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ThyssenKrupp Uhde
Aromatics
Our new name is
ThyssenKrupp Industrial Solutions
www.thyssenkrupp-industrial-solutions.com
Table of contents
22
	1.	 Company profile	 3
	2.	 Uhde and Aromatics	 5
	3.	 Aromatics – Sources, Demand and Applications	 6
	4.	 Process Configuration	 8
	4.1	 Aromatics from Pyrolysis Gasoline	 9
	4.2	 Aromatics from Reformate	 12
	4.3	 Aromatics from Coke Oven Light Oil 	 15
	5.	 Technology	 16
	5.1	 Hydrogenation Technology	 16
	5.1.1	 Hydrogenation of Pyrolysis Gasoline	 16
	5.1.2	 Hydrogenation of Reformate	 18
	5.1.3	 Hydrogenation of Coke Oven Light Oil	 19
	5.2	 Fractionation Technology	 20
	5.2.1	 Conventional Distillation	 20
	5.2.2	 Divided Wall Column Distillation	 20
	5.3	 Morphylane®
Extractive Distillation	 22
	5.3.1	 Conventional Morphylane®
Process	 22
	5.3.2	 Nitrogen Guard Bed	 22
	5.3.3	 Single-Column Morphylane®
Extractive Distillation	 23
	5.4	 Hydrodealkylation Technology	 25
	5.5	 Toluene Disproportionation Technology	 25
	5.6	 Toluene/C9+
Transalkylation Technology	 26
	5.7	 Para-Xylene Adsorption Technology	 26
	5.8	 Xylenes Isomerisation Technology 	 27
	6.	 Operating Results of Extractive Distillation Plants	 28
	7.	 Laboratory, Analytical and R&D Services	 30
	7.1	 Analytical Facilities	 30
	7.1.1	 Gas chromatography	 30
	7.1.2	 Physical and chemical methods	 30
	7.1.3	 Other analytical methods	 30
	7.2	 Determination of thermohysical properties	 30
	7.3	 Pilot Plant Tests	 31
	7.3.1	 Separation techniques	 31
	7.3.2	 Absorption/adsorption techniques	 31
	8.	 Services for our customers	 32
	9.	 Main references	 34
Uhde’s head office
Dortmund, Germany
33
1. Company profile
With its highly specialised workforce of more than 5,600 employees
and its international network of subsidiaries and branch offices, Uhde,
a Dortmund-based engineering contractor, has to date successfully
completed over 2,000 projects throughout the world.
Uhde’s international reputation has been built on the successful
application of its motto Engineering with ideas to yield cost-effective
high-tech solutions for its customers. The ever-increasing demands
placed upon process and application technology in the fields of
chemical processing, energy and environmental protection are met
through a combination of specialist know-how, comprehensive
service packages, top-quality engineering and impeccable punctuality.
4
Erection of the 60 meter high benzene
extractive distillation column for Titan
Petrochemicals, Pasir Gudang, Malaysia.
Capacity: 168,000 mtpy benzene and
toluene from pyrolysis gasoline.
5
Uhde’s extensive knowledge in extractive
distillation technology and its excellent labora-
tory facilities have led it to develop the most
advanced process configurations for recover-
ing aromatics and other products, such as
butenes, a-olefins, cumene, isoprene and
phenols, from different feedstocks.	
Uhde’s history in aromatics goes back to
the first decades of the 20th century when
Heinrich Koppers developed the Koppers
coke oven technology for the production of
coke for the steel industry. Right up to the
fifties, coke oven light oil, which is recov-
ered as a by-product of crude coke oven
gas in coke oven plants, was the world’s
main aromatics source.	
Due to the large quantity of impurities
(diolefins, olefins, nitrogen, oxygen and
sulphur compounds) the coke oven light
oil had to be purified before the aromatics
could be recovered. In those days, the lower
benzene quality requirements could be met
by sulphuric acid treatment and convention-
al distillation processes. However, the large
quantity of aromatics lost during sulphona-
tion and the relatively high sulphur content
in the benzene product were the driving
force in the development of a hydrogena-
tion process which was worked on together
with BASF AG, Ludwigshafen, Germany
and which solved the problems caused by
unsaturated and inorganic impurities in the
feedstock. The final purification of aromat-
ics continued to be achieved by distillation
only.	
At the beginning of the fifties, high-purity
aromatics recovered by liquid-liquid extrac-
tion in refineries came on to the market.
The superior quality of these aromatics made
it impossible for the aromatics distilled from
coke oven light oil to compete. In addition,
the improved purification process using
azeotropic distillation was linked with high
investment costs and inefficient energy util-
isation.	
The liquid-liquid extraction process could not
be used for coke oven light oil with an aro-
matics content of 95% as separable phases
are not able to form when the aromatics
content is this high. At the request of the
German coal and steel industry, Uhde initi-
ated intensive R&D activities and developed
a new process for coke oven light oil to ob-
tain aromatics of a similar or better quality
than those from refineries.
The process developed by Uhde was based
on a new solvent called N-formylmorpholine
and used a different separation principle in-
volving extractive distillation. The process
was able to produce all the product purities
required whilst reducing utilities consump-
tion considerably as compared to liquid-
liquid extraction processes.
The first commercial plant based on this
extractive distillation process (Morphylane®
process) went on-stream in 1968 and pro-
duced excellent results with regard to prod-
uct quality and utility consumption figures.
Based on the outstanding performance of
this plant, the Morphylane®
process was
subsequently adapted to other feedstocks,
such as pyrolysis gasoline and reformate.
The process has undergone continuous im-
provements and optimisation and its cost-
effectiveness has led it to replace liquid-
liquid extraction in all applications. Further-
more, by optimising the combination of all
the processes involved, such as hydrogena-
tion, fractionation and aromatics extractive
distillation, the complete process line for
recovering aromatics from all possible feed-
stocks was able to be improved to such an
extent that competitive processes were left
standing.
Up to now, Uhde has been awarded con-
tracts for more than 60 Morphylane®
plants
worldwide for recovering aromatics from
pyrolysis gasoline, reformate and coke oven
light oil. Leading aromatics producers, such
as Chevron Phillips, Dow, BASF, Total, Shell
and SK Corp., selected the Morphylane®
pro-
cess on the strength of its outstanding per-
formance figures and its optimised process
configuration after comparing it with com-
petitive technologies.
Uhde provides its customers with the fol-
lowing services in the field of aromatics
production:
•	Consulting services	
•	Analytical services	
•	Licensing	
•	Engineering	
•	Procurement	
•	Construction	
•	Plant operation	
•	Maintenance services
•	Plant optimisation services
Benzene Toluene Para-Xylene
5
2.	 Uhde and Aromatics
	 Remarkably long experience
Pyrolysis Gasoline 47%
Reformate 33%
HDA/TDP 15%
Coke Oven Light Oil 5%
Reformate 68%
Pyrolysis Gasoline 29%
Coke Oven Light Oil 3%
Pyrolysis Gasoline 47%
Reformate 33%
HDA/TDP 15%
Coke Oven Light Oil 5%
Reformate 68%
Pyrolysis Gasoline 29%
Coke Oven Light Oil 3%
6
3.	 Aromatics – Sources,
	 Demand and Applications
Sources	
The main sources of aromatics (benzene,
toluene, xylenes) are reformate from cata-
lytic reforming, pyrolysis gasoline from
steam-crackers and coke oven light oil from
coke oven plants (Fig. 3-01). The reformate
from catalytic reforming provides the basic
supply of benzