007.4106_char t s.xls
1.6.2 Benzene/Toluene
The costs of production of benzene from various sources employing different technologies are
summarized in Figure 1.5. The 2006 costs range from a low of $2.09 per gallon ($626 per metric
Benzene/Toluene 8
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
ton) for selective toluene disproportionation (STDP) to a high of $3.12 per gallon ($934 per
metric ton) for bulk dealkylation of pyrolysis gasoline. It is important to note that the economics
presented herein are in essence a “snapshot” in time. In Figure 1.5 we have tried to mitigate this
by comparing the fourth quarter 2006 costs with the five-year historical averages for feed and
product prices. In each analysis the results show similar, but lower costs of production when
using the 5-year average.
Figure 1.5
Benzene Cost of Production
(334 kta, USGC)
3.50
3.00
2.50
Dollars Per Gallon
2.00
1.50
1.00
0.50
0.00
SE SE Pygas ED Pygas Dealky Litol THDA TDP STDP
Reformate Pygas
4Q2006 5 Yr Avg
Q207_00101.0007.4106_chart s.xls
Benzene/Toluene 9
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
Table 1.3
U.S. Benzene Supply, Demand and Trade
(Thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 9,872 9,754 9,753 9,680 9,543 9,654 9,654 9,680 9,654 9,654
Speculative Capacity 0 0 0 0 0 0 151 250 301 501
Total Capacity 9,872 9,754 9,753 9,680 9,543 9,654 9,805 9,930 9,954 10,154
Production 6,844 7,398 7,898 7,960 7,326 7,962 8,037 8,070 7,984 8,101
Operating Rate 69% 76% 81% 82% 77% 82% 82% 81% 80% 80%
Net Exports (939) (1,236) (1,211) (1,237) (1,538) (1,293) (1,426) (1,440) (1,513) (1,349)
Consumption 7,783 8,633 9,110 9,197 8,864 9,266 9,470 9,519 9,513 9,465
Table 1.4
Western Europe Benzene Supply, Demand and Trade
(Thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 9,437 9,532 10,033 10,130 10,121 10,297 10,571 10,662 10,632 10,632
Speculative Capacity 0 0 0 0 0 0 0 100 100 (10)
Total Capacity 9,437 9,532 10,033 10,130 10,121 10,297 10,571 10,762 10,732 10,622
Production 7,635 7,884 8,242 8,430 8,456 8,901 9,091 9,134 9,066 8,746
Operating Rate 81% 83% 82% 83% 84% 86% 86% 85% 84% 82%
Benzene/Toluene 10
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
1.7.3 Asia/Pacific
Since the late 1900s the Asia Pacific region has been close to a balanced position in benzene,
with Taiwan and Indonesia the major importers and Japan, South Korea and Thailand providing
most of the exports within the region. In the last several years high benzene prices in other parts
of the world, especially the U.S. and surplus capacity in China provided opportunities for exports
to flow out of the region. For most of the outlook period, Asia Pacific is expected to be a small
net importer and occasionally a net exporter when opportunities arise. The Asia Pacific supply
and demand balance is shown in Table 1.5.
Table 1.5
Asia Pacific Benzene Supply, Demand and Trade
(Thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 14,716 15,123 15,614 15,927 16,505 17,883 18,707 19,550 20,116 20,465
Speculative Capacity 0 0 0 0 0 0 200 531 662 1,032
Total Capacity 14,716 15,123 15,614 15,927 16,505 17,883 18,907 20,082 20,778 21,497
Production 11,446 11,814 12,764 14,100 15,167 14,821 15,967 16,826 17,121 17,406
Operating Rate 78% 78% 82% 89% 92% 83% 84% 84% 82% 81%
Net Exports (78) (271) (354) 434 367 (387) (252) (74) (262) (578)
Consumption 11,524 12,085 13,118 13,666 14,799 15,220 16,245 16,917 17,418 18,010
1.8 CONCLUSIONS
Whether or not TDP or THDA units operate economically will not only depend on pricing
conditions (e.g., alternative value for toluene), but also on market position. Because THDA is
often the most expensive route for producing benzene, merchant THDA facilities tend to operate
only when the price of benzene exceeds the cost of production via THDA. Captive THDA units,
in contrast, usually serve to balance internal requirements for benzene and are run independently
of merchant market conditions. Historically the delta between the price of benzene and toluene
has been about 32 cents per gallon ($96 per metric ton) as shown in Figure 1.6. However, in the
past few years this delta has varied greatly. For the fourth quarter of 2004 it was almost $1.65
per gallon ($500 per metric ton), while for the second quarter of 2006 it was negative 8 cents per
gallon (-24 per metric ton). Currently (4th quarter 2006) this delta is about $1.10 per gallon
($332 per metric ton) while the cost of toluene hydrodealkylation is 23 cents per gallon ($68 per
metric ton).
Benzene/Toluene 11
PERP 06/07-6
Q207_00101.0007.4106
Section 1 Executive Summary
Figure 1.6
Benzene to Toluene Price Delta
600
500
Delta Benzene - Toluene, $/T
400
300
200
100
-100
1982-Q1 1984-Q1 1986-Q1 1988-Q1 1990-Q1 1992-Q1 1994-Q1 1996-Q1 1998-Q1 2000-Q1 2002-Q1 2004-Q1 2006-Q1
Q207_00101.0007.4106_chart s.xls
In addition to the economics, a variety of other issues must also be considered when choosing
process technology. Some of these considerations are listed below:
Access to feedstock
Outlet for byproducts
Investment requirements
Revamp and integration potential or strategy
Feedstock/product price fluctuations/forecasts
Technology availability/licensing terms
Technology risk
Security of supply/strategic importance
Table 1.6 summarizes Nexant’s view with respect to some of the strategic issues. In the final
analysis, the selection of any of these aromatic technologies will have to be based on a careful
case by case assessment.
Table 1.6
Reformate Process Selection
Benzene/Toluene 12
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
2.1 INTRODUCTION
Aromatics are produced as coproducts in refinery catalytic reformers, olefins plants, coal tar
processing, and toluene disproportionation (TDP) units. In addition, on-purpose supplies of
benzene are produced via toluene hydrodealkylation (THDA) units. THDA units are the swing
source and used when benzene supply is tight and prices get high enough to justify the
economics of those plants.
About 70 percent of the global production of benzene is by extraction from either reformate or
pyrolysis gasoline (pygas). The former is formed in the catalytic reforming of naphtha, a
technology primarily directed at the production of high octane gasoline components. The latter
is a liquid byproduct formed in the production of olefins by steam cracking liquid feeds, such as
naphtha or gas oil. Ethylene plants typically operate near full capacity, but the feedstock slate
may vary depending on market conditions. Extraction from reformate and pygas are the most
economical sources of benzene.
The composition of BTX (benzene, toluene and xylenes) depends on the source. Table 2.1
compares BTX from pygas and reformate. Pygas is typically rich in benzene, whereas xylenes
and toluene are the main components of reformate.
Table 2.1
Typical BTX Composition from Pygas and Reformate
(Weight percent)
Typical
Pygas¹ Reformate Demand Split
Standard Medium
Severity Severity CCR² SR³
BTX content 58 42 51 42 49
Benzene 48 44 17 14 49
Toluene 3 31 39 39 23
Xylenes 19 25 44 47 28
¹ Based on cracking full range naphtha
² Continuous catalytic regenerative reformer
³ Semi-regenerative reformer
Table 2.1 also very roughly shows the global demand for BTX products. In general, benzene is
present in the main feedstocks in proportions lower than market demand, whereas toluene is in
considerable excess, as are xylenes. To some extent this imbalance is corrected by their relative
values as gasoline components because refiners have the option of extracting BTX as chemical
products or blending them in fuel. Xylenes and toluene are more valuable as blendstocks than
benzene, and the benzene content in gasoline is restricted for environmental reasons.
Benzene/Toluene 13
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Essentially all of the BTX recovered in an oil refinery is produced in the catalytic reforming unit
(both continuous catalytic regenerative and semi-regenerative types). In a refinery which is not
integrated into petrochemical production, the reformate product, or C5+ stream, containing
benzene and heavier aromatics, is utilized as a high octane gasoline blendstock. In recent years,
the utilization of benzene in the U.S. gasoline pool has decreased as a result of the limits placed
on benzene content in gasoline by environmental regulations. Many U.S. refineries that are not
integrated with aromatics production remove the benzene precursors upstream of the reforming
unit, which minimizes benzene levels in the reformate. The benzene precursors are typically
utilized as isomerization unit feedstock for incorporation into the gasoline pool. Conversely,
refineries that are integrated with aromatics production maximize the production of benzene in
the reformer unit.
Benzene production can vary based on reformer operating rates and seasonal demand for
gasoline, feedstock slate and severity of the operations. Production from this source is expected
to grow tracking gasoline consumption growth.
Benzene and higher aromatics are produced in varying amounts in olefin plants. Benzene may
be recovered by extraction from the pygas coproduct stream. The quantity and composition of
the pygas varies with the feedstock cracked and cracker severity. Lighter feedstocks produce
little pygas, but there may be sufficient benzene content in pygas from liquids crackers to justify
extraction.
The slight trend toward heavier steam cracker feedstocks will result in higher benzene
production within the pygas and result in growth of benzene from pygas exceeding the overall
ethylene production growth.
A third source of BTX is light oil produced during the coking of coal. Although this was once
the only source of aromatics, it is now a minor contributor to the total supply amounting to only
6-7 percent of the global capacity (mostly in the Former Soviet Union and Eastern Europe).
Benzene extraction from coal tar operations is not expected to grow, since the output of the steel
industry has been essentially level for some years. Clean Air Act emission regulations restrict
output from this source.
In this section, technologies based on extraction and dealkylation are described, along with a
discussion of each major feedstock and estimates of reformate and benzene production costs. A
discussion of non-conventional routes to BTX is also included. The emphasis of the economic
analysis is placed on benzene because of its importance as a chemical product. A list of the
foremost licensors of aromatics technology is provided in Table 2.2.
Benzene/Toluene 14
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.2
Licensors of Aromatics Technology
The catalytic reforming process is used in the production of gasoline of desired octane number,
aromatics (benzene, toluene, mixed xylenes including ethyl benzene) and hydrogen for plant use
(e.g. hydrotreating of the naphtha feed). The only difference in operations for aromatics
production and motor fuel production is in the choice of operating parameters (especially
feedstock selection) to maximize the yields of benzene, toluene and mixed xylenes (BTX).
Benzene/Toluene 15
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
2.2.1 Chemistry
In a typical reforming process, the reactions include dehydrogenation, dehydrocyclization,
isomerization and hydrocracking. The dehydrogenation reaction typically will be the
dehydroisomerization of alkylcyclopentanes to aromatics, the dehydrogenation of paraffins to
olefins, the dehydrogenation of cyclohexanes to aromatics, and the dehydrocyclization of
paraffins to aromatics. The aromatization of the normal paraffins to aromatics is generally
considered to be the most important because of the high octane of the resulting aromatic product
compared to the low octane ratings for normal paraffins. The isomerization reactions include
isomerization of normal paraffins to isoparaffins and the isomerization of substituted aromatics.
The hydrocracking reactions include the hydrocracking of paraffins and hydrodesulfurization of
any sulfur that is remaining in the feedstock.
The reaction kinetics are such that naphthene dehydrogenation is the fastest and paraffin
dehydrocyclization is the slowest. While operating within these boundaries hydrocracking of
paraffins and naphthenes also occurs. However, for a given catalyst, lower operating pressures
will deemphasize hydrocracking, and thus make it possible to achieve better yields.
The maximum potential yields of aromatics that could be obtained from naphthenes and
paraffins if hydrocracking could be suppressed are determined by the thermodynamic equilibria
for aromatization reactions. These data show, first, that corresponding aromatic yields from the
various classes of compounds follow the order (from highest to lowest) alkylcyclohexanes,
alkylcyclopentanes, paraffins. Second, aromatic yields increase with the number of carbon
atoms per molecule; benzene from C6 paraffin has a lower yield than toluene from C7 paraffin.
Third, for a given reactant, the potential aromatics yield increases as the hydrogen partial
pressure is decreased.
As the catalyst ages, it is necessary to change the process operating conditions to maintain the
reaction severity and to suppress undesired reactions. The basic relationships are shown in
Table 2.3.
Benzene/Toluene 16
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.3
Basic Relationships in Catalytic Reforming
Naphthene
Reaction Hydrocracking Isomerization Dehydrocyclization Isomerization Dehydrogenation
Reaction rate Slowest Rapid Slow Rapid Fastest
Heat effect Exothermic Mildly Mildly Mildly Quite
Exothermic Endothermic Exothermic Endothermic
Effect of:
High pressure Aids Non Hinders None Hinders
High temperature Aids Aids Aids Aids Aids
High space velocity Hinders Hinders Hinders Hinders Hinders
Effect on:
Hydrogen production Absorb None Evolves None Evolves
RVP Increase Increase Decrease Decrease Decrease
Density Decrease Decrease Increase Increase Increase
Volume yield Varies Increase Decrease Increase Decrease
Octane Increase Increase Increase Decrease Increase
On a mole basis, naphthene conversion to aromatics is about 98 percent with the number of
carbon atoms in the precursor being retained in the product as follows:
For paraffins the following moles of aromatics are produced from one mole of paraffins having
the indicated number of carbon atoms:
1 mole of a six carbon paraffin yields 0.05 moles of a six carbon aromatic
1 mole of a seven carbon paraffin yields 0.10 moles of a seven carbon aromatic
1 mole of an eight carbon paraffin yields 0.25 moles of an eight carbon aromatic
1 mole of a nine carbon paraffin yields 0.45 moles of a nine carbon aromatic
1 mole of a ten carbon paraffin yields 0.45 moles of a ten carbon aromatic
Benzene/Toluene 17
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
between the catalyst beds in order to maintain the reaction temperatures. The dehydrogenation
reaction of alkylcyclohexane to aromatics is represented below by the reaction of
methylcyclohexane to toluene.
CH3 CH3
+ 3H2
All cyclohexanes dehydrogenate very rapidly and completely to aromatics. The cyclopentanes
react at a much slower rate and undergo both isomerization to form the corresponding
cyclohexanes and ring opening to form paraffins.
The dehydrogenation of cyclohexane derivatives is a much faster reaction than that of the
dehydrocyclization of paraffins represented below by the reaction of normal heptane to toluene.
Although the latter is also endothermic, it proceeds via multiple steps and at a relatively slow
reaction rate. It is the most difficult reforming reaction to promote. For instance, the reaction
rate for dehydrocyclization of hexane is only one-third that of hydrocracking. Thus, the fraction
of the normal hexane converted to benzene is relatively low.
CH3
n-C7H16 + 4H2
On the other hand, normal heptane hydrocracks at about the same rate as normal hexane, so the
faster rate of dehydrocyclization (about four times that of hexane) leads to significantly greater
fractional conversion to aromatics for normal heptane in comparison with hexane.
A third reaction necessary to obtain the high aromatic concentrations needed in the product to
produce a high octane is the dehydroisomerization of an alkylcyclopentane to an
alkylcyclohexane and then to an aromatic. These reaction steps are highly dependent on the
processing conditions. The reaction of methylcyclopentane to benzene via cyclohexane is as
follows:
Benzene/Toluene 18
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
CH3
Methylcyclo-
Cyclohexane
pentane
+ 3H2
Benzene Hydrogen
Q207_00101.0007.4106.cdx
Aromatics have a higher liquid density than paraffins or naphthenes with the same number of
carbon atoms so one volume of paraffins produces only about 0.77 volume of aromatics and one
volume of naphthenes produces about 0.87 volume of aromatics. At the same time the aromatics
production increases the gasoline end point of the naphtha. To summarize, aromatics yield is
increased by high temperature, low pressure, low space velocity, and low hydrogen-to-
hydrocarbon mole ratios. With reference to the latter, a sufficient hydrogen partial pressure must
be maintained to avoid excessive coke formation.
Isomerization yield is increased by high temperature, low space velocity, and low pressure.
2.2.1.3 Hydrocracking
Paraffin hydrocracking is slower than the isomerization reaction and is exothermic.
Hydrocracking yields are increased by high temperature, high pressure, and low space velocity.
The disappearance of paraffins from the gasoline boiling range via hydrocracking does
concentrate aromatics in the product, and thus contributes to octane improvement. The reaction
consumes hydrogen and results in lower yields. Hydrocracking is represented below by the
reaction of normal hexane to butane and ethane.
Benzene/Toluene 19
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Most operators prefer to minimize hydrocracking within the reformer reactors in order to
minimize the light naphtha (C5s) and LPG make (C3 and C4). Thus, careful control of the
operating conditions (i.e., temperature) is needed in order to obtain high product quality and
yields.
CH3CH2CH2CH2CH2CH3 + H2
n-Hexane Hydrogen
CH3CH2CH2CH3 + CH3CH3
Butane Ethane
Q207_00101.0007.4106.cdx
2.2.2 Catalyst
All of the reforming catalysts in general use today contain platinum (0.2-0.75 weight percent)
supported on a silica or silica-aluminum base. In most cases rhenium (0.2-0.78 weight percent)
is combined with platinum to form a more stable catalyst that permits operation at lower
pressure. Iridium and tin have also been used in place of rhenium. Chlorine (0.9-1.2 weight
percent) is often added as a promoter and to maintain the platinum well dispersed over the
catalyst surface. The catalyst shape may be cylindrical, spherical, or triple in sizes from one-
eighteenth to one-eighth inch in diameter. The density for extruded catalyst is between 37 and
48 pounds per cubic foot and for spherical catalyst is between 32 and 45 pounds per cubic foot.
Since a typical throughput limitation for a reformer unit is the amount of coke that can be burned
in the CCR regenerator, one method for increasing throughput and, thus, increase aromatics
production is to replace older generation catalyst (e.g., UOP’s R-134) with the latest generation
catalyst (e.g., UOP’s R-264). That is, newer generation catalyst should provide higher activity
and produce less coke.
Platinum is thought to serve as the catalytic site for hydrogenation and dehydrogenation
reactions and chlorinated alumina provides an acid site for isomerization, cyclization, and
hydrocracking reactions. Rhenium or iridium act as coke inhibitors. In early reforming units
employing a monometallic platinum catalyst high sulfur levels in the feedstock led to the need
for high metal content (0.6 to 0.75 weight percent platinum). The advent of the
platinum/rhenium catalyst (bimetallic) required that the sulfur level in the feed be reduced to less
than one wppm.
Benzene/Toluene 20
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Reforming catalyst activity is a function of surface area, pore volume, and active platinum and
chlorine content. Catalyst activity is reduced during operation by coke deposition and chloride
loss. Noble metal catalysts lose activity in the presence of sulfur or nitrogen compounds and are
poisoned by metals such as arsenic and lead at concentrations of far less than 1 ppm. The first
deactivation is reversible, whereas the second is irreversible.
For a semi-regeneration operation (high pressure) up to 200 barrels of charge can be processed
per pound of catalyst before regeneration is required. The activity of the catalyst can be restored
by high temperature oxidation of the carbon followed by chlorination. The activity of the
catalyst decreases during the on stream period and the reaction temperature is increased as the
catalyst ages to maintain the desired operating severity. The catalyst can normally be
regenerated at least three times before it has to be replaced and returned to the manufacturer for
reclamation. Regenerations may be required in cycles anywhere from 3 to 24 months.
Modern continuous reformers are being designed for pressures in the range of 50 to 100 psig. In
general, as reactor pressure is decreased, catalyst requirements decrease, gasoline yields increase,
and catalyst deactivation increases.
2.2.3.2 Temperature
Reactor bed temperature is the primary variable available to control product quality. Two
expressions are commonly used to define reactor temperature. Weighted average inlet
temperature (WAIT) is the fraction of catalyst in each reactor bed multiplied by its inlet
temperature. Weighted average bed temperature (WABT) is the fraction of catalyst in each bed
multiplied by the average of its inlet and outlet temperatures. Each feedstock has its own
temperature/octane relationship. By raising or lowering the reactor temperature, the plant
engineer can raise or lower the product octane number. As temperature is increased the catalyst
requirement is decreased, the gasoline yield increases, and catalyst deactivation increases.
Benzene/Toluene 21
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
The final boiling point or ASTM distillation end point (EP) is designed to exclude coke
precursors and is established at the crude fractionator or pipestill. The EP is usually set at 400°F
in order to eliminate the hydrocarbons, which form polycyclic aromatics. These latter aromatics
are responsible for carbon laydown on the catalyst and shortened cycle life. Decreasing the end
point will have the effect of increasing the catalyst requirement, decreasing the mogas yield and
decreasing catalyst deactivation.
The reformate product has a higher EP and a lower IBP than the feedstock. Thus, higher boiling
point hydrocarbons are present in the final reactor where the operating severity is the highest and
coking is most likely to occur. Because of extension of the IBP and EP during the reforming
process, some operators hold the feedstock EP well below the 400°F limit.
Benzene/Toluene 22
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
2.2.3.6 Impurities
Cracker stocks (thermal cracker, cat cracker, and coker naphthas) containing a significant
amount of olefins need to be hydrotreated as described below.
The active material in most catalytic reforming catalysts is platinum. Certain metals (lead, iron,
arsenic, etc.) as well as sulfur compounds, nitrogen compounds, chlorine, olefins, water, and
oxygen will cause catalyst deactivation. Hydrotreating of the feed is usually sufficient to remove
these materials. Hydrogen for the hydrotreater reactions is supplied from the downstream
catalytic reformer. A discussion of the hydrotreating process is presented in Section 2.2.5 Feed
Preparation.
The space velocity will determine the limits of product quality (i.e., octane number). The greater
the space velocity, the lower the limit or maximum octane possible. Reactor temperatures are
interchangeable with LHSV, and the two together determine product quality. Within normal
reforming design parameters, space velocity has little effect on catalyst stability (on a barrel per
pound basis). Higher LHSV results in a lower severity; conversely, lower LHSV results in a
higher severity.
An increase in the H:HC ratio will move the naphtha feed through the reactor at a faster rate and
supply a greater heat sink for the endothermic heat of reaction. It also increases the hydrogen
partial pressure and, therefore, the catalyst stability with little effect on product quality or yields.
On the other hand, lower ratios save energy (i.e., compression costs) and favor the naphthene
dehydrogenation and dehydrocyclization reactions.
At the low pressure levels designed for modern reformers, the typical H:HC ratio is in the range
of 2 to 5. Older high pressure units operate in the range of eight to ten. Increasing the recycle
rate will decrease the catalyst requirement, the gasoline yield and the catalyst deactivation.
Benzene/Toluene 23
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
2.2.4.1 Semi-regenerative
The semi-regenerative (SR) unit has the advantage of low capital costs. Regeneration requires
the unit to be taken off line. Depending on the severity of operation, regeneration is required at
intervals of three to six months. High hydrogen recycle rates and operating pressures are utilized
to minimize coke laydown and consequent loss of catalyst activity.
A process flow diagram is shown in Figure 2.1. The pretreated feed and recycle hydrogen are
heated to between 925 and 975°F before entering the first reactor. In the first reactor, the major
reaction is the dehydrogenation of naphthenes to aromatics, and since this is strongly
endothermic, a large drop in temperature occurs. To maintain the reaction rate, the gases are
reheated before being passed over the catalyst in the second reactor. As the charge proceeds
through the reactors, the reaction rates decrease and the reactors become larger and less reheat is
needed. Three reactors are usually sufficient to provide the desired degree of reaction and
heaters are needed before each reactor to bring the mixture up to reaction temperature. In
practice, either separate heaters can be used or one heater can contain several separate coils. The
reaction mixture from the last reactor is cooled and the liquid products condensed. The
hydrogen-rich gases are separated from the liquid phase in a separator and the liquid from the
separator is sent to a fractionator to be debutanized.
The hydrogen-rich gas stream is split into a hydrogen recycle stream and a net hydrogen
byproduct used in hydrotreating or hydrocracking operations or as fuel.
The operating pressure is typically in the range of 100 to 350 psig and uses a hydrogen rate of
4,000 to 8,000 SCF/bbl of fresh feed. LHSV is in the range of 2 to 3.
A process flow diagram of UOP's CCR Platforming™ process scheme is shown in Figure 2.2.
The catalyst flows by gravity from the last (bottom) reactor in to a catalyst collector vessel,
which maintains uniform catalyst withdrawal. After depressuring and purging, the catalyst is
lifted to a catalyst hopper. Catalyst then flows to the regeneration tower, where the carbon is
burned off and the catalyst chloride level is adjusted. Net regeneration gas is vented.
Benzene/Toluene 24
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Regenerated catalyst is then returned to the first (top) reactor. In this scheme the reactor operates
only in its primary function, providing the catalytic environment for the reforming reactions; thus
it is not exposed to the severe regeneration conditions. The Axens flow scheme (not shown)
employs a "smooth-flowing," moving bed process. The Axens reactors are not stacked and the
catalyst moves from one vessel to another.
The second generation of UOP's CCR process is the result of still lower operating pressure and
development of improved catalyst. The typical operating conditions of UOP's second generation
CCR are a reactor pressure of 50 psig, a space velocity of 1.7, and a H:HC ratio of less than 2.5.
The system continuously regenerates up to 4,500 pounds per hour of catalyst. The Axens
continuous design also operates at the lower pressure of 50 psig.
Axens proposes a modified regeneration system, RegenC™, which includes a primary burn zone
equipped with a dry burn loop to minimize the moisture level during combustion; a finishing
burn zone; an oxychlorination zone with an independent gas loop; and a calcination zone. The
dry burn loop has been found to extend catalyst life in industrial units by reducing surface area
loss during coke burning.
Most new grass roots aromatics projects involve the continuous reforming technologies of either
UOP or Axens.
2.2.4.3 Cyclic
The cyclic process is a compromise between the semi-regenerative and the continuous process
described above. It is characterized by having a swing reactor in addition to those on stream, as
shown in Figure 2.3. The catalyst in a cyclic unit can be regenerated without shutting the unit
down as required for a semi-regenerative unit. When the activity of the catalyst in one of the on
stream reactors drops below the desired level, this reactor is isolated from the system and
replaced by the swing reactor. The catalyst in the replaced reactor is then regenerated by
admitting hot air into the reactor to burn the carbon off the catalyst. After regeneration it is used
to replace the next reactor needing regeneration.
The cyclic design is more expensive then the semi-regenerative scheme. All the reactors in the
cyclic process are the same size. A complete spare reactor is required as well as a complex
piping manifold. Regeneration is typically performed on a 24 or 48 hour cycle. On the plus side
the cyclic process offers the advantage of a lower pressure operation then the semi-regenerative
process and higher yields of reformate at the same severity.
Benzene/Toluene 25
PERP 06/07-6
Q207_00101.0007.4106
Section 2
Steam FIRED
HEATERS
Gas
STABILIZER
REACTORS
LPG
REBOILER
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
Reformate
HYDROGEN Net
RECYCLE Hydrogen
COMPRESSOR
HYDROGEN
SEPARATOR
Hydrotreated
Naphtha Feed
Figure 2.1
Semi-regenerative Reformer
Process Flow Diagram
Current Commercial Technology
26
Q207_00101.0007.4106.vsd
REACTORS Low pressure High pressure
Section 2
Separation Recontactor
Net Gas
Regeneration
Section
(simplified)
HEATER
Combustion
Zone {
Chlorination
Zone
{
0
Drying Zone {
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
Air
Reformate
to Stabilizer
Recycle Hydrogen
Lift LOCK
Gas HOPPER
#2
LOCK
Spent Catalyst HOPPER
#1
27
Q207_00101.0007.4106.vsd
Purge
Section 2
SWING
REACTOR
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
FIRST SECOND THIRD
PREHEAT HEATER HEATER HEATER
FURNACE
LOWER REACTION HEADER
SEPARATOR
Hydrotreated DRUM
Naphtha Feed DRIER
RECYCLE GAS
Reformate
COMPRESSOR Figure 2.3
to Stabilizer
Cyclic Catalytic Reformer
Process Flow Diagram
Current Commercial Technology
28
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
In the hydrotreater the sulfur and nitrogen compounds are converted to hydrogen sulfide and
ammonia and easily removed via stripping of the hydrotreated stream. Olefins are saturated to
paraffins. The metals in the feed are retained on the hydrotreater catalyst. Finally, a small
amount of cracking occurs in the hydrotreater and the light hydrocarbons, which are produced
must be removed in the stabilizer in order to establish the initial boiling point as described above.
A process flow diagram for a naphtha hydrotreater is presented in Figure 2.4. The feed is usually
taken from a naphtha splitter where the light portion (C5/C6) is distilled off and sent to an
isomerization unit or directly to the gasoline pool. The heavy portion is directed to the
hydrotreater where the feed is pumped to operating pressure and heated with the reactor effluent
before final heating is done in a fired heater.
The reactor inlet usually has some sort of receptor to collect scale and fines. A downflow or
radial flow reactor can be employed. Only one reactor is typically needed for virgin naphtha
service. The reactions are exothermic so there is a small temperature increase across the reactor.
The effluent is cooled first against the fresh feed and then against air and/or water. The
condensed product is pumped to the stabilizer where the hydrogen sulfide, ammonia, and light
gasses are stripped out.
The hydrogen is recycled from the high pressure separator back to the front end of the unit. A
small purge is removed in order to limit the buildup of inerts and fresh hydrogen. Makeup from
the reformer is added in order to maintain the hydrogen partial pressure within the reactor.
The two main concerns with the operation of the hydrotreater are catalyst deactivation and
pressure drop. Hydrotreaters are typically designed to run one to two years before the catalyst
must be regenerated (usually to coincide with a plant turnaround). Pressure drop increases over
the run due to scale, catalyst fines, coke, and polymer deposits at the top of the reactor bed
(downflow reactor). The top of the catalyst bed can usually be skimmed via an inert entry
procedure with minimal downtime. At the same time fresh catalyst is installed to replace the
catalyst skimmed off during the procedure.
The operating conditions within the hydrotreater reactor depend upon the particular feed and
impurities. They are typically 525°F to 850°F at a pressure of 400 to 800 psig. The space
velocity (LHSV) is in the range of 2 to 6 per hour. The hydrogen partial pressure is maintained
above 100 psia in the reactor in order to assure complete hydrotreating. Hydrogen consumption
is in the range of 50 to 150 SCF per barrel for a low sulfur virgin naphtha, but can be several
times this value for a cracked naphtha containing a significant amount of olefins and diolefins.
Benzene/Toluene 29
PERP 06/07-6
Q207_00101.0007.4106
Section 2
MAKE-UP
HYDROGEN
COMPRESSOR
Stabilizer
overhead gas
REACTOR
COOLER
STABILIZER
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
SEPARATOR
Hydrotreated
product to
reformer
NAPHTHA
FEED
HEATER
Reactor
effluent-to-feed
exchanger Figure 2.4
Naphtha Hydrotreater
Process Flow Diagram
Current Commercial Technology
30
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
The boiling range of the precursors are an indication of the type of aromatics produced.
Thus, benzene precursors are in the 160-180°F boiling range; toluene precursors are in
the range of 180-250°F boiling range; and xylene precursors boil between 250 and 350°F.
Cracked naphthas are premium feedstock for BTX production (i.e., rich sources of
aromatics and naphthenes).
The higher the aromatic content of the feed to a reformer, the higher the yield of aromatic
based on feed.
Benzene/Toluene 31
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.4
Reformer Yield From Medium Quality Full Range Naphtha
(weight percent)
Catalyst A B
Semi-regenerative Unit, Continuous
Bimetallic Catalyst Regeneration Unit
25 Bar, 96 RON High Stability
9 Bar, 102 RON
Hydrogen 1.7 3.0
Gases 4.5 3.8
LPG 12.8 9.8
C5 reformate 81.0 83.4
Total 100.0 100.0
Reformate quality
Nonaromatics (C5-C8) 45.4 29.3
Benzene 5.8 9.0
Toluene 16.9 21.0
Xylenes 20.6 23.7
C9 11.3 17.0
Total 100.0 100.0
(1)
P/N/A:60/25/15, nominal range 70 to 170°C. (158 to 338°F)
(2)
Yield structure A is typical of the least rich reformates, likely to be used for BTX extraction;
yield B is typical of the richest reformates.
(3)
The data are based on actual unit performance; the quality of naphtha in B is very similar
to, but slightly heavier than that in A.
When reforming for aromatics only, the naphtha may be prefractionated to produce a reformer
feedstock of appropriate composition, depending on which BTX products are required. Another
process scheme involves the use of a blocked reformer. A light cut passes to the aromatics
section of the reformer for production of aromatics and gasoline, whereas the heavier cut is fed
to a gasoline-only part of the reformer. Fractionation and associated tanks would not be needed
to produce gasoline alone, so their cost, if used, should be assigned to the recovered aromatics.
Benzene/Toluene 32
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Typical yields for UOP's and Axens’ reforming processes are presented in Table 2.5 and 2.6,
respectively. Typical utilities for UOP are compared with Axens’ in Table 2.7.
Table 2.5
Typical Yields of UOP’s Reforming Processes
Table 2.6
Typical Yields of Axens’ Reforming Processes
Benzene/Toluene 33
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.7
Typical Utilities of UOP and Axens Reforming Processes
(per barrel)
UOP Axens
Electrical power kW 0.900 1.008
Steam-600 Thousand lb 0.042 0.033
Boiler feed water Thousand lb 0.066 0.072
Fuel fired Million Btu 0.252 0.274
Nitrogen Thousand SCF 0.002 0.004
(1)
CCR Platforming™ unit operating at 50 psig average reactor pressure, 102 C5+ RONC with
a 1,500 lb/hr catalyst regeneration section (excluding recontacting utilities that are dependent
on battery limits pressure)
(2)
Average of gasoline and aromatics operations
Although most new continuous reformers designed for gasoline production produce reformate
with a RON of about 102, reformers designed for BTX production produce reformate with a
RON of at least 104 and some as high as 108. Older SR reformers produce reformate with a
RON of about 96 to 100. It is important to understand that a high octane reformate stream will
contain low levels of C8 paraffins, such that a simpler and less costly recovery flow scheme is
required. A low C8 paraffin concentration allows the C8+ portion of the reformate to be separate
by distillation. High levels of C8 paraffins will require an extraction process.
2.2.8 Commercial Technology
2.2.8.1 UOP
UOP has designed and licensed more than 600 fixed bed plus 154 operating CCR Platforming™
units throughout the world ranging in size from 15,000 to 63,000 BPSD. UOP first introduced
its Platforming process using the first commercial platinum catalyst in 1949. The first generation
continuous catalyst regeneration (CCR) reformer was commercialized in 1971. The second
generation CCR technology characterized by very low pressure operation (approximately 50
psig) has been available since 1990, and a low platinum catalyst (R-34) version of UOP’s
standard reforming catalyst, R-32, is also available. UOP’s R-134 catalyst is its “standard” in
this area. The second generation CCR was commercialized toward the end of 1988 and has had
numerous units designed since.
2.2.8.2 Axens
Axens is the only other licensor to offer a continuous catalyst regeneration reformer. Its
Octanizing® and Aromizing™ processes are well tested with over 50 licenses awarded. The
Aromizing process (Aromatics mode) is a high severity process that uses a specially tailored
catalyst to produce chemical grade aromatics.
Axens’ latest innovation is the “dry burn loop,” and advanced regenerator design (RegenC™).
This new regenerator is claimed to provide longer catalyst life and reduced catalyst costs of 30 to
70 percent. Axens’ latest catalyst, CR 401, has demonstrated improved C5+ and hydrogen yield
and lower attrition levels.
Benzene/Toluene 34
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
2.2.8.3 Other
Semi-regenerative reformer designs are available for license from ExxonMobil (Powerforming)
and Engelhard (Magnaforming) as well as UOP and Axens. The Englehard (Magnaforming)
technology and technical service to these units has been transferred to Axens. ExxonMobil also
offers its cyclic reforming technology.
Chevron Phillips and BP are not presently licensing their reforming technology (Rheniforming
and Ultraforming, respectively).
Pyrolysis gasoline yields are determined by the severity of the cracking operation and the
composition of feedstocks. Pygas is only a byproduct of an olefin unit, so these two factors are
determined by the overall economics of the plant. The effects of feedstock on BTX yields are
summarized in Figures 2.5.
Figure 2.5
Effect of Steam Cracker Feedstock on Aromatics Yield
0.60
0.50
Ton Per Ton of Ethylene
0.40
0.30
0.20
0.10
0.00
Ethane Propane n-Butane Light Full Range Light AGO HVGO
Naphtha Naphtha
Benzene Propane n-Butane Light Naphtha
Q207_00101.0007.4106_char t s.xls
The effect of increasing severity of the cracker operation is to increase the yield of aromatics.
This is shown in Figure 2.6 for a full range naphtha (FRN) feedstock. The severity (defined by
the propylene to ethylene ratio) is varied from a high severity operation (P/E=0.48) to a medium
Benzene/Toluene 35
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
severity (P/E=0.59). The BTX content is lowered from 69 to 42 percent of the pygas and the
benzene drops from 39 to 19 percent. As the yield of ethylene is also increasing, the ratio of
aromatics to ethylene falls and then rises.
Figure 2.6
Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed
1.2
P/E=0.590
1.0
Ton Per Ton of Ethylene
P/E=0.540
0.8 P/E=0.516
P/E=0.478
0.6
0.4
0.2
0.0
High Standard Intermediate Medium
Benzene Toluene Xylenes Other
Q207_00101.0007.4106_chart s.xls
Pyrolysis gasoline contains significant quantities of diolefinic materials that, when left standing
for any period of time, tend to form gum, even at ambient conditions. The stream is therefore
hydrogenated prior to addition to the gasoline pool. This hydrotreater uses nickel or palladium
catalysts and requires a hydrogen source. The diolefins are converted to primary olefins, and the
product from the first stage hydrotreater is of motor gasoline quality.
If chemical grade aromatics are required, all olefins must be removed from the feed prior to
aromatics extraction. This necessitates a second stage hydrotreater operating under more severe
conditions to ensure complete saturation of the olefins. There are a number of possible
configurations of the two hydrotreatment stages and the two distillation columns, whose
selection depends on factors such as the cost of hydrogen and the destination of the other product
streams. In any case, the second hydrotreatment stage is needed only if aromatics are to be
extracted and the costs of this processing should be properly borne by the aromatic products.
A representative analysis for a first stage hydrotreated pyrolysis gasoline derived from naphtha is
given in Table 2.8.
Benzene/Toluene 36
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.8
Pyrolysis Gasoline Analysis
(weight percent)
Composition Minimum Maximum
C4s 0.0 1.0
Benzene 27.0 35.0
Toluene 15.0 25.0
Xylenes 4.0 9.0
Ethylbenzene 1.0 1.5
Styrene 0.0 0.5
Properties
Diene value 2 max
Existing gum 4 mg/100mL max
Gravity 0.75-0.82 gm/cc
Boiling range
IBP 40-60°C
50 Percent 80-100°C
FBP 170-200°C
RVP 0.4-0.6 kgm/cc
Viscosity 0.7-0.8 cP
Bromine number 20 gm Br/100 gm
RON 10
Sulfur 0.1 max
Azeotropic distillation, which uses a low boiling point solvent with an affinity for
nonaromatics. The solvent is distilled overhead with the nonaromatic raffinate.
Extractive distillation (ED), which employs a high boiling point solvent with an affinity
for aromatics. The influence that a solvent has on the boiling temperature of the various
components is shown in Table 2.9. The effect of the aromatics is significant. For
benzene the boiling temperature increases by almost 100°F, whereas for cyclohexane the
delta is about 13°F. Thus, the nonaromatics can be distilled overhead, whereas the
bottoms product will consist of solvent loaded with aromatics. The aromatics can then be
separated from the solvent by distillation. In the ED step, the light nonaromatics are
preferentially removed because of their lower boiling point, although this can be partly
compensated for by a high light/heavy selectivity of the solvent. As a result, the
aromatics product contains relatively small quantities of light nonaromatics. This means
that a benzene of reasonable quality may be obtained from C6-C8 cut, but the toluene and
Benzene/Toluene 37
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
xylenes would be poorer quality. For this reason, ED is normally used when the feed is a
heart cut of the appropriate boiling range.
Table 2.9
Extractive Distillation: Effect of N-Formylmorpholine Solvent on
Boiling Temperatures at One Atmosphere, °F
Pure Component 15% Component/
85% Solvent¹
Aromatics
Benzene C6H6 176.27 275.82
Toluene C7H8 231.16 321.27
Naphthenes
Cyclohexane C6H12 177.34 190.17
Methylcyclohexane C7H14 213.71 225.52
trans-1,2-Dimethylcyclopentane C7H14 197.32 209.49
cis-1,4-Dimethylcyclohexane C8H16 255.80 266.48
Paraffins
n-Heptane C7H16 209.91 218.65
n-Octane C8H18 258.17 132.46
2-Methylheptane C8H18 243.77 256.06
Olefins
4-Methyl-1-hexene C7H14 188.12 204.22
1-Hexene C6H12 145.20 148.90
1-Heptene C7H14 200.57 218.38
1-Octene C8H16 250.25 275.47
¹N-Formylmorpholine (NFM)
Liquid/liquid solvent extraction (LLE), which uses solvents that form a separate liquid
phase. Aromatics are considerably more soluble than nonaromatics in the solvents
employed. The aromatics are extracted from the feed stream in a liquid/liquid contactor,
and the extract stream is stripped to recover the aromatic product and the solvent. In this
case, the aromatic product would tend to be more contaminated by the light nonaromatics
that are preferentially stripped off in the second stage. For liquid/liquid extraction, a low
light/heavy selectivity is required (i.e. fewer light nonaromatics pass into the solvent).
Within each type, there are a number of solvents available. However, for a given process design
the solvent type is not replaceable. LLE is usually employed where recovery of benzene and
toluene are important with respect to yield and quality. ED is usually employed where the key
product is benzene and/or the yield is not so critical. Properties of various solvents are shown in
Table 2.10.
The complementary features of the ED and the liquid/liquid extraction systems are often
combined when extraction of the full BTX range is required. In this case, the extract from the
liquid/liquid stage passes to an ED column, where nonaromatics and some aromatics are
removed as overheads product, which recycles to the liquid/liquid extraction stage. The bottoms
product from the ED volume passes to a stripper to separate the purified aromatics and the
solvent.
Benzene/Toluene 38
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Table 2.10
Properties of Extraction Distillation Solvents
Sulfolane N-Methylpyrrolidone Dimethysulfoxide N-Formylmorpholine
(NMP) (DMS) (NFM)
Formula C4H8O2S C5H9NO H3CSOCH3 C5H9NO2
Molecular weight 120.6 99.13 78.13 115.13
bp @ 1.0 Kg/Cm2, °C 287 205 189 243
Freezing point, °C 27 -25 19 23
Flash point, °C 177 91 89 119
Miscible with water Yes Yes Yes Yes
Smell/odor Oil-like Faintly ominous None Very faint
Stability Good Very good Decomp @ 190°C Very good
Boiling point difference(1) 71 14 -- 26
Operating Conditions
Temperature, °C 100 20-40 20-30 180-200
Pressure, bar 2 1 1 1
Ratio of solvent to raw material 3-6:1 4-5:1 3-5:1 5-6:1
(1)
Benzene boiling point – methylcyclohexane bp (in the presence of solvent)
In general LLE processes are more capital intense and have higher utility requirements, but
produce a higher product yield and are suitable for BTX separation. ED processes have lower
capital requirements and lower utility requirements. The ED processes tend to give a lower
product yield and are suitable for benzene separation. LLE is normally selected where there is a
need for high quality, high yield of toluene, particularly for subsequent conversion (e.g., TDP).
Lurgi’s ArosolvanTM process for the recovery of BTX aromatics is such a system. The solvent is
a mixture of N-methylpyrrolidone (NMP) and water or monoethylene glycol or diethylene
glycol. This process has been commercial since the late 1950s.
UOP developed the UdexTM process jointly with Dow Chemical in the early 1950s. It used a
mixture of liquid/liquid extraction and distillation with solvents based on glycol.
In the early 1960s, UOP entered an exclusive licensing deal with Shell for a process based on
Sulfolane, or tetrahydrothiophene-1,1-dioxide. Some of Sulfolane’s advantages are its high
selectivity and high yield. The disadvantage of thermal instability at its boiling point is
Benzene/Toluene 39
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
countered by the addition of small quantities of water to depress the boiling point. More than 90
new Sulfolane units and eight conversions to Udex have been licensed to date, with a total
capacity in excess of 0.95 million barrels per day of feed.
Where only two components, such as benzene and toluene, are desired, there is the option of
cutting to a C6 and a C7 fraction and sending each to a separate ED system. Krupp Uhde offers
this approach via its Morphylane® process, based on N-formylmorpholine (NFM). For full BTX
extraction, however, Krupp Uhde offers a combined liquid/liquid plus ED process called
MorphylexTM based on the same solvent. Krupp Uhde has applied divided-wall column (DWC)
technology to its ED process and claims an energy savings of up to 35 percent and capital
savings up to 20 percent. (A dividing-wall in a vertical column permits two distillation steps to
be performed in one piece of equipment, with a reduced number of heat exchangers and
peripheral equipment items).
Reformate and pygas can be treated together in a BTX extraction unit. In the case of reformate,
a full C6+ cut is often treated, allowing recovery of xylenes. For pygas, a C6-C7 cut may be used
as feedstock because of the high proportion of less desirable ethylbenzene in the C8 aromatics.
The Sulfolane process is described as an example of a widely used technology, and a typical
flowsheet for a Sulfolane unit is shown in Figure 2.7. The capital investment requirements and
utility consumption for a sulfolane extraction unit is directly linked to the feedstock composition
and the particular needs of the client.
The reformate feedstock may be prefractionated if the purpose of the system is to remove only
selected aromatics, although, as described previously, the system is designed for full BTX
removal. The feed cut enters the extractor, which is typically a rotating disc contactor. The feed
flows upward countercurrent to a stream of Sulfolane solvent, where aromatic hydrocarbons are
selectively dissolved. Undissolved hydrocarbons, comprising mainly nonaromatics, are removed
from the top of the extractor as the raffinate phase.
The extract phase, or rich solvent, flows from the bottom of the extractor to the extract stripper.
This is the extractive distillation step, where light nonaromatics are stripped. Light nonaromatics
are condensed and returned as a reflux to the extractor since they contain some aromatics
unavoidably volatilized in the extract stripper. This extractive distillation step is a product purity
control; the light reflux, which displaces heavy nonaromatics from the solvents, is also
beneficial.
One of the features of the process is the ability to use a “secondary solvent.” Instead of all
solvent passing through the liquid/liquid extracting column, a portion of recycled solvent can be
bypassed to extractive distillation. This permits the promotion of high volatility nonaromatics in
extractive distillation while taking advantage of relatively high hydrocarbon loading in
liquid/liquid extraction.
The bottoms stream from the extract stripper contains the net aromatics product and the
Sulfolane solvent. This passes to the recovery column, where the aromatics are stripped from the
high boiling solvent. A light reflux reduces solvent carryover with the aromatics. High purity
aromatics are recovered as product, and the solvent is recycled. The aromatics product is clay
treated to remove residual contaminants that may affect the acid wash color test.
Benzene/Toluene 40
PERP 06/07-6
Q207_00101.0007.4106
Clean Condensate M/U
Section 2
CONDENSER CONDENSER
Raffinate
EXTRACTOR
C.W.
RECOVERY
COLUMN
RAFFINATE EXTRACT
WATER WASH STRIPPER HP
COLUMN Stm.
Depentanized
Feed
HP
MP Stm.
Stm.
PERP 06/07-6
Q207_00101.0007.4106
Solvent
Benzene/Toluene
HP
Stm.
REGENERATOR
WATER
STRIPPER
Figure 2.7
Shell/UOP Sulfolane Process
Current Commercial Technology
41
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Raffinate from the top of the extractor requires a water wash to recover dissolved solvent. It is
washed countercurrently with solvent free water before export. The solvent is recovered from
the water in a water stripper where the heat of evaporation is provided by indirect exchange with
hot lean solvent. Steam generated in the stripper supplies the extract recovery column. This is a
key feature of the heat integration of the process. Sulfolane degradation, primarily related to
oxidation loss, can be minimized by using proper gas blanketed feed and by reducing equipment
leakage. Intermittently, a regenerator distills solvent overhead and retains degraded material for
discharge.
The aromatics product stream passes to a distillation system to separate the benzene, toluene, and
xylenes products, as shown in Figure 2.8.
A block flow diagram for BTX recovery in conjunction with a liquid/liquid solvent extraction
unit is shown in Figure 2.11. The corresponding material balances for pygas and reformate feeds
are given in Tables 2.11 and 2.12, respectively. The one case (pygas) has a high benzene (34
percent) and low xylenes (13 percent) concentration. The other case (reformate) has a low
benzene (less than 6 percent) concentration and a high xylenes concentration (almost 20 percent),
typical of a reformer operating in a gasoline mode. The basis for the pygas is typical production
for a steam cracker employing a naphtha feed at standard severity (approximately 0.5 pounds of
propylene per pound of ethylene) at ethylene capacity of 1 billion pounds per year. The
optimum BTX fractionation design is based on work done by Chung et al.
Table 2.11
BTX Recovery Material Balance (Pygas)
Stream Number 1 2 3 4 5 6 7 8 9
DeC5 C9+
Stream Name Feed Ovhd Raffinate Extract Bz Drag Benzene Toluene Xylenes aromatics
Properties
Temperature, °F 104 105 105 105 178.1 120 120 120 120
Pressure, psia 72.5 30.0 140.0 140.0 15.0 45.0 55.0 20.0 45.0
Vapor Fraction 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
Mole Flow, Lb mol/hr 977 268 45 665 8 351 166 101 39
Mass Flow, Lb/hr 81,426 18,253 4,391 58,783 601 27,416 15,431 10,717 4,621
Volume Flow, cu. ft./hr 1,651 440 105 1,109 12 517 295 203 88
Composition, wt pct
C5 - 22.2% 98.9% 0.6% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%
C6-C8 non aromatics 5.9% 1.0% 99.4% 0.4% 35.1% 0.1% 0.1% 0.0% 0.0%
Benzene 34.2% 0.2% 0.0% 47.3% 64.9% 99.9% 0.1% 0.0% 0.0%
Toluene 18.9% 0.0% 0.0% 26.2% 0.0% 0.1% 99.8% 0.1% 0.0%
Xylenes 13.2% 0.0% 0.0% 18.3% 0.0% 0.0% 0.1% 99.8% 1.6%
C9 + 5.6% 0.0% 0.0% 7.7% 0.0% 0.0% 0.0% 0.1% 98.4%
Benzene/Toluene 42
PERP 06/07-6
Q207_00101.0007.4106
CONDENSER CONDENSER
Extract From
Section 2
Sulfolane Unit
CLAY TREATER
CHARGE TANK
Water To
BENZENE Sour Water
COLUMN Stripper
Benzene Drag
TOLUENE
COLUMN
Toluene
Benzene
HP CLAY
TREATER MP HP
Stm.
Stm. Stm.
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
XYLENES
COLUMN
Mixed Xylenes
Heavy Aromatics
Figure 2.8
Aromatics Fractionation Section
Current Commercial Technology
43
Q207_00101.0007.4106.vsd
Section 2
2
C5-
Feed 1 DEPENTANIZER
Raffinate
3
5
SOLVENT Bz Drag
H/T
EXTRACTION
6 Benzene
BENZENE
4 7 Toluene
COLUMN
TOLUENE
COLUMN
8 Xylenes
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
XYLENES
COLUMN
9 C9+ Aromatics
Figure 2.9
BTX Recovery Block Flow Diagram
Current Commercial Technology
44
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Table 2.12
BTX Recovery Material Balance (Reformate)
Stream Number 1 2 3 4 5 6 7 8 9
DeC5 Bz C9+
Stream Name Feed Ovhd Raffinate Extract Drag Benzene Toluene Xylenes aromatics
Properties
Temperature, °F 104 105 105 105 178.1 120 120 120 120
Pressure, psia 72.5 30.0 140.0 140.0 15.0 45.0 55.0 20.0 45.0
Vapor Fraction 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
Mole Flow, Lb mol/hr 1,457 268 45 665 5 90 219 245 132
Mass Flow, Lb/hr 133,342 18,294 45,396 69,669 391 7,062 20,356 26,034 15,823
Volume Flow, cu. ft./hr 2,846 440 105 1,109 8 133 389 494 302
Composition, wt pct
C5 - 19.1% 99.1% 16.3% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%
C6-C8 non aromatics 28.7% 0.9% 83.7% 0.1% 0.5% 0.1% 0.1% 0.1% 0.0%
Benzene 5.6% 0.0% 0.0% 10.7% 99.5% 99.9% 0.1% 0.0% 0.0%
Toluene 15.2% 0.0% 0.0% 29.2% 0.0% 0.0% 99.7% 0.1% 0.0%
Xylenes 19.7% 0.0% 0.0% 37.8% 0.0% 0.0% 0.0% 99.8% 2.2%
C9 + 11.6% 0.0% 0.0% 22.2% 0.0% 0.0% 0.0% 0.0% 97.8%
As noted previously, extractive distillation is often more appropriate for the extraction of a single
aromatic product from a heart cut than is liquid/liquid extraction. One distinct advantage that ED
has over LLE is that only two major towers (extractive distillation column and aromatics
recovery column) are required instead of four towers (extractor, wash column, stripper, and
recovery). Also, since a heart cut (C6/C7) is usually fed to an ED facility, the unit throughput is
usually less.
Lurgi, for example, offers its combined liquid/liquid and ED processes, Arosolvan, for full BTX
extraction; and its ED process, Distapex, for single aromatic components. The solvent used is
the same in both: N-methylpyrrolidone (NMP). Distapex is appropriate when the aromatics
component has a high concentration (e.g., 60-70 percent) in the feedstock cut. This makes it
suitable for the recovery of benzene or toluene from pygas. An ED system, such as Distapex, is
also suitable for extraction of aromatics from coke oven light oil, following a hydrorefining step
to remove impurities such as sulfur, nitrogen, and oxygen.
Benzene/Toluene 45
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
As described in Section 2.2, Krupp Uhde also offers its Morphylane® process, based on the
solvent N-formylmorpholine (NFM). This is aimed at feedstocks with high aromatics
concentrations. Others include UDEXTM (licensed by UOP) and GT-BTX® (licensed by GTC
Technology Corp).
The Morphylane® extractive distillation process has been modified for the recovery of aromatics
from catalytic reformate. This process, called Octenar®, can be used in a number of applications.
To upgrade the octane value of reformate, the Octenar® process can be used to separate an
aromatics-rich stream containing BTX. This stream is of lower purity than that of a system such
as Sulfolane, but is intended as a high octane blending component. Another variant involves
taking a portion of the benzene overhead from the extractive distillation column; the extract
passing to the stripper is high in aromatics and low in benzene, and is suitable for gasoline
blending.
In designing an extraction system, there are a number of options relating to whether and how the
reformate feed is precut – which will impact the need for fractionation after extraction to take a
benzene product stream. The process described here is a typical Octenar® system for extracting
an aromatics concentrate from a (C6-) reformate cut.
Figure 2.10 shows a simplified process flowsheet. The feedstock reformate is charged to the
extractive distillation column, and lean cool solvent enters the top. The nonaromatics leave in
the column overheads product, together with a small amount of aromatics and solvents.
The bottoms product from the ED column consists primarily of solvent and aromatics. This
flows by pressure differential to the aromatics recovery column, where the aromatics are
separated by distillation under vacuum. A portion of the condensed aromatics is refluxed to
achieve purity and reduce solvent carryover.
The overhead stream from the ED column is condensed and some is returned to the column as
reflux. No water wash is applied to the raffinate. A solvent recovery column is not included in
this design. The total solvent loss by all means is quoted as approximately 22 ppm, expressed on
the benzene steam.
Extensive use is made of the heat content of the hot solvent from the stripped column. It
provides part of the heat load for the ED column and the stripper column itself.
A side stream of hot lean solvent is intermittently fed to a solvent regeneration unit, where it is
distilled from high boiling decomposition products under vacuum before being returned to the
solvent circuit. A solvent drum, supply pump, and drain tank are also required, although not
shown on the diagram.
Benzene/Toluene 46
PERP 06/07-6
Q207_00101.0007.4106
Nonaromatics
Section 2
PREFRACTIONATION
COLUMN
Benzene
EXTRACTIVE
DISTILLATION
COLUMN
AROMATICS
RECOVERY
COLUMN
Reformate
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
HP
Steam
LP
Stm MP
Stm
C7+ Fraction
Figure 2.10
®
Morphylane Extractive Distillation
Process Flow Diagram
Current Commercial Technology
47
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Table 2.13
Benzene Product Quality from the Octenar® Process
2.5.2 Hydrodealkyation
A summary of hydrodealkylation processes is shown in Table 2.14.
Table 2.14
Hydrodealkylation Processes
Process Process
Company Name Type Feedstock
UOP/Marathon Ashland Petroleum Hydeal Catalytic Toluene/higher aromatics
Houdry(1) Detol® Catalytic Toluene/higher aromatics
HRI/Axens HDA Thermal Toluene/higher aromatics
Gulf THD Thermal Toluene/higher aromatics
Houdry(1) Pyrotol® Catalytic Pygas/reformate
Mitsubishi MHC Thermal Pygas/reformate
Houdry(1) Litol® Catalytic Light oil
UOP THDA Catalytic Toluene/higher aromatics
(1)
Licensing rights held by ABB Lummus Global
Benzene/Toluene 48
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
All the commercial processes involve the same basic chemistry. For toluene, the reaction is as
follows:
C6H5CH3 + H2 C6H6 + CH4
Q207_00101.0007.4106.cdx
Similar reactions occur with higher alkylated benzenes. Xylenes dealkylate in two steps,
whereas ethylbenzene dealkylates directly to benzene and ethane. Side reactions result in the
formation of diphenyls or polymers. These are normally burnt as fuel with the offgas. Around
83 percent of the toluene is ultimately converted to benzene product, and the balance is lost to
fuel. No solvent extraction of benzene is necessary and high purity benzene may be recovered
by simple distillation. Small quantities of sulfur compounds are eliminated; the hydrogen sulfide
leaves in the gaseous effluent.
Dealkylation processes may be catalytic or thermal. Typical operating conditions for the
catalytic type are 575°C to 650°C and 25-60 bar. A higher temperature, of up to 760°C, is used
in the thermal processes. The basic process flowsheet is similar for both. Hydrogen-rich gas is
recycled to control the temperature in the exothermic reaction stage. The liquid product is
stabilized with the removal of light ends, clay treated, and fractionated to produce the benzene
product. Toluene and heavies are recycled.
ARCO and Hydrocarbon Research developed the HDA thermal process, operating at low
concentrations to give greater benzene yields. The THD process developed by Gulf is similar.
These processes are suitable for the conversion of process streams that consist substantially of
aromatics such as toluene from BTX separation.
Bulk dealkylation is also practiced. In the Houdry Pyrotol® process, the nonaromatics content of
the feed can be up to 30 percent. The process uses a pretreatment reactor for the selective
hydrogenation of olefinics. Pyrotol® can be used for the bulk dealkylation of pyrolysis gasoline.
It requires more hydrocracking of the non-aromatics than the Litol® process (see below), but a
smaller amount of desulfurization, as well as a comparable amount of hydrodealkylation.
The Mitsubishi MHC process is a thermal process that also handles feeds with significant
nonaromatics components. Hydrogen of relatively low purity may be used, reducing the makeup
requirements.
Another variation is required for recovery of benzene from coke oven light oil. The Houdry
Litol® process uses a pretreatment reactor in a fashion similar to the Pyrotol® process, and
produces a polymer residue stream. Another important requirement is to hydrogenate sulfur and
nitrogen impurities that are present in higher quantities than in other feedstocks.
To illustrate the technology employed, the three Houdry dealkylation processes are briefly
described. The economics of dealkylation of pyrolysis gasoline and coke oven light oil are
included in the sections on economics later in this report.
Benzene/Toluene 49
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
The heated mixture flows through the first reactor where a portion of the dealkylation reaction
occurs. Since the net effect of the reaction is a temperature rise in the reactor, the first reactor
effluent is quenched by a portion of cold recycle gas before it is sent to the second reactor. In
large plants, additional reactors are employed in order to maximize catalyst utilization.
The effluent from the last reactor is cooled by exchange with reactor feed and stabilizer feed, and
is used to supply reboiler heat to the stabilizer and benzene tower. Final cooling and partial
condensation of the effluent is done in the air cooled condenser.
The overheads gas from the stabilizer is chilled so that benzene is recovered and returned to the
stabilizer reflux drum. The remaining vapor is vented.
The stabilizer bottoms product is pumped directly to the clay treaters. These vessels contain clay
beds, which, through polymerization and adsorption, serve to remove trace impurities from the
aromatics product. Two reactors are provided to be run in either parallel or series flow. Each
reactor can be dumped and reloaded while the other treater remains on stream.
Benzene/Toluene 50
PERP 06/07-6
Q207_00101.0007.4106
Section 2
MAKEUP
HYDROGEN
STEAM
BFW
FRESH
RECYCLE
FEED REACTOR
GAS
COMPRESSOR
FUEL
GAS
REACTOR CONDENSOR
H PURIFICATION
2
FLASH UNIT
DRUM
CLAY TREATERS
RECYCLE
PERP 06/07-6
TOLUENE
Q207_00101.0007.4106
Benzene/Toluene
AND CHILLER
HEAVIER
FUEL
GAS BENZENE
PRODUCT
STABILIZER BENZENE
TOWER
Figure 2.11
Detol® Unit Simplified Flowsheet
Current Commercial Technology
51
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Product Recovery
The clay treated aromatics are charged to the benzene tower. This tower produces a high purity
overheads benzene product, a toluene and heavier bottoms product that also contains crude
diphenyl, and a small amount of benzene. The overheads benzene product stream is cooled and
pumped to storage. Most of the bottoms stream is recycled to extinction; a small part is used in
the hydrogen purification unit.
Catalyst Regeneration
Catalyst regeneration is required occasionally to restore the catalyst to its original activity.
Regeneration of the reactors occurs in an inert atmosphere, with air bled into an inert
recirculating stream at a controlled rate to control temperature in the reactors. The unit is
offstream during these periods. In addition to the equipment common to normal operation,
regeneration requires a source of nitrogen for purging and a source of compressed air or oxygen
for the regeneration itself.
The light oil is first prefractionated to remove material heavier than C8 aromatics. The top
product has a nominal end point of 150°C. The aromatics recovered from the stabilizer
overheads product are added to this cut. The total feed is pumped to reactor pressure, preheated,
and passed to the vaporizer.
In the vaporizer, a part of the preheated hydrogen recycle stream is used to vaporize the feed. A
small amount of high boiling polymer is formed, returned to the prefractionator tower, and leaves
with the bottoms product. Vaporized feed is mixed with the remaining recycle hydrogen and
enters the pretreatment reactor, which hydrogenates materials that would form coke and severely
reduce the onstream life of the catalyst in subsequent reactors.
The pretreated feed stream is combined with recycle from the bottoms product of the benzene
tower and brought to dealkylation reaction temperature in a fired heater. The heater effluent
flows through the first reactor, thus purifying the aromatics through conversion of sulfur and
nitrogen compounds to hydrogen sulfide and ammonia, and by hydrocracking the nonaromatics.
In this reactor some benzene is formed from a portion of the higher homologs (e.g. toluene, C8
aromatics) that are dealkylated. Since the net effect of the reactions results in a temperature rise,
the effluent from the first reactor is quenched by a cold hydrogen recycle gas stream from the
high pressure flash drum (via the recycle gas compressor). The effluent then flows to the second
reactor where similar heat release occurs due primarily to the dealkylation reactions. The reactor
inlet temperatures are increased gradually through the cycle to maintain the desired production
rates and product purity.
Benzene/Toluene 52
PERP 06/07-6
Q207_00101.0007.4106
Section 2
TO ATMOS
PRETREATMENT
REACTOR
PREFRACTIONATOR
TOWER
REACTOR REACTOR
LIGHT VAPORIZER
OIL HP
STEAM
BFW
PREFRAC
BOTTOMS
MAKE UP
CHILLER RECYCLE H
BENZENE 2
FUEL COMPRESSOR
TOWER GAS HYDROGEN
COMPRESSOR
VENT
BENZENE GAS
CAUSTIC
PERP 06/07-6
FLASH
Q207_00101.0007.4106
PRODUCT
Benzene/Toluene
DRUM
STABILIZER
CAUSTIC
TREATER
CLAY TREATERS
Figure 2.12
Litol® Unit Simplified Flowsheet
Current Commercial Technology
53
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Heat is recovered from the hot reactor effluent by raising steam and by several process heat
exchangers before being partly condensed and flashed. Part of the flashed vapor is taken as an
effluent to remove hydrogen sulfide and light hydrocarbons from the circuit. There may be
recovery of aromatics from this purge stream. The remaining vapor is mixed with compressed
hydrogen; some is used to cool the effluent from the first reactor and the remainder is mixed with
the feed to the pretreatment reactor.
As with the Detol® process, the liquid from the flash drum is stabilized and the overheads
product is chilled to recover benzene. The stabilizer bottoms product is clay treated and sent to
the benzene tower. The bottoms product from the benzene tower is recycled and added to the
pretreated reactor feed.
The product benzene is treated with dilute sodium hydroxide to wash out trace sulfur
contaminants.
2.5.2.3 Pyrotol®
Houdry’s Pyrotol® process is primarily aimed at the dealkylation of aromatics within a pyrolysis
gasoline stream.
The flowsheet of the Pyrotol® process fed by raw pyrolysis gasoline is very similar to that of the
Litol® process, with feed prefractionation as necessary.
The feed is prefractionated to depentanize and to remove at least part of the C9+ components.
The feed cut is vaporized and passed to a pretreatment reactor where dienes, cyclodiolefins, and
styrene are selectively hydrogenated. In the Pyrotol® reactors, aromatics are dealkylated to
benzene. Other reactions include the cracking of nonaromatics to light hydrocarbons, primarily
C1 to C3, and desulfurizing. Unreacted toluene and heavier aromatics are recycled to the reaction
stage.
2 +
CH3
Q207_00101.0007.4106.cdx
Some processes also accept C9 feedstock, from which xylenes are produced via transalkylation.
The advantage of disproportionation lies in its high conversion to liquid products and its low
consumption of hydrogen compared to dealkylation. It also provides a means of producing
Benzene/Toluene 54
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
xylenes from feedstocks such as pyrolysis gasoline, where the C8 cut is relatively small and has a
high proportion of ethylbenzene.
Processes have been available for licensing since the early 1970s, but most are now licensed by
either UOP (TatorayTM) or Axens (ExxonMobil’s MTDP-3); the latter is available for license
only in grassroots aromatics complexes. Revamps and individual units are still licensed through
ExxonMobil.
Although ExxonMobil's MTDP-3 process can handle C9 aromatics on a limited basis, UOP
claims that its Tatoray process can handle up to 100 percent C9 aromatics and has operated
commercially with up to 10 percent C10 aromatics in the feed. ExxonMobil has developed and
commercialized a heavy aromatics transalkylation process, TransPlusSM, which can handle up to
100 percent C9+ with up to 25 percent C10 aromatics. This process was developed with CPC of
Taiwan and commercialized in June 1997. UOP and Toray have entered into an agreement to
further commercialize the latter’s TAC-9 process. This technology produces a high yield of
mixed xylenes from feeds containing up to 100 percent C9 and C10 aromatics. Pilot work by
Atofina on its T2BX process indicates that this unit also could run with heavy aromatics in the
feed, at up to 25 percent.
Increasing the content of heavier aromatics in the feed increases the formation of heavy products,
which reduces the overall yield of benzene and xylenes. It does increase, however, the yield of
xylenes relative to benzene, and the optimum C9 aromatics concentration ranges from 40 to 60
percent of the feedstock depending on economics.
One of the disadvantages of toluene disproportionation is that the xylenes product is usually an
equilibrium mix of isomers, which does not correspond to the split of market demand. Both
UOP and ExxonMobil offer Selective Toluene Disproportionation processes, which produce a
xylenes stream with around 90 percent of para-xylene, the desired isomer. Details of these
technologies were discussed in PERP report 05/06-8, Xylenes.
The toluene disproportionation processes of the different licensors are similar. A typical process
is shown in Figure 2.13 and described below.
Dry toluene feed with recycle gas is preheated by indirect heat exchange with reactor effluent,
and by a fired heater, before entering the catalytic reactor. The reactor product is cooled and sent
to a phase separator. Most of the hydrogen-rich vapor phase is recycled with a small purge to
maintain the appropriate hydrogen partial pressure in the reactor. The separator liquid is
stabilized to remove minor quantities of light ends and is clay treated to remove trace olefins.
The reactor conditions vary with the proprietary process, but are typically 40-45 bar and 320-
350°C. The ExxonMobil Selective Toluene Disproportionation process operates at 22-35 bar
and 400-470°C with initial coking pretreatment at higher temperature and pressure.
Benzene/Toluene 55
PERP 06/07-6
Q207_00101.0007.4106
Section 2
Purge
Gas
Light
Ends
CW
Gas
REACTOR
SEPARATOR
STABILIZER
FIRED
HEATER RECYCLE
COMPRESSOR
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
Steam
CW
CLAY Product
TOLUENE FEED TREATER Stream
FEEDSTOCK DRYERS
Figure 2.13
Toluene Disproportionation
Typical Flowsheet
Current Commercial Technology
56
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Light oil arises as a byproduct in the coking of coal, largely to provide a carbon source in steel
making. To make coke, coal is pyrolyzed at around 1,000°C; temperatures vary widely in
practice. About 70 percent of the product is solid coke, consisting primarily of carbon. The
remainder is volatilized, and leaves through the top of the coke ovens. This gaseous stream is
fractionated, and its cuts are used in various ways:
A light hydrocarbon gas, around 20 percent of the product, is recycled to fire the coke
ovens.
Ammonia is less than 0.5 percent of the product.
Coal tars, around 4 percent of the product, are separated and refined to yield polycyclic
compounds such as naphthalene, anthracene, pyridine, and phenanthrene.
Crude benzole, or coke oven light oil, is about 1 percent of the product.
Crude benzole is recovered by washing the gaseous stream, already cooled to 25-35°C (77-
95°F), with a petroleum fraction with a boiling point of 300-350°C (572-662°F). The petroleum
wash is then recovered by steam distillation and recycled.
Table 2.15
Typical Composition of Benzole
(Weight percent)
Benzene 60-70
Toluene 12-16
Xylenes 4-8
Styrene 2-4
C5-C8 nonaromatics 5-9
Carbon disulfide 0.4-0.6
Sulfur compounds 0.5-0.7
C9 hydrocarbons 2-3
Coke Oven Light Oil (COLO) is a byproduct of coke manufacture from coal. The oil derived is
a foul smelling amber liquid composed of mononuclear aromatic hydrocarbons, olefins, styrene,
sulfur, and nitrogen compounds, etc. The Lyondell process requires: (1) two-stage hydrotreating
reaction, which saturates of diolefins, styrene, mono-olefins and converts sulfur nitrogen
compounds to H2S, NH3 respectively. (2) Fractionation removes light ends, produces a
concentrated aromatics stream for downstream aromatics extraction. This unique process
Benzene/Toluene 57
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
operates at lower temperature and pressure than competitors and recovers the maximum possible
quantity of benzene from COLO, with minimum aromatics loss due to saturation.
Asahi Chemical’s Alpha Process, which has been operating at the company’s Mizushima
complex in Okayama, Japan, since 1993, employing an olefinic feed (licensed by Stone
& Webster).
The first commercial operation of BP/UOP’s CyclarTM Process was in 1999 at Saudi
Basic Industries Corporation (SABIC).
CP Chem’s Aromax® Process, which is operating at its Pascagoula refinery, at Saudi
Chevron Phillips Chemical using a second generation Aromax® catalyst and CEPSA,
Spain.
UOP’s RZ PlatformingTM process started up its first commercial unit in second quarter
1998.
2.7.1.1 Chemistry
The proposed reaction mechanism has light olefins such as pentenes, butenes, and propylene
forming from paraffinic material by dehydrogenation and/or cracking. This is followed by
oligomerization, cyclization, and dehydrogenation to aromatics. Along with oligomerization, the
olefins disproportionate rapidly and redistribute to an equilibrium composition. Therefore,
almost the same BTX distribution is obtained in the product irrespective of the feed composition.
Temperature is more of a factor in determining the BTX distribution. The rate controlling step in
these reactions is the dehydrogenation and cracking of paraffins that require a large amount of
energy.
Benzene/Toluene 58
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Olefins are the preferred feedstock although paraffins can be handled. An olefinic feed allows a
simpler design. The more paraffins in the feed, the more catalyst and energy required. Diolefins
promote coking and deactivation. Thus, selective dehydrogenation of the feed may be required
upstream.
The feed is preheated in the feed/effluent heat exchanger. Final reactor inlet temperature is
obtained by a fired heater. The reactor effluent is cooled first against feed, followed by water
and refrigerant. The liquid product is then separated and sent to a stabilizer column, where the
C5 and lighter hydrocarbons are separated from the BTX components. No further treatment is
required before feeding the BTX to an aromatics plant. The light hydrocarbon byproducts (C5-)
are almost pure paraffins and are very good steam cracker feedstocks.
The first commercial plant with a capacity of 3,500 BPD has been operating since July, 1993 at
Sanyo’s Mizushima plant in Okayama. The feed is a C4/C5 raffinate, which is approximately 50
percent olefins.
The catalyst is a sphere consisting of a proprietary zeolite incorporated with a non-noble metal
promoter in an inert binder. The zeolitic component in the catalyst provides acidity, and the
metal promoter combines with the zeolite to provide dehydrogenation activity. The inert binder
and shape-selective properties of the zeolite retard the formation of coke. UOP claims that 30
percent less catalyst is required with second generation catalyst.
Benzene/Toluene 59
PERP 06/07-6
Q207_00101.0007.4106
Section 2
Fuel Gas
3-7 500-
kg/cm2 550°C
REACTORS
C.W.
FEED/EFFLUENT
HEAT STABILIZER
EXCHANGERS Light
FIXED HEATERS
Paraffin
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
CATALYST
REGENERATOR
C.W.
Refrigerant
Feed Aromatics
Figure 2.14
Alpha Process Flow Diagram
Current Commercial Technology
60
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
Olefins By-products
Q207_00101.0007.4106-1.cdx
UOP offers two alternative designs: the low pressure design that produces the maximum
aromatics yield; and high pressure design (but still less than 100 psig) that requires only half the
catalyst and therefore has a lower investment (approximately 25 percent less) and lower
operating costs. However, the high pressure design produces about 20 percent less aromatics
product than the low pressure design. UOP’s Continuous Catalyst Regeneration (CCR)
technology is employed for the reactor design. A process flow diagram for the CyclarTM Process
is shown in Figure 2.15.
Fresh feed is combined with a small recycle stream consisting of unconverted feed. After being
heated to the required reactor inlet temperature, the stream is converted to aromatics in a series
of four reactors with interstage heating. This configuration allows high conversion despite the
highly endothermic nature of the CyclarTM reaction. The reactors are low pressure drop, radial
flow, and stacked to allow gravity flow of the catalyst between reactors, as in the UOP
Platforming process and the CCR system. The effluent from the fourth reactor exchanges heat
with the combined feed, is cooled, and partly condensed. Liquid form the low pressure separator
is recovered and fed to a stripper where C6 and heavier aromatics are recovered as a bottoms
product.
Aromatics from the stripper bottoms are sent to a conventional, three tower BTX distillation train
where individual cuts of benzene, toluene, and mixed xylenes are distilled overhead. C9+
aromatics are recovered from the xylenes tower bottoms. The combined toluene and C9s could
be sent to a toluene disproportionation (e.g. Tatoray) unit, which would convert these to mixed
xylenes. The mixed xylenes could further be processed in a Parex-type unit to produce para-
xylene.
Vapor from the low pressure separator is compressed and sent to a gas recovery section where
hydrogen and light byproducts are separated from the unconverted feed. The unconverted feed is
recycled to the reactors along with the stripper overheads. The small amount of aromatics that
are recovered in the gas separation section are also sent to the stripper.
Benzene/Toluene 61
PERP 06/07-6
Q207_00101.0007.4106
Section 2
STACKED
REACTORS
CONTINUOUS CATALYST
REGENERATION SECTION
Hydrogen
Net
LP Fuel Gas
SEPARATOR
BOOSTER
COMPRESSOR
GAS
From
Reactor RECOVERY
SECTION
C.W.
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
Recycl e To R eactor
STRIPPER
LPG
C6+
Aromatic
Produc t
Figure 2.15
UOP/BP CyclarTM Aromatization
Process Flow Diagram
Current Commercial Technology
62
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
The hydrogen stream could be recovered in several ways, depending on the purity desired, and
the economics:
Catalyst flowing from the final reactor is transferred by lift gas to the top of the regeneration
tower where it is separated from the lift gas and proceeds by gravity flow through the
regenerator. Operating conditions that fully restore catalyst performance and protect the catalyst
from hydrothermal damage are established. Regenerator catalyst inventory is limited to a small
fraction of what is required in the reactor.
The regenerated catalyst proceeds through small transfer lines into flow control and surge
hoppers and finally into the regenerator lock hopper. Lift gas then transports the catalyst back to
the top of the first reactor in the stack, thus completing the catalyst circuit. Catalyst movement is
very gradual, with the rate controlled at the outlet of the regeneration tower. From this control
point, level control devices regulate all catalyst transfers. The catalyst from the fourth reactor
allows a constant and high level of catalyst activity and selectivity to be maintained in the
reactors. This steady-state catalyst condition eliminates the need for changes in process
temperatures to compensate for catalyst deactivation that might be typical of a semiregenerative
type reformer.
The desired conversion level, yield, and product quality are continuously maintained. The
regenerator section is sized to be compatible with a wide range of plant capacities while
maintaining the desired optimal steady state catalyst quality in the reactor.
The reactor and regenerator are independent. Each operates at its own ideal set of conditions.
Individual reactors do not cycle between reaction and regeneration conditions. This simplifies
metallurgy, heater sizing, and hydraulics since these can be designed for specific duties.
Although the aromatization reaction sequence involves some exothermic steps, the
preponderance of dehydrogenation and cracking reactions causes the overall reaction to be
highly endothermic. The reaction product is separated into hydrogen and light byproduct (for
fuel) with unconverted alkanes recycled to extinction. In this example the hydrogen purity of the
net hydrogen stream is 95 percent (via a cold box). The aromatics product is very rich in BTX.
Typically, the level of nonaromatics is less than 0.1 percent. This means that solvent extraction
is not needed to meet most product specifications.
Benzene/Toluene 63
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
One of the major drawbacks of this process is the high yield of toluene, which is of the lowest
commercial value of the three major aromatics. The toluene could be further processed in a
disproportionation unit to produce benzene and mixed xylenes. The mixed xylenes could further
be processed in a separation unit to produce the desired end product, para-xylene.
A general flow scheme for an Aromax® unit is shown in Figure 2.16. The feed must be very
effectively desulfurized to ensure that catalyst activity is maintained throughout the run. A
typical residual sulfur level of less than 0.1 ppm is cited by Chevron Phillips Chemical (CP
Chem).
CP Chem has developed a two stage proprietary sulfur and water control system that is shown
inside the dotted box in the figure.
The first stage absorber, containing a supported cupric oxide adsorbent, operates at about 300°F
to adsorb residual hydrogen sulfide form the stripped feed; the second stage reactor/absorber
operates at a high temperature in the presence of recycle hydrogen to remove the last traces of
sulfur-containing species from the feed naphtha.
The reforming section is a fixed bed design requiring on site regeneration once per year. The
refrigeration section has been added to reduce benzene losses in the separator drum overhead gas
to an acceptable level. Countercurrent liquid extraction could also be used for this step. The low
pressure operation (100 psig reactor outlet pressure), narrow boiling range of the feedstock, and
high hydrogen yield make liquid benzene recovery more difficult. The recycle gas dryer is
assumed to also contain a portion of sulfur adsorbent material to keep the sulfur content in the
recycle to a very low level.
Recycle gas is circulated by a centrifugal compressor that compresses the gas to suitable pressure
for recontacting in the upstream absorber/deethanizer for BTX and LPG recovery. The separator
liquid is sent to a debutanizer where the C4 material is separated and sent overhead to the
absorber/deethanizer for LPG recovery. A C5-rich side stream may also be withdrawn here to
purge out any accumulation of C5 material that may be present either because it was not
recovered in the upstream fractionation facilities or generated via cracking reactions in the
reaction section.
Benzene/Toluene 64
PERP 06/07-6
Q207_00101.0007.4106
Section 2
Hydrogen
Rich Gas To
Absorber /
Deethanizer
SULFUR RECYCLE/MAKE GAS
CONTROL REFORMING COMPRESSOR
REACTOR REACTORS
Lt. AND C4 & Lighter
Naphtha To Absorber /
FURNACES
Deethanizer
RECYCLE GAS
DRYER/SULFUR
TRAP
C5 To
Gasoline Blending
FEED ( If Required )
PREHEATER
FEED/EFFLUENT DEBUTANIZER
EXCHANGER
SULFUR
PERP 06/07-6
Q207_00101.0007.4106
ABSORBER
Benzene/Toluene
C.W. Refrig.
CONDENSERS BTX
Product
PRODUCT
SEPARATOR
Raffinate Recycle
from BTX Extraction
Figure 2.16
®
Aromax (Chevron Phillips ) Paraffins to
BTX Process Flow Diagram
Current Commercial Technology
65
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
The debutanizer bottoms stream is routed to the BTX extraction unit where product is extracted
and unconverted paraffins are recovered for recycle to the Aromax® reformer.
A summary of the design parameters for the Aromax® process is shown in Table 2.16.
The product mix depends on the feedstock. Feeds containing C6 through C7 components will
produce benzene and toluene, whereas a C6 through C8 feed will produce xylenes as well. The
feed cut points and resulting product mix are shown in Table 2.17.
Table 2.16
Aromax® Reforming Design Parameters
Table 2.17
Aromax® Product Mix versus Feed Cut Point
Feedstocks to the reforming unit using the RZ-100 catalyst can range from extraction unit
raffinates to BTX naphthas. Most streams will require hydrotreating and rerunning to remove
the C5s before processing in the RZ-100 unit. Although the RZ-100 catalyst is similar in many
ways to conventional reforming catalyst, it differs greatly in the production of benzene and
toluene. The selectivity of RZ-100 for these light aromatics is greatly improved over
conventional catalyst.
Figure 2.17 shows a process flow diagram of the UOP’s RZ PlatformingTM process.
Benzene/Toluene 66
PERP 06/07-6
Q207_00101.0007.4106
Section 2
Steam
FIRED HEATERS Fuel
Gas
LPG
STABILIZER
REBOILER
Net
PERP 06/07-6
Q207_00101.0007.4106
Benzene/Toluene
Hydrogen
HYDROGEN
RECYCLE
COMPRESSOR
HYDROGEN
Raffinate & SEPARATOR
Hydrotreated
Naphtha C 6+ Feed
From Depentanizer
Figure 2.17
UOP RZ-Platforming Process
Flow Diagram
Current Commercial Technology
67
Q207_00101.0007.4106.vsd
Section 2 Current Commercial Technology
An RZ PlatformingTM unit can be used in parallel with a second conventional reforming unit to
optimize the production of desired aromatics by processing different fractions of the hydrotreated
feed. In such cases, the conventional reformer can be dedicated to processing the heavier feed
fraction, taking advantage of its ability to produce xylenes.
A light naphtha stream, which is rich in C6 and C7 components, can be routed to the RZ
PlatformingTM unit, where selectivity for converting light paraffins to benzene and toluene is
greater. A reformer raffinate stream could also be recycled to the RZ unit.
The RZ process is identical to other semi-regenerative (SR) reformer processes. Feed from the
hydrotreater and raffinate from the sulfolane unit are treated in a sulfur guard bed. The feed is
then combined with recycle hydrogen, preheated by exchange with reactor effluent, heated to
reaction temperature by a charge heater, and passed to the first reactor.
Since endothermic reactions cause the temperature to decrease, the effluent is reheated to
reaction temperature and sent to the second reactor. Effluent from the second reactor is reheated
and sent to the third reactor and so on. Effluent from the last reactor is cooled before being
passed to the products separator drum.
Products separator gas, which is hydrogen-rich, is compressed and combined with fresh feed to
the unit. Net gas is taken from the products separator and compressed in a two stage
countercurrent recontacting scheme that maximizes recovery of C5+ liquids to the fractionation
section. This also increases the purity of the byproduct hydrogen stream.
Benzene/Toluene 68
PERP 06/07-6
Q207_00101.0007.4106
Section 2 Current Commercial Technology
Figure 2.18
Aromatics Distribution in Non-Conventional Routes
100%
80%
60%
40%
20%
0%
CCR CYCLAR RZ AROMAX ALPHA
PLATFORMING
Benzene Toluene Mixed Xylenes C9+ Aromatics
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene 69
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
Since the last PERP report on this subject there have been numerous patents and patent
applications dealing with the production of aromatics. A majority of these have been awarded to
the two major licensors of aromatics technology, namely UOP and IFP (Axens). Nexant has
reviewed the recent developments for the production of benzene and toluene. The more
interesting developments are discussed in this section.
In their patents (U.S. Patent 6,372,680 and 6,489,528), 10 g of SAPO-34 was mixed with 10 g of
colloidal silica solution and the mixture extruded into 1/16"-diam pellets and dried at room
temperature. The dried pellets were then calcined at 538°C (1000°F) for 6 hours. For the
second-stage catalyst, 28 g of HZSM-5 was mixed with 2.8 g of zinc hexaborate and 32.4 g of
colloidal silica solution. The mixture was then extruded into 1/16"-diam pellets, dried, and
steamed for 650°C (1202°F) for 4 hours.
To demonstrate the requirement to use the two catalysts in sequence, runs using each catalyst
alone were performed first. A MeOH–H2O feedstock (20:80 mole ratio) was passed through a
stainless steel tube reactor containing the SAPO-34 catalyst at 450°C (842°F) and 0 psig at a rate
of 25 mL/h. After 7.2 hours on stream it was found that MeOH was 100 percent converted, but
no aromatics were formed. A similar experiment was performed using only the zeolite catalyst.
Again, 100 percent conversion of the MeOH was achieved, but with only ~1 percent selectivity
to aromatics.
A third experiment was run with both catalysts placed in sequence in the tubular reactor (SAPO-
34 was the upper catalyst) and run under the conditions described above. This time, dramatically
different results were obtained. With 100 percent MeOH conversion, 31.3 wt percent selectivity
to aromatics was achieved with a very high 81 percent of the aromatics being xylenes.
Interestingly, if the two catalysts are physically mixed, then only about 10 wt percent selectivity
to aromatics is achieved. It should be kept in mind that MeOH "contains" 56 wt percent water
and only 44 wt percent hydrocarbons. Thus, the maximum weight yield of aromatics that could
be achieved is ~42 percent.
Unfortunately, the patent does not give enough information to truly understand the mechanism of
this unusual catalysis. For instance, in the runs that used only the individual catalysts, the patent
Benzene/Toluene 70
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
does not reveal what products are formed from the complete conversion of the MeOH. It can be
surmised that the likely products are mostly olefins because SAPO-34 is the key catalyst in the
UOP/Hydro Methanol to olefins (MTO) process. Then, exposure of the formed olefins to the
zeolite catalyst could convert them to aromatics à la Mobil's MTG process that used ZSM-5.
Japan’s Mitsui Chemicals Inc. said it will open a research and development center on
Singapore’s Jurong Island to develop a catalyst to produce benzene from natural gas.
The company aims to produce at least 600 kta of benzene from gas after about 5 years of
R&D.
Mitsubishi Chemical has established an industrial process for producing benzene and
hydrogen from coke oven gas (COG) and carbon dioxide (CO2) contained in plant waste
gas. The company plans to start constructing a 150-250 kta benzene plant based on the
process as early as 2008.
Details about the Mitsui and Mitsubishi technologies are not yet available. However, Conoco
Phillips Company was awarded a patent (U.S. patent 6,552,243) for a catalyst and process for
producing aromatics from methane. This patent comprises an invention for the non-oxidative
aromatization of methane using a crystalline aluminosilicate molecular sieve catalyst exhibiting a
high conversion and a high selectivity to aromatics hydrocarbons such as benzene, toluene,
xylene and naphthalene.
The catalyst exhibits the MFI crystal structure (e.g., ZSM-5) and has a silica-to-alumina ratio of
about 50:1. In addition the crystalline aluminosilicate has the external surface acidity selectively
passivated by means of an amorphous silica layer.
The process comprises a one or multiple fixed-bed reactors in series that contacts a methane feed
stream with the catalyst at the preferred temperature of 675-750°C (1247-1382°F), at a preferred
pressure of between 0.5 and 2 bar and a preferred weight hourly space velocity (WHSV) of 0.1-4
hr-1. In the multi-stage design the products are recovered by means of an intermediate separation
step between the reactors. At the same time hydrogen is removed from the intermediate stream
in order to drive the reaction toward completion. Low molecular weight hydrocarbons can be
recycled to extinction. Hydrogen can also be recycled.
The patent examples show methane conversions as high as 25 percent and aromatic yields (C6-
C10) as high as 15 percent, but only for short periods. After about an hour the conversion and
yields drop significantly to 15-20 percent and 7-8 percent, respectively.
Benzene/Toluene 71
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
The yields from an Advanced Pygas Upgrading Unit (APU) are compared with those from an
extraction unit in Table 3.1. A quick analysis shows that the gain in BTX is about 6.5 weight
percent when employing the APU technology.
Table 3.1
APU Yields and Products
(kmta)
The historical pricing of benzene raffinate, C9 aromatics (equal to its mogas blending value) and
LPG is shown in Figure 3.1 for the USGC. This shows that historically LPG has had a lower
value than C9 aromatics and is about equal in value to benzene raffinate. (The latter can also be
recycled to the steam cracker for additional ethylene and propylene productions although the
yield of ethylene and propylene is lower than for LPG). Based on this pricing data, it is
uncertain whether adding an APU unit will improve the economics of an aromatics facility. The
application of the APU technology will be very site specific depending very much on the values
applied to the products in question.
Benzene/Toluene 72
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
Figure 3.1
Historical C9 Aromatics, LPG and Benzene Raffinate Pricing (USGC)
(US dollars per metric ton)
1,200
1,000
800
$/MT
600
400
200
0
2000 2001 2002 2003 2004 2005 2006
C9 AROMATICS LPG Raffinate (Bz)
Q207_00101.0007.4106_char t s.xls
SK Corporation has taken the APU process a step further and integrated it with a pyrolysis unit
(re. U.S. patent application 2006/0287561). The latest invention produces increased aromatics
by processing the pygas in the APU and recycling the LPG to the pyrolysis unit to improve the
productivity of light olefins.
A block flow diagram of the invention is shown in Figure 3.2. The significant features of this
integration scheme are:
the pygas from the steam cracker is recycled to the APU unit
the hydrogen from the steam cracker cold box is recycle to the APU unit
the reformer grade hydrogen (60-75 mol percent) and LPG from the APU unit is recycle
to the steam cracker
the non-aromatics from the APU unit are recycled to the steam cracker
Within the APU unit the flow is much like a hydrotreater. Pygas from the steam cracker is
combined with hydrogen. The hydrogen is recycled from the steam cracker and make-up
hydrogen (H2 MU) is added to maintain the hydrogen purity. The feed mix is preheated with
reactor effluent before reaching the final reactor inlet temperature in a fired heater. Within the
reactor several reactions take place: dealkylation, transalkylation and hydrogenation. The
catalyst is 10-95 wt percent zeolites which at least one selected from the group consisting of
mordenite, a beta type of zeolite and a ZSM-5 type of zeolite and which has a silica/alumina
molar ratio of 200 or less. This is mixed with 5-90 wt. percent inorganic binder to produce a
Benzene/Toluene 73
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
support and either platinum/tin or platinum/lead is supported on the mixture. Typical yields for
the APU unit are provided in Table 3.2.
Table 3.2
APU Yields
(weight percent)
The reactor effluent is cooled first by preheating the feed and then finally by air and/or cooling
water to about 30-50°C (86-122°F). The resulting mixed phase is separated and the liquid sent to
a conventional fractionation system where the aromatic components (benzene, toluene and
xylenes) are separated and recovered. The gas, which is 60-75 mol percent hydrogen and 25-40
mol percent hydrocarbon (methane, ethane, LPG) is sent to the steam cracker compression
section for recovery of the LPG and recycle of the hydrogen. The LPG is recovered via
fractionation and recycled to the pyrolysis furnaces as additional feed. Since the example used
herein is a naphtha cracker, the LPG would normally be recycled to separate pyrolysis furnaces
for optimum cracking.
Benzene/Toluene 74
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
Figure 3.2
Integrated APU/Pyrolysis Unit Block Flow Diagram
Separator
Benzene
Toluene
Furnace
Fractionation
Section
Xylenes
Reactor
C9+ aromatics
Steam Cracker
Ethylene
Q207_00101.0007.4106.ppt
Benzene/Toluene 75
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
consequently the yield is too low for industrial purposes. Operating above 600°C reduces the
yield due to interference from secondary reactions such as hydrocracking and coking.
The acidity and basicity of the modifier are opposite to those of the main solvent. Addition of
the modifier into the composite solvent can solve the deviation of the separated aromatics from
neutrality caused by the main solvent. For instance, when sulfolane is used as a main solvent,
the separated aromatic product is also weakly acidic as sulfolane is weakly acidic per se.
Therefore, a post treatment of the product is needed to neutralize its acidity. Similarly when
weakly basic N-formylmorpholine or N-methylpyrrolidone is used as the main solvent, the
separated product is also weakly basic. Therefore, an acid treatment of the product is needed to
neutralize the basicity thereof.
The process for separating aromatics by extractive distillation using the composite according to
this invention is:
Introducing the lean composite solvent to the upper portion of the ED column.
Introducing the hydrocarbon mixture to the middle of the Ed column.
Withdrawing the non-aromatics from the top of the ED column.
Passing the rich composite solvent containing the aromatics from the bottom of the ED
column to the middle of a solvent recovery column.
Recovering the aromatics (benzene or benzene/toluene mixture) from the top of the
recovery column.
Recovering the lean composite solvent from the bottom of the recovery column and
sending it to the top of the ED column.
The operating conditions are:
Benzene/Toluene 76
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
Due to the addition of the solutizer, the composite solvent enhances the solubility enabling the
composite solvent to have sufficiently high recovery rates when used to recover aromatics from
feedstock with low aromatic content, thus, expanding the applicable area of the device. The
addition of the modifier ensures the neutrality of the aromatic product and thereby reduces or
omits the post treatment.
3.3.4 ExxonMobil
U.S. patent 6,864,203 proposes a bound zeolite catalyst for use in alkylation, transalkylation or
isomerization of aromatic hydrocarbons. Synthetic zeolites are normally prepared by the
crystallization of zeolites from a supersaturated synthesis mixture. The resulting crystalline
product is then dried and calcined to produce a zeolite powder. Although the zeolite powder has
good adsorptive properties, its practical applications are severely limited because it is difficult to
operate fixed beds with zeolite powder. Therefore, prior to using the powder in commercial
processes, the zeolite crystals are usually bound. This is typically done by forming a zeolite
aggregate such as a pill, sphere, or extrudate. The extrudate is usually formed by extruding the
zeolite in the presence of a non-zeolitic binder and drying and calcining the resulting extrudate.
The binder materials used are resistant to the temperatures and other conditions (e.g., mechanical
attrition) which occur in various hydrocarbon conversion processes. Examples of binder
materials include amorphous materials such as alumina, silica, titania and various types of clays.
The performance of the zeolite catalyst (e.g., activity, selectivity, activity maintenance, or
combinations thereof), can be reduced because of the binder. For example, since the binder is
typically present in an amount of up to about 50 weight percent of the zeolite, the binder dilutes
the adsorption properties of the zeolite aggregate and may block access to the pores of the
zeolite, thus, slowing the rate of mass transfer and the effectiveness. Finally the binder may
affect the chemical reactions that are taking place or may catalyze undesirable reactions. The
bound zeolite catalyst of this patent comprises crystals of a large pore first zeolite and a binder
comprising smaller crystals of a second zeolite. This provides a means of controlling
undesirable reactions taking place in or near the external surface of the first zeolite crystals and
can improve the mass transfer of reactants by providing access to and from the pores of the first
zeolite. In addition, the second zeolite binding crystals can have catalyst activity. The patent
examples show a higher activity and higher xylene selectivity than an alumina bound mordenite
catalyst.
Benzene/Toluene 77
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
benzene). In addition the amount of para-xylene produced in the patent examples was greater
than equilibrium.
U.S. patents 6,504,076 and 6,846,964 provide a method for conversion of heavy
alkylaromatic compounds, particularly those in the C8-C12 range, into more valuable
aromatics (BTX) utilizing a toluene disproportionation (TDP) unit containing a nickel,
palladium or platinum-modified mordenite catalyst. This invention allows a large
amount of heavy alkylaromatic compounds to be processed without adversely affecting
the catalyst activity or catalyst life. The feed can be a mix of toluene and heavy
aromatics or heavy aromatics alone.
U.S. patent 6,706,937 offers a metal modified zeolite transalkylation catalyst. The
temperature is progressively increased while continuing the operation of the
transalkylation zone to maintain a condition of constant reaction severity.
U.S. patent 6,803,493 presents a catalyst (nickel-promoted mordenite) and a process for
the disproportionation of less than pure toluene (80-90 percent pure), the rest being C6-C8
non-aromatics. The non-aromatics are cracked to LPG in the process. Catalyst activity
was shown to be enhanced by increasing the temperature, reactor pressure, the hydrogen
to oil ratio and by decreasing the space velocity. By appropriate adjustment of these
factors, a feedstock having a diluted toluene content can be employed to effectively
disproportionate the toluene to benzene and xylenes accompanied by cracking of the
substantial non-aromatic content of the feed to produce lower molecular weight
hydrocarbons.
U.S. patent 6,897,346 provides a process for the transalkylation of polyalkylated aromatic
compounds over a high porosity zeolite-Y molecular sieve having a surface of no more
than 500 m2/g.
Benzene/Toluene 78
PERP 06/07-6
Q207_00101.0007.4106
Section 3 Developing Technologies
facilitated para-xylene separation. Finally the yield of light compounds (C1-C4) increased to the
detriment of the heavy compound yield which favors the stability of the catalyst and was due to
the dealkylating properties of this novel catalyst.
In U.S. patent 6,605,566, IFP has discovered a catalyst with substantially improved properties
with respect to previous reforming catalyst. This novel supported bimetallic catalyst comprises a
group VIII metal such as platinum or tin, a portion of which interacts strongly with the group
VIII metal with the catalyst in the reduced state. In particular it is noted that the presence of a
large quantity (greater than 10 percent) of a reduced tin species with oxidation state 0 and closely
associated with a group VIII metal in a bimetallic catalyst that is partially oxidized (by oxidation
carried out under perfectly controlled conditions with discontinuous injection of oxygen), reveals
a strong interaction in the reduced state of the catalyst between the group VIII metal and at least
a fraction of the tin, guaranteeing a beneficial bimetallic effect on the performance of the
hydrocarbon transformation units, such as catalyst reforming units, in terms of activity and
stability. Better activity and better stability increase the aromatics yield, the target products of
catalytic reforming. In the case of reforming, the catalyst of this invention results in a better
quality of reformate having a higher RON and deactivates more slowly than know catalysts.
3.3.7 SABIC
With respect to the CyclarTM process (re. Section 2.7.2), SABIC has been awarded several
patents (U.S. patents 6,784,333, 7,186,871 and 7,186,872) for improvements to the process and
catalyst. The catalyst is a crystalline zeolite on which platinum has been deposited, specifically a
platinum containing ZSM-5. The catalyst demonstrates a correlation between platinum loading
and selectivity to ethane. As the platinum loading is lowered the selectivity to BTX is lower as
well. An advantage to this catalyst is that the fuel gas produced has a higher content of ethane
relative to methane. Whereas a methane-rich fuel gas would primarily be used for its heat value,
an ethane-rich stream could be used as feed to a steam cracker after recovering the ethane.
3.3.8 UOP
UOP has developed a new family of zeolites (re. U.S. patent 7,091,390) identified as UZM-8 and
UZM-8HS which have unique x-ray diffraction patterns. These zeolites can be used in
alkylation of aromatics, transalkylation of aromatics, isomerization of aromatics and alkylation
of isoparaffins. The UZM-8 compositions are alumino-silicates having Si/Al molar ratio from
about 6.5 to about 35. Although UZM-8 compositions have some similarities to a layered
material identified as MCM-56, there are sufficient differences that UZM-8 compositions are
structurally different from MCM-56 materials and, thus, are unique new zeolite structures.
The reader is referred to PERP report 05/06-S6, Optimizing Aromatics Production, for a
discussion and analysis of UOP’s patented flow scheme for the production of aromatics (re. U.S.
patents 6,740,788, 7,169,368, and 7,179,434).
Benzene/Toluene 79
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
4.1 BASIS
4.1.1 Pricing Basis
The pricing basis for the economics analysis that follows is summarized in Table 4.1 for the
USGC fourth quarter 2006.
Table 4.1
Price and Utility Basis
(USGC, fourth quarter 2006)
Units $/Unit
Feedstock/Byproducts
Naphtha Gallon 1.364
LPG Gallon 1.013
C5-C6 Gallon 1.323
Propane Gallon 0.950
Butanes Gallon 1.120
Raffinate (Bz extraction) Gallon 1.323
Reformate Gallon 1.860
Pyrolysis gasoline Gallon 1.810
Hydrogen (reformer grade) Thousand SCF 3.383
Benzene Gallon 3.653
Toluene, contract value Gallon 2.511
Toluene, mogas value Gallon 2.087
Mixed xylenes, contract value Gallon 2.570
Mixed xylenes, mogas value Gallon 2.151
C9 Aromatics Gallon 2.223
Utilities
Power, purchased kWh 0.059
Cooling water Thousand Gal 0.108
LP Steam Thousand Lb 10.149
MP Steam Thousand Lb 10.310
HP Steam Thousand Lb 11.622
Boiler Feed Water Thousand Gal 1.956
Inert Gas Thousand SCF 1.706
Fuel Million Btu 6.436
Manpower
Operators $/Year 44,681
Foremen $/Year 50,716
Supervisor $/Year 61,199
Benzene/Toluene 80
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
For all the cases considered, investment costs assume "instantaneous" construction or
implementation in the designated year. This is a simplification because initiation, design, and
construction can take several years to complete. In order to undertake the instantaneous analysis,
phased investment costs and associated financial charges are consolidated into a single overall
project cost. The elements of Nexant ChemSystems capital cost estimates are presented in the
Appendix. All investments are for the U.S. Gulf Coast (USGC) for the fourth quarter 2006.
The buildup of the installed (direct) cost is developed starting with the purchased equipment cost
and using historical factors to estimate the bulk equipment costs (piping, electrical,
instrumentation and communication, paint and insulation, civil and structural), as well as labor.
The indirect costs are added also using historical factors. These include prorateable costs (fringe
benefits; burdens; insurance), field expenses (consumables; small tools; equipment rental; field
services; temporary construction facilities; field construction supervisor) and home office costs
plus fees (engineering plus incidentals; purchasing; construction management). The sum of the
direct and indirect equals the total installed cost (TIC).
Working capital is calculated to reflect raw materials, byproducts and supplies inventories,
accounts receivable, cash requirements, etc. with credit for accounts payable.
The detailed economics analysis which follows can be separated into two discrete categories:
Variable costs - raw material (e.g., naphtha, LPG), including catalysts and chemicals;
utilities, such as purchased electricity, cooling water, natural gas and boiler feedwater
(BFW); and byproducts.
Benzene/Toluene 81
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Fixed costs - direct operating costs, such as labor, maintenance, and direct overheads;
allocated costs, such as general plant overhead, insurance, environmental and taxes.
Utilities and byproduct credits are considered variable costs since they are, to a large extent,
dependent on the plant's operating rate or rate of fuel consumption. Fixed operating and
allocated costs, as their title indicates, are largely independent of the operating rate. The sum of
variable and fixed costs is termed the "total cash cost of production." This is the out-of-pocket
expense and owner incurs before including working capital, capital investment depreciation and
any return on capital employed (ROCE). Depreciation is assumed to be 20 years for OSBL and
10 years for ISBL including the capitalized other project costs (OPC). The return on capital
employed (ROCE) is assumed to be 10 percent unless otherwise noted. The on-stream factor
assumed for this evaluation is based on operating for 8,000 hours per year.
4.2 ECONOMICS
4.2.1 Investment
The capacities and ISBL investment for the various reforming technologies discussed herein are
presented in Table 4.2. Capacities are based on a world scale capacity of 500 kta. Investment is
for the USGC in the fourth quarter of 2006. The lowest cost investment source of reformate is
either via CCRTM or RZ PlatformingTM. The highest capital investment per ton of reformate
product is for the CyclarTM process.
Table 4.2
Capacities and Investment
(USGC, fourth quarter 2006)
Benzene/Toluene 82
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
If a 30 percent discount is applied to the LPG feedstock price (pricing one might find in the
Middle East), the CyclarTM economics are competitive with the low cost technologies. The
individual process costs are discussed in the sections which follow and the sensitivities of these
economics are noted in Section 4.2.4.
Figure 4.1
Reformate Cost of Production
(500 kta, USGC, fourth quarter 2006)
3.00
2.50
Dollars Per Gallon
2.00
1.50
1.00
0.50
0.00
AROMAX CCR RZ ALPHA CYCLAR
PLATFORMING
NET RAW MATERIALS UTILITIES DIRECT FIXED COSTS
ALLOCATED FIXED COSTS DEPRECIATION ROCE
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene 83
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.3
Cost of Production Estimate for: Reformate
Process: Continuous Catalyst Regeneration Reformer (includes Hydrotreater)
DIRECT FIXED COSTS Labor, 30 Men 44.68 Thousand U.S. $ 0.008 1.34
Foremen, 5 Men 50.72 Thousand U.S. $ 0.002 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.000 0.06
Maint., Material & Labor 3 % of ISBL 0.012 1.97
Direct Overhead 45 % Labor & Supervision 0.004 0.74
TOTAL DIRECT FIXED COSTS 0.026 4.37 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.016 2.62
Insurance, Property Tax 1 % Total Plant Capital 0.006 0.95
Environmental 0.5 % Total Plant Capital 0.003 0.48
TOTAL ALLOCATED FIXED COSTS 0.024 4.05 8
TOTAL CASH COST 1.632 270.88 542
Benzene/Toluene 84
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
4.2.2.2 RZ PlatformingTM
The cost of production estimate for producing reformate via RZ PlatformingTM with a capacity of
500 thousand metric ton per year is shown in Table 4.4. Net raw materials are estimated to be
$1.52 per gallon ($506 per metric ton). Utility costs add 5.6 cents per gallon ($19 per metric ton)
bringing the variable cost to $1.58 per gallon ($525 per metric ton). After adding in the fixed
costs, the total cash cost is estimated to be $1.63 per gallon ($542 per metric ton). Depreciation
of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds another 6.3 cents per
gallon ($21 per metric ton) to the cost of production. Return on total capital employed of 10
percent adds 9.5 cents per gallon ($31 per metric ton). The final cost of production including
return on investment is estimated to be $1.79 per gallon ($594 per metric ton).
4.2.2.3 CyclarTM
The cost of production estimate for producing reformate from LPG using UOP’s CyclarTM
technology in a 500 thousand metric ton per year unit is shown in Table 4.5. Net raw materials
are estimated to be $1.96 per gallon ($652 per metric ton). Utility costs add 28.7 cents per gallon
($95 per metric ton) bringing the variable cost to $2.25 per gallon ($748 per metric ton). After
adding in the fixed costs, the total cash cost is estimated to be $2.34 per gallon ($778 per metric
ton). Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds
another 15.5 cents per gallon ($51 per metric ton) to the cost of production. Return on total
capital employed of 10 percent adds 21.3 cents per gallon ($71 per metric ton). The final cost of
production including return on investment is estimated to be $2.71 per gallon ($900 per
metric ton).
4.2.2.4 Aromax®
The cost of production estimate for producing reformate via Aromax® employing a unit with a
capacity of 500 thousand metric ton per year is shown in Table 4.6. Net raw materials are
estimated to be $1.30 per gallon ($432 per metric ton). Utility costs add 16.3 cents per gallon
($54 per metric ton) bringing the variable cost to $1.46 per gallon ($486 per metric ton). After
adding in the fixed costs, the total cash cost is estimated to be $1.52 per gallon ($504 per metric
ton). Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds
another 7.1 cents per gallon ($24 per metric ton) to the cost of production. Return on total
capital employed of 10 percent adds 10.6 cents per gallon ($35 per metric ton). The final cost of
production including return on investment is estimated to be $1.70 per gallon ($563 per
metric ton).
Benzene/Toluene 85
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.4
Cost of Production Estimate for: Reformate
Process: RZ PlatformingTM
DIRECT FIXED COSTS Labor, 30 Men 44.68 Thousand U.S. $ 0.008 1.34
Foremen, 5 Men 50.72 Thousand U.S. $ 0.002 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.000 0.06
Maint., Material & Labor 3 % of ISBL 0.012 1.93
Direct Overhead 45 % Labor & Supervision 0.004 0.74
TOTAL DIRECT FIXED COSTS 0.026 4.33 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.016 2.60
Insurance, Property Tax 1 % Total Plant Capital 0.006 0.97
Environmental 0.5 % Total Plant Capital 0.003 0.49
TOTAL ALLOCATED FIXED COSTS 0.024 4.06 8
TOTAL CASH COST 1.632 270.98 542
Benzene/Toluene 86
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.5
Cost of Production Estimate for: Reformate
Process: CyclarTM
DIRECT FIXED COSTS Labor, 30 Men 44.68 Thousand U.S. $ 0.008 1.34
Foremen, 5 Men 50.72 Thousand U.S. $ 0.002 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.000 0.06
Maint., Material & Labor 3 % of ISBL 0.029 4.75
Direct Overhead 45 % Labor & Supervision 0.004 0.74
TOTAL DIRECT FIXED COSTS 0.043 7.15 14
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.026 4.29
Insurance, Property Tax 1 % Total Plant Capital 0.014 2.37
Environmental 0.5 % Total Plant Capital 0.007 1.19
TOTAL ALLOCATED FIXED COSTS 0.047 7.85 16
TOTAL CASH COST 2.342 388.78 778
Benzene/Toluene 87
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.6
Cost of Production Estimate for: Reformate
Process: Aromax®
DIRECT FIXED COSTS Labor, 30 Men 44.68 Thousand U.S. $ 0.008 1.34
Foremen, 5 Men 50.72 Thousand U.S. $ 0.002 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.000 0.06
Maint., Material & Labor 3 % of ISBL 0.013 2.18
Direct Overhead 45 % Labor & Supervision 0.004 0.74
TOTAL DIRECT FIXED COSTS 0.028 4.58 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.017 2.75
Insurance, Property Tax 1 % Total Plant Capital 0.007 1.09
Environmental 0.5 % Total Plant Capital 0.003 0.54
TOTAL ALLOCATED FIXED COSTS 0.026 4.38 9
TOTAL CASH COST 1.519 252.15 504
Benzene/Toluene 88
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Figure 4.2
Benzene Cost of Production
(334 kta, USGC)
3.50
3.00
2.50
Dollars Per Gallon
2.00
1.50
1.00
0.50
0.00
SE (1) SE (2) ED (2) Dealky Litol THDA TDP STDP
Reformate Pygas Pygas Pygas
NET RAW MATERIALS UTILITIES DIRECT FIXED COSTS
ALLOCATED FIXED COSTS DEPRECIATION ROCE
(1)
Solvent Extraction
(2)
Extractive Distillation
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene 89
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.7
Cost of Production Estimate for: Reformate
Process: Alpha
DIRECT FIXED COSTS Labor, 30 Men 44.68 Thousand U.S. $ 0.008 1.34
Foremen, 5 Men 50.72 Thousand U.S. $ 0.002 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.000 0.06
Maint., Material & Labor 3 % of ISBL 0.017 2.88
Direct Overhead 45 % Labor & Supervision 0.004 0.74
TOTAL DIRECT FIXED COSTS 0.032 5.28 11
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.019 3.17
Insurance, Property Tax 1 % Total Plant Capital 0.007 1.19
Environmental 0.5 % Total Plant Capital 0.004 0.59
TOTAL ALLOCATED FIXED COSTS 0.030 4.95 10
TOTAL CASH COST 1.959 325.25 650
Benzene/Toluene 90
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Benzene/Toluene 91
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.8
Cost of Production Estimate for: Benzene
Process: Reformate Extraction (Sulfolane) plus BTX Distillation
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.037 3.67
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.048 4.77 14
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.029 2.86
Insurance, Property Tax 1 % Total Plant Capital 0.017 1.65
Environmental 0.5 % Total Plant Capital 0.008 0.83
TOTAL ALLOCATED FIXED COSTS 0.053 5.34 16
TOTAL CASH COST 2.436 243.57 730
RETURN ON TOTAL CAPITAL INVESTMENT (Incl. WC) @ 10 Percent 0.382 38.16 114
Benzene/Toluene 92
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.9
Cost of Production Estimate for: Benzene
Process: Solvent Extraction of Pygas
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.018 1.79
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.029 2.90 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.017 1.74
Insurance, Property Tax 1 % Total Plant Capital 0.009 0.91
Environmental 0.5 % Total Plant Capital 0.005 0.46
TOTAL ALLOCATED FIXED COSTS 0.031 3.10 9
TOTAL CASH COST 1.848 184.82 554
Benzene/Toluene 93
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Benzene/Toluene 94
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.10
Cost of Production Estimate for: Benzene
Process: Extractive Distillation of Pygas
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.024 2.39
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.035 3.50 10
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.021 2.10
Insurance, Property Tax 1 % Total Plant Capital 0.011 1.08
Environmental 0.5 % Total Plant Capital 0.005 0.54
TOTAL ALLOCATED FIXED COSTS 0.037 3.71 11
TOTAL CASH COST 2.715 271.42 813
Benzene/Toluene 95
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.11
Cost of Production Estimate for: Benzene
Process: Bulk Dealkylation of Pygas
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.021 2.15
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.033 3.25 10
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.020 1.95
Insurance, Property Tax 1 % Total Plant Capital 0.010 1.04
Environmental 0.5 % Total Plant Capital 0.005 0.52
TOTAL ALLOCATED FIXED COSTS 0.035 3.51 11
TOTAL CASH COST 2.823 282.23 845
Benzene/Toluene 96
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.12
Cost of Production Estimate for: Benzene
Process: Litol Process (from coke oven light oil)
RAW MATERIALS Coke oven light oil pound 1.0900 1.6944 1.847 92.34
Hydrogen - reformer grade kSCF 0.0471 3.3833 0.159 7.96
Catalyst & Chemicals 1.0000 0.0550 0.055 2.75
TOTAL RAW MATERIALS 2.061 103.05 617
BY-PRODUCT CREDITS Fuel MM Btu (0.0204) 6.4359 (0.131) (6.55)
Light/heavy ends (fuel value) MM Btu (0.0219) 6.4359 (0.141) (7.05)
TOTAL BY-PRODUCT CREDITS (0.272) (13.60) (600)
NET RAW MATERIALS 1.789 89.45 536
UTILITIES Power kwh 0.2737 0.0589 0.016 0.81
Cooling Water M Gal 0.0539 0.1080 0.006 0.29
Steam, HP M Lb (0.0016) 11.6220 (0.019) (0.94)
Fuel MM Btu 0.0204 6.4359 0.131 6.56
TOTAL UTILITIES 0.134 6.72 40
NET RAW MATERIALS & UTILITIES 1.923 96.17 576
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.009 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.005 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.031 1.54
Direct Overhead 45 % Labor & Supervision 0.007 0.34
TOTAL DIRECT FIXED COSTS 0.053 2.65 16
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.032 1.59
Insurance, Property Tax 1 % Total Plant Capital 0.015 0.75
Environmental 0.5 % Total Plant Capital 0.007 0.37
TOTAL ALLOCATED FIXED COSTS 0.054 2.71 16
TOTAL CASH COST 2.030 101.52 608
Benzene/Toluene 97
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
The cost of production estimate for producing benzene via selective toluene disproportionation
(TDP) is shown in Table 4.15 for a 334 kta (100 million gallon per year) unit. para-Xylenes are
considered a byproduct for this analysis and valued at their market price. Net raw materials are
estimated to be $1.53 per gallon ($458 per metric ton). Utility costs add 18.5 cents per gallon
($55 per metric ton) bringing the variable cost to $1.72 per gallon ($514 per metric ton). After
adding in the fixed costs, the total cash cost is estimated to be $1.78 per gallon ($533 per metric
ton). Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds
another 11.6 cents per gallon ($35 per metric ton) to the cost of production. Return on total
capital employed of 10 percent adds 19.5 cents per gallon ($59 per metric ton). The final cost of
production including return on investment is estimated to be $2.09 per gallon ($626 per metric
ton).
Benzene/Toluene 98
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.13
Cost of Production Estimate for: Benzene
Process: Toluene Hydrodealkylation (THDA)
RAW MATERIALS Toluene - mogas value Gallons 1.2200 2.0866 2.546 254.53
Hydrogen - reformer grade kSCF 0.0442 3.3833 0.149 14.94
Catalyst & Chemicals 1.0000 0.0020 0.002 0.20
TOTAL RAW MATERIALS 2.697 269.66 808
BY-PRODUCT CREDITS Fuel Gas pound (0.0425) 6.4359 (0.273) (27.33)
TOTAL BY-PRODUCT CREDITS (0.273) (27.33) (603)
NET RAW MATERIALS 2.424 242.34 726
UTILITIES Power kwh 0.3076 0.0589 0.018 1.81
Cooling Water M Gal 0.0100 0.1080 0.001 0.11
Steam, HP M Lb (0.0007) 11.6220 (0.009) (0.86)
Steam, MP M Lb 0.0024 10.3095 0.025 2.50
Boiler Feedwater M Gal 0.0002 1.9560 0.000 0.04
Fuel MM Btu 0.0074 6.4359 0.048 4.78
TOTAL UTILITIES 0.084 8.40 25
NET RAW MATERIALS & UTILITIES 2.508 250.73 751
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.015 1.53
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.026 2.63 8
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.016 1.58
Insurance, Property Tax 1 % Total Plant Capital 0.008 0.77
Environmental 0.5 % Total Plant Capital 0.004 0.39
TOTAL ALLOCATED FIXED COSTS 0.027 2.74 8
TOTAL CASH COST 2.561 256.11 767
Benzene/Toluene 99
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.14
Cost of Production Estimate for: Benzene
Process: Toluene Disproportionation (TDP)
RAW MATERIALS Toluene - mogas value Gallons 2.3856 2.0866 4.978 497.71
Hydrogen - pure Pounds 0.0650 2.9061 0.189 18.88
Catalyst & Chemicals 1.0000 0.0193 0.019 1.93
TOTAL RAW MATERIALS 5.186 518.51 1,553
BY-PRODUCT CREDITS Fuel Gas, MM Btu MM Btu (0.0301) 6.4359 (0.194) (19.37)
C9 Aromatics, Gal Gallons (0.2278) 2.2081 (0.503) (50.29)
Mixed xylenes, Gal Gallons (0.9435) 2.5701 (2.425) (242.46)
TOTAL BY-PRODUCT CREDITS (3.122) (312.12) (6,882)
NET RAW MATERIALS 2.064 206.39 618
UTILITIES Power kwh 0.6839 0.0589 0.040 4.03
Cooling Water M Gal 0.1026 0.1080 0.011 1.11
Steam, HP M Lb 0.0000 11.6220 0.000 0.00
Steam, MP M Lb 0.0205 10.3095 0.212 21.15
Fuel MM Btu 0.0274 6.4359 0.176 17.60
TOTAL UTILITIES 0.439 43.89 131
NET RAW MATERIALS & UTILITIES 2.503 250.28 750
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.019 1.86
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.030 2.96 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.018 1.78
Insurance, Property Tax 1 % Total Plant Capital 0.009 0.87
Environmental 0.5 % Total Plant Capital 0.004 0.43
TOTAL ALLOCATED FIXED COSTS 0.031 3.08 9
TOTAL CASH COST 2.564 256.32 768
Benzene/Toluene 100
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Table 4.15
Cost of Production Estimate for: Benzene
Process: Selective Toluene Disproportionation (STDP)
RAW MATERIALS Toluene - mogas value Gallons 2.3219 2.0866 4.845 484.43
Hydrogen - pure Pounds 0.0903 2.9061 0.262 26.24
Catalyst & Chemicals 1.0000 0.0029 0.003 0.29
TOTAL RAW MATERIALS 5.110 510.96 1,531
BY-PRODUCT CREDITS Fuel Gas, MM Btu MM Btu (0.0253) 6.4359 (0.163) (16.27)
C9 Aromatics, Gal Gallons (0.0454) 2.2081 (0.100) (10.01)
Mixed xylenes, Gal Gallons (0.0375) 2.5701 (0.096) (9.64)
para-xylene Pounds (6.0204) 0.5350 (3.221) (322.05)
TOTAL BY-PRODUCT CREDITS (3.580) (357.98) (7,893)
NET RAW MATERIALS 1.530 152.98 458
UTILITIES Power kwh 0.3709 0.0589 0.022 2.19
Cooling Water M Gal 0.0205 0.1080 0.002 0.22
Steam, LP M Lb 0.0001 10.1488 0.001 0.07
Steam, MP M Lb 0.0065 10.3095 0.067 6.70
Fuel MM Btu 0.0144 6.4359 0.093 9.30
TOTAL UTILITIES 0.185 18.47 55
NET RAW MATERIALS & UTILITIES 1.715 171.45 514
DIRECT FIXED COSTS Labor, 10 Men 44.68 Thousand U.S. $ 0.004 0.45
Foremen, 5 Men 50.72 Thousand U.S. $ 0.003 0.25
Super., 1 Men 61.20 Thousand U.S. $ 0.001 0.06
Maint., Material & Labor 3 % of ISBL 0.018 1.81
Direct Overhead 45 % Labor & Supervision 0.003 0.34
TOTAL DIRECT FIXED COSTS 0.029 2.91 9
ALLOCATED FIXED COSTS General Plant Overhead 60 % Direct Fixed Costs 0.017 1.75
Insurance, Property Tax 1 % Total Plant Capital 0.011 1.15
Environmental 0.5 % Total Plant Capital 0.006 0.57
TOTAL ALLOCATED FIXED COSTS 0.035 3.47 10
TOTAL CASH COST 1.779 177.83 533
Benzene/Toluene 101
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
4.2.4 Sensitivity
4.2.4.1 Five-Year Average Pricing
It is important to note that the economics presented herein are in essence a “snapshot” in time.
In Figures 4.3 and 4.4 we have tried to mitigate this by using five-year historical averages for
feed and product prices. The results of this sensitivity are shown in Figure 4.3 for the reformate
cases and Figure 4.4 for the benzene cases. In each analysis the results show similar, but lower
costs of production when using the 5-year average.
Figure 4.3
Cost of Production of Reformate – Sensitivity to Pricing
(500 kta, USGC)
3.00
2.50
2.00
Dollars Per Gallon
1.50
1.00
0.50
0.00
AROMAX CCR RZ ALPHA CYCLAR
PLATFORMING
4Q2006 5 Yr Avg
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene 102
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Figure 4.4
Cost of Production of Benzene – Sensitivity to Pricing
(334 kta, USGC)
3.50
3.00
2.50
Dollars Per Gallon
2.00
1.50
1.00
0.50
0.00
SE SE Pygas ED Pygas Dealky Litol THDA TDP STDP
Reformate Pygas
4Q2006 5 Yr Avg
Q207_00101.0007.4106_chart s.xls
Benzene/Toluene 103
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Figure 4.5
Sensitivity of Cost of Production of Reformate to Feed Price
(500 kta, USGC, fourth quarter 2006)
4.00
3.50
3.00
2.50
Dollars Per Gallon
2.00
1.50
1.00
0.50
0.00
60% 70% 80% 90% 100% 110% 120% 130% 140%
Percent of Base Case Feed Price
CCR ALPHA CYCLAR RZ PLATFORMING AROMAX
Q207_00101.0007.4106_chart s.xls
Figure 4.6 shows that producing benzene via recovery from reformate employing liquid/liquid
extraction (Sulfolane) is the most sensitive to feedstock pricing while the Litol process is the
least sensitive followed closely by THDA. As toluene prices increase THDA is more
economical than TDP. However, TDP economics are also a function of the credit derived from
the mixed xylene byproduct and is therefore, a function of mixed xylene pricing as well. This
sensitivity is shown in Figure 4.7. As the price of mixed xylenes is varied by plus or minus 30
percent the cost plus return of benzene via TDP varies by plus or minus 73 cents per gallon
($218 per metric ton).
Benzene/Toluene 104
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Figure 4.6
Sensitivity of Cost of Production of Benzene to Feed Price
(334 kta, USGC, fourth quarter 2006)
9.00
8.00
7.00
6.00
5.00
Dolars Per Gallon
4.00
3.00
2.00
1.00
0.00
60% 70% 80% 90% 100% 110% 120% 130% 140%
Percent of Base Case Feed Price
SULFOLANE SE PYGAS ED PYGAS DEALKYL PYGAS
LITOL THDA TDP STDP
Q207_00101.0007.4106_chart s.xls
Figure 4.7
Sensitivity of Cost of Production via TDP to Mixed Xylenes Price
(334 kta, USGC, fourth quarter 2006)
4.00
3.50
3.00
Dollars Per Gallon
2.50
2.00
1.50
1.00
0.50
0.00
60% 70% 80% 90% 100% 110% 120% 130% 140%
Percent of Base Case Mixed Xylenes Price
Q207_00101.0007.4106_chart s.xls
Benzene/Toluene 105
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
4.3 CONCLUSIONS
Whether or not TDP or THDA units operate economically will not only depend on pricing
conditions (e.g., alternative value for toluene), but also on market position. Because THDA is
often the most expensive route for producing benzene, merchant THDA facilities tend to operate
only when the price of benzene exceeds the cost of production via THDA. Captive THDA units,
in contrast, usually serve to balance internal requirements for benzene and are run independently
of merchant market conditions. Historically the delta between the price of benzene and toluene
has been about 32 cents per gallon ($96 per metric ton) as shown in Figure 4.8. However, in the
past few years this delta has varied greatly. For the fourth quarter of 2004 it was almost $1.65
per gallon ($500 per metric ton), while for the second quarter of 2006 it was negative 8 cents per
gallon (-24 per metric ton). Currently (4th quarter 2006) this delta is about $1.10 per gallon
($332 per metric ton) while the cost of toluene hydrodealkylation is 23 cents per gallon ($68 per
metric ton).
Figure 4.8
Benzene to Toluene Price Delta
600
500
Delta Benzene - Toluene, $/T
400
300
200
100
-100
1982-Q1 1984-Q1 1986-Q1 1988-Q1 1990-Q1 1992-Q1 1994-Q1 1996-Q1 1998-Q1 2000-Q1 2002-Q1 2004-Q1 2006-Q1
Q207_00101.0007.4106_chart s.xls
In addition to the economics, a variety of other issues must also be considered when choosing
process technology. Some of these considerations are listed below:
Access to feedstock
Outlet for byproducts
Investment requirements
Revamp and integration potential or strategy
Feedstock/product price fluctuations/forecasts
Technology availability/licensing terms
Benzene/Toluene 106
PERP 06/07-6
Q207_00101.0007.4106
Section 4 Economic Analysis
Technology risk
Security of supply/strategic importance
Table 4.16 summarizes Nexant’s view with respect to some of the strategic issues. In the final
analysis, the selection of any of these aromatic technologies will have to be based on a careful
case by case assessment.
Table 4.16
Reformate Process Selection Matrix
Rz
TM
CCR PlatformingTM CyclarTM Aromax® Alpha
Feedstock Naphtha Naphtha LPG Naphtha C5/C6
sensitivity to Low Low Moderate High Moderate
feed price
Benzene/Toluene 107
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
5.1 APPLICATIONS
5.1.1 Benzene
5.1.1.1 Introduction
One of the major uses of benzene is as a gasoline component. It is contained within streams that
contribute to the gasoline pool, primarily catalytic reformate. For non-fuel benzene applications,
it is extracted or otherwise produced as described in Section 2. This market analysis is
concerned only with the non-fuel uses of benzene.
Benzene has many uses, and demand continues to grow despite increasing restrictions and
environmental regulations. Creation of styrene monomer is the largest use of benzene, followed
by cumene/phenol, cyclohexane, and nitrobenzene. Those derivatives are used to produce a wide
range of plastics, fibers, resins and films. Benzene is also an excellent solvent for waxes, resins,
rubber and various other organic materials, but toxicological properties greatly limit use.
5.1.1.2 Ethylbenzene/Styrene
Over half of the world's benzene production is used in ethylbenzene (EB) and styrene monomer
(SM) production. The dominant route involves the alkylation of benzene with ethylene,
followed by direct dehydrogenation to styrene. This route has been operated commercially since
the 1930s, although it has undergone considerable improvement and modifications since then.
The alkylation can be effected in either the liquid phase or the vapor phase. The ethylbenzene is
dehydrogenated to styrene and hydrogen over a catalyst in the presence of steam. Both benzene
and toluene are formed as byproducts; this is one of the minor sources of toluene.
Styrene is also produced from ethylbenzene by indirect dehydrogenation, using the OXIRANE
process. In this process ethylbenzene is converted to a hydroperoxide by direct air oxidation,
and the hydroperoxide is converted to an alcohol in an epoxidation reaction with propylene.
Finally, the alcohol is dehydrated to styrene. Propylene oxide is a coproduct of this process.
Some ethylbenzene is also removed from the C8 fraction of BTX aromatics, but this is a small
quantity in comparison to synthesis from benzene.
About two thirds of the styrene in the United States, Western Europe, and Japan is used to
produce polystyrene. The polymer is produced in a number of forms. The pure homopolymer
(crystal grade) is transparent and has a high refractive index that gives it a sparkling appearance.
Polystyrene can be made less brittle by incorporating 5 to 10 percent of rubbery polymers into
the material during polymerization. This results in high impact polystyrene (HIPS), which
accounts for about two thirds of polystyrene production. Foamed polystyrene is produced by
blending crystal polystyrene with a low boiling point hydrocarbon. The blend is extruded and a
foam is produced as the solvent volatilizes. Expanded polystyrene (EPS) is different from the
foamed product, since it is made from beads impregnated with blowing agents and has very
different properties.
Benzene/Toluene 108
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Polystyrene applications include the use of general purpose and high impact grades in moldings
and extruded sheet. Their good appearance and rigidity make them suitable for attractive
packaging and displays, housewares, appliances, furniture applications, toys, and miscellaneous
other applications. Foamed polystyrene is used in packaging, insulation, building, and furniture.
Expanded polystyrene is used mainly as insulation in construction and as packaging.
All the polymer products compete on price and performance with other materials, but it is
anticipated that styrenics will largely hold their position. One potentially significant trend is the
increasing regulatory requirement for recycling of polymers in the United States and Western
Europe. Depending on specific future regulations, the demand growth rate of polystyrene and
other styrenics will be reduced somewhat, but not to the extent that a market decline will result.
5.1.1.3 Cumene/Phenol
Benzene consumption in the production of cumene is the second largest market, accounting for
around 21 percent of global demand. Cumene is made by the vapor phase alkylation of benzene
with propylene. It is important to also consider phenol as well as cumene. Virtually all cumene
is used to produce phenol, and most phenol production is derived from cumene.
Solutia has developed a direct route to phenol that uses nitrous oxide, a byproduct of adipic acid
production, to oxidize benzene to phenol. No acetone is produced in this route. Shell is
considering a world-scale phenol plant to be built in Singapore using a new technology based on
benzene and butenes, producing methyl ethyl ketone (MEK) as a coproduct and less byproduct
acetone than in traditional processes. (re. PERP report 04/05-S12).
Three of the main outlets for phenol are phenolic resins, bisphenol A, and caprolactam. Phenolic
resins such as phenol/formaldehyde are mature products used in applications such as wood glues
and molded electrical equipment. The demand in developed countries is growing at less than
GNP due to competition with newer polymers and some environmental concerns relating to
formaldehyde.
Benzene/Toluene 109
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
The third main product from phenol is caprolactam, which is used primarily as an intermediate in
producing nylon fibers, and to a lesser extent film. Caprolactam can also be produced from
cyclohexane. Nylon demand in the three main industrial regions remains flat.
Acetone is coproduced with phenol. A large volume of acetone is used as a solvent. This is a
highly fragmented market, in which the pharmaceutical sector is increasing in importance. The
largest single acetone use is in the production of methyl methacrylate, which is polymerized to
products such as Perspex. Acetone is also used with phenol in bisphenol A production and in the
manufacture of a number of other derivatives.
Although important to the economics of phenol production, acetone demand is unlikely to dictate
production rates since it can also be produced from isopropanol.
5.1.1.4 Cyclohexane
Cyclohexane is a basic nylon intermediate that is produced from benzene by hydrogenation.
Producers are usually back integrated to benzene. The process is simple and can be switched on
and off to use surplus benzene and hydrogen.
Cyclohexane is used as a feedstock in one of the routes to caprolactam production. This route is
competitive with that derived from phenol and is more economical than toluene based processes.
The other important cyclohexane derivative is adipic acid, a precursor to nylon 6,6. The use of
cyclohexane in adipic acid and caprolactam accounts for 95 percent of demand.
5.1.1.5 Nitrobenzene
Nitrobenzene refers to a single product, a benzene ring with an NO2 group attached. Benzene is
nitrated in a reaction with nitric acid in the presence of concentrated sulfuric acid. The
technology is well proven and licensed by three vendors.
Nitrobenzene is mainly consumed as a feedstock to make aniline, which in turn is used primarily
to produce methylene diisocyanate (MDI) used primarily in polyurethane foams. The rest goes
into production of hydroquinone, acetaminophen, and other low volume products. Nitrobenzene
is not exported; it is scarcely traded. Trade is conducted in aniline.
About three quarters of aniline is used as a feedstock in the polyurethane manufacturing process.
The aniline is reacted with formaldehyde to yield diphenylmethane diamine and this is reacted
with phosgene to yield para-, para′-methylene diphenyldiisocyanate (MDI). In practice, a
mixture of MDI isomers is produced and referred to as “polymeric” MDI (PMDI) or sometimes
as polyisocyanate. The mixture is subsequently polymerized to polyurethane.
Aniline can also be produced from phenol, but this route is less economical and is not widely
practiced.
Aniline is also consumed in the production of rubber chemicals, dyes, pharmaceutical products,
agricultural products, and other chemicals.
Benzene/Toluene 110
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Nitrobenzene demand is heavily dependent on polyurethane demand, which has shown strong
historical growth rates. Polyurethane consumption in the automotive and construction sectors is
linked to economic growth.
5.1.1.6 Chlorobenzene
The term chlorobenzene applies to the chlorinated benzene derivatives. The primary commercial
products are monochlorobenzene, ortho-dichlorobenzene, para-dichlorobenzene,
trichlorobenzene, and tetrachlorobenzene. Benzene is chlorinated in the presence of a ferric
chloride catalyst or via oxychlorination using hydrochloric acid. As reaction temperature and the
proportion of chlorine is increased, so does the percentage of polychloro derivatives in the
product.
Monochlorobenzene used to be an intermediate for phenol and was a feedstock for the pesticide
DDT, but cumene has displaced chlorobenzene in the former instance and DDT has been banned.
Monochlorobenzene is still used to make nitrochlorobenzene and other fine chemicals, and it has
solvent uses as well. Dichlorobenzene is a feedstock for polyphenylene sulfide (PPS), has
solvent applications, and is a component of flame retardants. Trichlorobenzene is used as a
dyestuff carrier. All of the chlorobenzenes are used as feedstocks for pesticides.
PPS is chlorobenzene's high growth sector. Demand is gaining 10-15 percent per year.
Production is concentrated in Japan and the United States, but new capacity is unlikely in
Western Europe during the 1990s.
5.1.1.7 Alkylbenzene
Alkylbenzene is the term for three commercial products, linear alkylbenzene (LAB),
dodecylbenzene (DDB), and dialkylbenzene. DDB is known by at least two other names,
branched alkylbenzene and hard alkylbenzene.
LAB is, as its name suggests, a benzene ring with a linear alkyl group attached. The alkyl group
varies slightly in length - an average of C12. DDB is a benzene ring with a branched C12 group
attached. LAB is the most significant of the three products, constituting over 90 percent of
commercial alkylbenzene.
LAB is used to make linear alkylbenzene sulfonate (LAS), an anionic surfactant. LAS is the
largest volume anionic, with applications in liquid and powder detergents and household
cleaners. It is not consumed in personal care products, which use surfactants based on natural
products.
Benzene/Toluene 111
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
LAS's portion of the detergent market is expected to be static. On the one hand, demand for
anionics will be stimulated by the introduction of concentrated detergent powders, which already
are gaining market share in the Far East. On the other hand, detergent formulators are likely to
avoid LAS and choose competing anionics when possible, because of questions about its
degradability and image problems associated with benzene in consumer products.
DDB is used to make alkylbenzene sulfonate, another anionic surfactant and an isomer of LAS.
Alkylbenzene sulfonate consumption has declined steadily for about two decades. Starting in the
United States, one country after another has banned its use in detergents because of its poor
biodegradability. The ban is complete throughout the developed world (including Western
Europe) and is widely spread among the less developed countries. The switch from ABS to LAS
has largely run its course, and there is little substitution potential remaining.
Dialkylbenzene is a small volume product, used as a lubricant, plasticizer, and heat transfer fluid
additive.
End uses for maleic anhydride are largely mature. The main use is in unsaturated polyester resin,
which is used with glass fiber for boat building, construction, and electrical applications, and in
synthetic marble. Other established uses are the production of food acids and agricultural
chemicals. New uses for maleic anhydride are butanediol, a chemical intermediate used in
polyurethanes, polybutylene terephthalate, and tetrahydrofuran production.
Maleic anhydride is not made from benzene in the United States, and production by this route is
expected to be displaced by n-butane oxidation in the rest of the world. Globally, there will be a
significant drop in consumption of benzene for maleic anhydride production in coming years.
5.1.1.9 Other
Other uses of benzene include the production of resorcinol, which is a benzene ring with two
hydroxyl groups in the ortho-configuration. Most resorcinol is consumed in the manufacture of
high performance adhesive used in tires and laminated beams. The rest is used in pharmaceutical
and dye manufacturing.
Benzene is also used in making a variety of other products such as biphenyl and triphenyl. Some
benzene is used as a solvent, but this application has declined because of health concerns relating
to benzene's carcinogenic properties.
Benzene/Toluene 112
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
5.1.2 Toluene
5.1.2.1 Introduction
Toluene is primarily used as a component in gasoline, and is extracted from reformate or other
sources. Controls on the total aromatics content in gasoline will be less stringent than those
relating to benzene; the blending value of toluene is around 10 percent higher than benzene's.
Of the toluene extracted or otherwise produced, the largest single use is for the production of
benzene by dealkylation or the production of both benzene and xylenes by disproportionation.
The other toluene applications are outlined below.
5.1.2.2 Solvents
Toluene, a powerful organic solvent, is used in many applications including paints and coatings,
adhesives and sealants, printing inks, metal cleaners, and pesticides.
There is a general trend away from the use of organic solvents, particularly aromatics because of
direct health concerns and curbs on VOC emissions.
TDI is the basic raw material of polyurethane foam production. The polyurethane is produced by
the reaction of TDI with glycerol, polypropylene oxide, with a reaction product of
trimethylolpropane and propylene oxide, or other appropriate polyols. Water is often used as the
foaming agent because it generates carbon dioxide and amines in reaction with TDI.
The main demand is for flexible urethane foams, followed by elastomeric foams and rigid foams
for appliances such as refrigerators.
5.1.2.4 Phenol
Phenol, for the most part, is produced from cumene. A small quantity is derived from toluene.
The toluene is first oxidized to benzoic acid, then undergoes decarboxylation with oxygen to
form phenol and carbon dioxide.
5.1.2.5 Caprolactam
Caprolactam is produced by a number of routes, including those based on phenol and
cyclohexane. The process based on toluene includes oxidation to benzoic acid, followed by
hydrogenation to cyclohexane and carboxylic acid. Caprolactam is then produced by reaction
with nitrosylsulfuric acid.
Benzene/Toluene 113
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Nylon demand, and thus caprolactam demand, is declining in the main industrial regions. The
toluene based production processes are likely to close first.
5.1.2.6 Other
Other uses of toluene include the production of:
Benzoic acid, an intermediate in the production of benzoyl chloride and plasticizers such
as butyl benzoate
Benzyl chloride, which can be produced directly by chlorination of toluene and which is
used as an intermediate in the production of various plasticizers, and in soaps, perfumes,
and flavoring agents
Toluenesulfonic acid, used mainly for conversion to para-cresol, from which antioxidants
are produced
Toluenesulfonyl chloride
More than 75 percent of the toluene chemical use is for benzene and xylenes (para-xylene)
production via dealkylation, disproportionation and transalkylation. The next largest chemical
usage for toluene is TDI. Toluene is also used as a solvent, but this end use has been declining
due to more stringent air quality regulation.
Benzene/Toluene 114
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Figure 5.1
U.S. Benzene End-Use Pattern
Nitrobenzene
10%
LAB/BAB
2%
Cyclohexane
13%
Styrene
Others 45%
2%
Cumene
28%
Q207_00101.0007.4106_chart s.xls
5.2.2 Supply
The benzene and toluene capacity within the United States has been essentially flat since the late
1990s reflecting a lack of new naphtha cracking complexes for ethylene production and
investment in new refineries, the two main sources of benzene production. Furthermore rising
gasoline prices and weak para-xylene margins over the past few years have discouraged
investment in alternative sources. There are currently no firm plans to add benzene or toluene
production capacity and net imports have been rising.
A list of the United States benzene and toluene capacities is shown in Table 5.1.
Benzene/Toluene 115
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.1
U.S. Benzene and Toluene Capacity, 2006
Benzene/Toluene 116
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.2
U.S. Benzene Supply, Demand and Trade
(thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 9,872 9,754 9,753 9,680 9,543 9,654 9,654 9,680 9,654 9,654
Speculative Capacity 0 0 0 0 0 0 151 250 301 501
Total Capacity 9,872 9,754 9,753 9,680 9,543 9,654 9,805 9,930 9,954 10,154
Production 6,844 7,398 7,898 7,960 7,326 7,962 8,037 8,070 7,984 8,101
Operating Rate 69% 76% 81% 82% 77% 82% 82% 81% 80% 80%
Net Exports (939) (1,236) (1,211) (1,237) (1,538) (1,293) (1,426) (1,440) (1,513) (1,349)
Consumption 7,783 8,633 9,110 9,197 8,864 9,266 9,470 9,519 9,513 9,465
Toluene is produced in greater quantities than required for chemical uses and is therefore
consumed as a gasoline blendstock and converted into benzene and xylenes.
Benzene/Toluene 117
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Figure 5.2
Western Europe Benzene End-Use Pattern
Nitrobenzene
12%
LAB/BAB
2%
Cyclohexane
11%
Styrene
Others
49%
3%
Cumene
23%
Q207_00101.0007.4106_chart s.xls
5.3.2 Supply
There are numerous sources of aromatics production in Western Europe and each aromatics
complex is unique. Traditionally, a significant quantity of the aromatics produced in European
reformers has been blended into gasoline. This practice has been restricted under the European
Auto Oil legislation. However, the effect of the 35 percent upper aromatics limit in gasoline is
not expected to be dramatic, as most producers have already moved to within a few percent of
the limit. Gasoline producers operating fluid catalytic cracker (FCC) units normally have no
problem in meeting the 35 percent aromatics limit, and can blend in a proportion of aromatic
streams as long as they do not contain significant quantities of benzene. Aromatics raffinate
streams typically have a high octane rating, and are low in sulfur, and therefore are attractive to
gasoline blenders. Smaller refineries without FCC units typically use significant quantities of
reformate to reach the required octane level. The second phase of the aromatics reduction is
leading to more MTBE, an alternate octane enhancer, being blended into gasoline. In 2005, high
gasoline prices and refinery disruption along the USGC caused by severe hurricanes led to record
high prices for gasoline blend components including MTBE and aromatics. However, MTBE
supplies are expected to increase as the U.S. phases out MTBE use and the Middle East invests
in new capacity. The next phase of gasoline legislation changes will be driven by the European
Union’s initiative toward renewable sources of energy and biodiesel fuels such as ethanol and
ETBE.
Benzene/Toluene 118
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Production of benzene from benzole has enjoyed a small revival as its economics are more
attractive in periods of high oil/benzene pricing. The market price of benzole is flexible
however, so much of the benefit from the recent high benzene prices is believed to have gone to
the coke/benzole producers.
For most producers of aromatics, toluene is surplus to chemical requirements, and dealkylation is
available as an alternative to blending toluene back into gasoline.
There are several benzene expansion planned in the next few years. In 2006 CEPSA started up a
new aromatics plant employing Chevron’s Aromax® technology at its existing refinery in
Huelva, Spain. The benzene will be used to feed a new cumene/phenol plant by the company’s
petrochemical subsidiary Ertisa. Also in 2006, in Tarragona, Spain Repsol YPF has
commissioned a benzene extraction unit to feed the company’s POSM unit. The additional
benzene will be extracted from both pygas and reformate sources. In Antwerp BASF is adding a
new furnace to its naphtha cracker for commissioning in late 2007. With this investment, an
increase in benzene extraction capacity is also expected.
A list of the Western Europre benzene and toluene capacities is shown in Table 5.3.
Benzene/Toluene 119
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.3
Western Europe Benzene and Toluene Capacity, 2006
Benzene/Toluene 120
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.4
Western Europe Benzene Supply, Demand and Trade
(thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 9,437 9,532 10,033 10,130 10,121 10,297 10,571 10,662 10,632 10,632
Speculative Capacity 0 0 0 0 0 0 0 100 100 (10)
Total Capacity 9,437 9,532 10,033 10,130 10,121 10,297 10,571 10,762 10,732 10,622
Production 7,635 7,884 8,242 8,430 8,456 8,901 9,091 9,134 9,066 8,746
Operating Rate 81% 83% 82% 83% 84% 86% 86% 85% 84% 82%
Currently Japan is the largest consumer of benzene in the region, but China is expected to take
the lead by 2008. India and Thailand are expected to show rapid growth from a much smaller
base. Overall benzene consumption is expected to show moderate growth rates during the
outlook period. Asia Pacific benzene consumption is shown in Figure 5.3.
More than 50 percent of the toluene consumed in Asia for chemical use is used in the production
of benzene and xylenes via toluene disproportionation and for on-purpose benzene production
via toluene hydrodealkylation. The second largest use is for solvents, which is expected to show
moderate growth.
Benzene/Toluene 121
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Figure 5.3
Asia Pacific Benzene End-Use Pattern
Others
28%
Styrene
55%
Cumene
17%
Q207_00101.0007.4106_chart s.xls
5.4.2 Supply
Most new major aromatics capacity additions will come on-line in Asia and the Middle East in
the outlook period. The massive ethylene demand growth in China has given rise to several new
large scale liquid based crackers in China with extraction facilities to recover benzene. Several
new additions were added in 2005/2006 (BASF-YPC, Jilin Chemical, Secco, and Maoming
Petrochemical). Others will be added between 2007 and 2009 (CNOOC/Shell and Fujian
Refinery & Chemical). This trend will continue in the forecast period and China will continue to
be nearly self-sufficient in benzene. In addition Zhenhai Refining, Fujian Refinery and LG
Chem are adding benzene from reformate extraction in China during the same timeframe.
Additional benzene will be extracted from Zhenhai Refining’s planned cracker complex slated
for 2010.
In Japan Idemitsu Petrochemical restarted its mothballed HDA unit in Chiba in 2006. Nippon
Oil has announced plans to add benzene extraction capacity from reformate at the Sendai
refinery in 2008. Similarly Kashima Aromatics is adding 170 kta of benzene extraction capacity
from reformate at its plant.
In South Korea, Samsung Total is continuing its expansion by adding an additional 150 kta of
benzene from reformate by 2008. SK Corp started-up its BTX facility in 2006 (80 kta).
Reliance (India), FCFC (Taiwan), Aromatics Thailand and Thai Oil (Thailand), and TPPI
(Indonesia) are adding or have recently added new capacity. In summary Asia Pacific is
expected to add over 3 million tons per year of new capacity between 2006 and 2010.
A list of the Asia Pacific benzene and toluene capacities is shown in Table 5.5.
Benzene/Toluene 122
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006
Country Company Location Capcity, kta Process
Benzene Toluene
China Baling Petrochemical Baling, Hunan 38 102 Reformate extraction
China BASF-YPC Nanjing, Jiangsu 128 Pygas extraction
China CNOOC Dongfang, Hainan 10 27 Reformate extraction
China CNOOC Huizhou, Guangdong 0 Reformate extraction
China CSPC Huizhou, Guangdong 226 Pygas extraction
China Dalian Petrochemical Dalian, Liaoning 45 121 Reformate extraction
China Daqing General Daqing, Heilongjiang 120 Pygas extraction
China Daqing General Daqing, Heilongjiang 15 40 Reformate extraction
China Dushanzi Petrochemical Karamay, Xinjiang 65 Pygas extraction
China Fujian Refinery & Chemical Fuzhou, Fujian 0 Pygas extraction
China Fujian Refinery & Chemical Fuzhou, Fujian 0 Reformate extraction
China Fujian Refinery & Chemical Fuzhou, Fujian 0 Transalkylation
China Fushun Petrochemical Fushun, Liaoning 0 Pygas extraction
China Fushun Petrochemical Fushun, Liaoning 37 100 Reformate extraction
China Fushun Petrochemical Fushun, Liaoning 30 TDP
China Gaoqiao Petrochemical Pudong, Shanghai 30 Pygas extraction
China Guangzhou Petrochemical Guangzhou, Guangdong 35 Pygas extraction
China Guangzhou Petrochemical Guangzhou, Guangdong 15 Pygas extraction
China Jilin Chemical Jilin, Jilin 20 HDA
China Jilin Chemical Jilin, Jilin 160 Pygas extraction
China Jilin Chemical Jilin, Jilin 45 Pygas extraction
China Jilin Chemical Jilin, Jilin 39 105 Reformate extraction
China Jinling Petrochemical Nanjing, Jiangsu 45 121 Reformate extraction
China Jinxi Refinery Jinxi, Liaoning 25 67 Reformate extraction
China Jinzhou Petrochemical Jinzhou, Liaoning 15 40 Reformate extraction
China Jiujiang Petrochemical Jiujiang, Jiangxi 10 27 Reformate extraction
China Lanzhou Petrochemical Lanzhou, Gansu 30 Pygas extraction
China Lanzhou Petroleum Lanzhou, Gansu 37 100 Reformate extraction
China Liaoyang Petrochemical Liaoyang, Liaoning 9 Isomerization and fractionation
China Liaoyang Petrochemical Liaoyang, Liaoning 20 Pygas extraction
China Liaoyang Petrochemical Liaoyang, Liaoning 42 113 Reformate extraction
China Liaoyang Petrochemical Liaoyang, Liaoning 100 TDP
China Luoyang Petrochemical Luoyang, Henan 105 282 Reformate extraction
China Maoming Petrochemical Maoming, Guangdong 157 Pygas extraction
China Maoming Petrochemical Maoming, Guangdong 40 108 Reformate extraction
China Qilu Petrochemical Zibo, Shandong 3 Isomerization and fractionation
China Qilu Petrochemical Zibo, Shandong 185 Pygas extraction
China Qilu Petrochemical Zibo, Shandong 50 134 Reformate extraction
China Qilu Petrochemical Zibo, Shandong 15 TDP
China Qingdao Lidong Qingdao, Shandong 50 538 Reformate extraction
China Secco Caojing, Shanghai 180 Pygas extraction
China Shanghai Petrochemical Jinshanwei, Shanghai 10 Isomerization and fractionation
China Shanghai Petrochemical Jinshanwei, Shanghai 240 Pygas extraction
China Shanghai Petrochemical Jinshanwei, Shanghai 40 TDP
China Shijiazhuang Refinery Shijiazhuang, Hebei 9 24 Reformate extraction
China Taiyuan Chemical Tiayuan, Shanxi 42 Coal tar
China Tianjin Petrochemical Dagang, Tianjin 0 Pygas extraction
China Tianjin Petrochemical Tianjin, Tianjin 120 323 Reformate extraction
China Tianjin Petrochemical Tianjin, Tianjin 22 TDP
China Urumqi Petrochemical Urumqi, Xinjiang 2 Isomerization and fractionation
China Urumqi Petrochemical Urumqi, Xinjiang 25 67 Reformate extraction
China Urumqi Petrochemical Urumqi, Xinjiang 10 TDP
China Various China Various China, China 556 Coal tar
China Wuhan Petrochemical Wuhan, Hubei 24 42 Reformate extraction
China Yangzi Petrochemical Nanjing, Jiangsu 34 Isomerization and fractionation
China Yangzi Petrochemical Nanjing, Jiangsu 190 Pygas extraction
China Yangzi Petrochemical Nanjing, Jiangsu 85 229 Reformate extraction
China Yangzi Petrochemical Nanjing, Jiangsu 108 TDP
China Yanhua Petrochemical Beijing, Beijing 40 HDA
China Yanhua Petrochemical Beijing, Beijing 142 Pygas extraction
China Yanhua Petrochemical Beijing, Beijing 10 27 Reformate extraction
China Zhenhai Refining Ningbo, Zhejiang 0 Pygas extraction
China Zhenhai Refining Ningbo, Zhejiang 57 153 Reformate extraction
China Zhenhai Refining Ningbo, Zhejiang 100 269 Reformate extraction
China Zhenhai Refining Ningbo, Zhejiang 30 TDP
China Zhongyuan Petrochemical Puyang, Henan 52 Pygas extraction
Japan Adchemco Fukuyama 0 Coal tar
Japan Cosmo Matsuyama Matsuyama, Ehime 96 258 Reformate extraction
Japan Fuji Oil Chiba 100 HDA
Japan Fuji Oil Chiba 75 202 Reformate extraction
Japan Idemitsu Petrochemical Chiba 126 HDA
Japan Idemitsu Petrochemical Tokuyama, Yamaguchi 80 HDA
Japan Idemitsu Petrochemical Chiba 80 Pygas extraction
Japan Idemitsu Petrochemical Tokuyama, Yamaguchi 100 Pygas extraction
Japan Idemitsu Petrochemical Chiba 302 812 Reformate extraction
Japan Idemitsu Petrochemical Tokuyama, Yamaguchi 100 269 Reformate extraction
Benzene/Toluene 123
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006 (cont’d)
Benzene/Toluene 124
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006 (cont’d)
Benzene/Toluene 125
PERP 06/07-6
Q207_00101.0007.4106
Section 5 Market Analysis
Table 5.6
Asia Pacific Benzene Supply, Demand and Trade
(thousand metric tons)
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Firm Capacity 14,716 15,123 15,614 15,927 16,505 17,883 18,707 19,550 20,116 20,465
Speculative Capacity 0 0 0 0 0 0 200 531 662 1,032
Total Capacity 14,716 15,123 15,614 15,927 16,505 17,883 18,907 20,082 20,778 21,497
Production 11,446 11,814 12,764 14,100 15,167 14,821 15,967 16,826 17,121 17,406
Operating Rate 78% 78% 82% 89% 92% 83% 84% 84% 82% 81%
Net Exports (78) (271) (354) 434 367 (387) (252) (74) (262) (578)
Consumption 11,524 12,085 13,118 13,666 14,799 15,220 16,245 16,917 17,418 18,010
Benzene/Toluene 126
PERP 06/07-6
Q207_00101.0007.4106
Appendix A Elements of Nexant's ChemSystems Capital Cost Estimates
The inside battery limits (ISBL) portion of a plant can be thought of as a boundary over which
are imported raw materials, catalysts and chemicals, and utility supply streams. In a like manner,
main products, byproducts, and spent utility return streams are exported over this boundary.
ISBL investment includes the cost of the main processing blocks of the chemical plant necessary
to manufacture products. It represents an "instantaneous" investment (i.e., no escalation) for a
plant ordered from a contractor and built on a prepared site with normal load-bearing and
drainage characteristics of a developed country.
Battery limits investment includes the installed cost of the following major items:
Process equipment: vessels and internals, heat exchangers, pumps and compressors,
drivers, solids handling
Major spare equipment/parts (e.g., spare rotor for turbine or compressor)
Building housing process units
Process and utility pipes and supports within the major process areas
Instruments, including computer control systems
Electrical wires and hardware
Foundations and pads
Structures and platforms
Insulation
Paint/corrosion protection
Process sewers
Fire water pipes and monitors
Utility stations
The installed cost also includes construction overhead: fringe benefits, payroll burdens, field
supervision, equipment rentals, small tools (expendables), field office expenses, site support
services, temporary facilities, etc.
Benzene/Toluene A-1
PERP 06/07-6
Q207_00101.0007.4106
Appendix A Elements of Nexant's ChemSystems Capital Cost Estimates
Outside battery limits (OSBL) investment includes the plant investment items that are required in
addition to the main processing units within the battery limits. These auxiliary items are
necessary to the functioning of the production unit, but perform in a supporting role rather than
being directly involved in production. A distinguishing characteristic is the potential for sharing
offsite facilities among several production units in a large plant, in which case investment cost
would be allocated or prorated.
OSBL investment includes the installed cost of the following major items:
Storage for feeds, products, byproducts, including tanks/silos, dikes, inerting, process
warehouse, and bagging/palletizing equipment
Steam generation units
Cooling water systems, including cooling towers and circulation pumps
Process water treatment systems and supply pumps
Boiler feed water treatment systems and supply pumps
Refrigeration systems, including chilled water/brine circulating pumps
Heat transfer medium systems, including organic vapor, hot oil, molten salts
Electrical supply, transformers, and switchgear
Loading and unloading arms, pumps, conveyors, lift trucks, including those to handle
barge, tank/hopper car, and tank/hopper/other truck traffic; weigh scales
Auxiliary buildings, including all services, furnishings, and equipment:
− Central control room
− Maintenance
− Stores warehouse
− Laboratory
− Garages/fire station
− Change house/cafeteria
− Medical/safety
− Administration
General utilities, including plant air, instrument air, inert gas, stand-by electrical
generator, fire water pumps
Site development, including roads and walkways, parking, railroad sidings, electrical
main substation, lighting, water supply, fuel supply, clearing and grading, drainage,
fencing, sanitary and storm sewers, and communications
Benzene/Toluene A-2
PERP 06/07-6
Q207_00101.0007.4106
Appendix A Elements of Nexant's ChemSystems Capital Cost Estimates
Yard pipes, including lines for cooling water, process water, boiler feed water, fire water;
fuel; plant air, instrument air, inert gas; collection of organic wastes, aqueous wastes, and
flare/incinerator feeds; and process tie-ins to storage
These charges are typically 15 to 25 percent of installed ISBL and OSBL costs and are included
proportionately in the ISBL and the OSBL investments. Contractor charges include the
following major items:
Detailed design and engineering, including process and offsites design and general
engineering, equipment specifications, plant layout, drafting, cost engineering, scale
models
Administrative charges, including project management, engineering supervision,
procurement, expediting, inspection, travel and living, home office construction
expenses, general home office overhead
Contractor profit
A project contingency allowance is typically 15 to 25 percent of installed ISBL and OSBL costs
and is included proportionately in the ISBL and the OSBL investments.
A project contingency allowance is applied to the total of the above costs to take into account
unknown elements of the process being estimated. For well-defined processes where primary
input has come from engineering contractors, a contingency of 10 to 20 percent would be typical.
At the other end of the spectrum, a capital estimate for a speculative process developed from
patent and literature data alone might warrant a contingency of 20 to as much as 50 percent in
extreme cases.
These costs are very site/project specific; however, they typically range from 20 to 40 percent of
installed ISBL + OSBL costs. A norm value of 25 percent will be used in the absence of more
specific information.
For the purpose of our study, other project costs normally include startup/commissioning costs,
miscellaneous owner’s costs, etc. They are described below:
Startup/Commissioning Costs
Benzene/Toluene A-3
PERP 06/07-6
Q207_00101.0007.4106
Appendix A Elements of Nexant's ChemSystems Capital Cost Estimates
− Licensor representatives
− Contractor personnel
− Equipment supplier/other vendor representatives
Benzene/Toluene A-4
PERP 06/07-6
Q207_00101.0007.4106
Appendix A Elements of Nexant's ChemSystems Capital Cost Estimates
Accounts receivable (products and byproducts shipped but not paid by customer),
typically one month's gross cost of production (COP)
Cash on hand (short-term operating funds), typically one week's gross COP minus
depreciation
Minor spare equipment and parts inventory, percentage of replacement BL capital
Credit for accounts payable (feedstocks, catalysts, chemicals, and packaging materials
received but not paid to supplier), typically one month's delivered cost
Value of product and byproduct inventories, typically two weeks' gross COP
Value of raw material inventory, typically two weeks' delivered cost
Benzene/Toluene A-5
PERP 06/07-6
Q207_00101.0007.4106
Appendix B PERP Program Title Index
This index is intended to be a handy and convenient tool for quickly identifying PERP reports of
interest. It should be noted, however, that this is a title index only. For a more complete search,
dating back to 1972, the full subject indices should be used. See your local technical information
service department for the PERP subject indices or contact Nexant. To browse all Nexant
ChemSystems reports, please visit: www.chemsystems.com
Acetic Acid 02/03-1 09/03 Aromatics from Light Olefins 97/98S1 04/99
Acetic Acid/Acetic Anhydride 97/98-1 01/99 Aromatics Production, Optimizing 05/06S6 02/07
Acetic Acid via Ethane Oxidation 99/00S5 01/01 Ascorbic Acid and Sorbitol 97/98S11 03/99
Acetic Anhydride/Cellulose Acetate 03/04S1 06/04 Barrier Monomers for PET 02/03S12 12/03
Acetone/Phenol/Cumene 01/02-2 10/02 Benzene, Styrene from Ethane and 05/06S3 11/06
Adipic Acid 03/04-3 11/04 Biotech Route to Lactic Acid/Polylactic Acid 00/01S3 05/02
Benzene/Toluene B-1
PERP 06/07-6
Q207_00101.0007.4106
Appendix B PERP Program Title Index
Chlor Alkali 01/02S4 03/03 Ethane Oxidation, Acetic Acid via 99/00S5 01/01
Coal Gasification Technologies 03/04S11 01/05 Ethane Partial Oxidation, Ethylene via
Catalytic 03/04S2 07/04
Coal to Olefins 05/06S5 04/07
Ethane and Benzene, Styrene from 05/06S3 11/06
Compounding, Polypropylene 04/05S6 12/05
Ethanol 04/05-8 01/06
Copolyester and Copolyamide Elastomers,
Thermoplastic 02/03S9 10/03 Ethanol 99/00-8 08/01
Developments in PET Recycling 99/00S4 07/00 Extending the Methane Value Chain 99/00S9 10/00
Benzene/Toluene B-2
PERP 06/07-6
Q207_00101.0007.4106
Appendix B PERP Program Title Index
Formaldehyde and Derivatives 04/05S10 01/06 LNG Technologies, Advances in 03/04S10 10/04
Fuel Cells for Transportation 02/03S5 12/03 Maleic Anhydride 03/04-7 02/05
Fuel Switching with NGLs/Small Scale LNG 04/05S1 08/05 Managing Technology Development in
the Chemical Industry 97/98S2 06/99
Gasification, Biomass 06/07S5 *
MDI/TDI 98/99S8 09/99
Gasification Technologies, Coal 03/04S11 01/05
Medium Quality Terephthalic Acid 03/04S6 10/04
Gas Processing and NGL Extraction: Natural
Gas Conditioning 04/05S8 03/06 MEK/Phenol Co-Product Process 04/05S12 02/06
Glycerin 00/01S4 11/01 Methane Value Chain, Extending the 99/00S9 10/00
High Density Polyethylene 01/02-1 12/02 Modified Polyphenylene Oxide (MPPO) 02/03S3 03/03
High Temperature Polymers, Crystalline 04/05S3 02/06 MTBE Facilities, Alternative Uses of 99/00-7 03/01
High Temperature Thermoplastic Nylons 01/02S3 06/02 MTBE Phaseout on Chemical Markets,
Impact of 00/01S2 06/01
Hydrocarbon Resins 99/00S10 03/01
Nanocomposites, Thermoplastic 00/01S11 09/01
Hydrogen Peroxide 03/04-5 10/04
NGL Extraction and Gas Processing:
Hydrogen Peroxide 98/99-8 09/99 Natural Gas Conditioning: 04/05S8 03/06
Hydrogen Production in Refineries 06/07S1 10/07 NGLs/Small Scale LNG, Fuel Switching with 04/05S1 08/05
Benzene/Toluene B-3
PERP 06/07-6
Q207_00101.0007.4106
Appendix B PERP Program Title Index
Petroleum Coke Utilization Options 97/98S10 03/99 Propionic Acid 98/99S10 06/99
Polylactic Acid/Lactic Acid, Biotech Route to 00/01S3 10/02 Receiving Terminals, LNG 05/06S12 01/07
Polymers, Super Absorbent (SAP) 03/04S3 04/04 Routes to Propylene 97/98S3 02/00
Polyolefin Elastomers 05/06S7 02/07 Sorbitol and Ascorbic Acid 97/98S11 03/99
Polyphenylene Sulfide (PPS) 02/03S4 04/03 Specialty LDPE Copolymers 03/04S9 12/04
Benzene/Toluene B-4
PERP 06/07-6
Q207_00101.0007.4106
Appendix B PERP Program Title Index
Benzene/Toluene B-5
PERP 06/07-6
Q207_00101.0007.4106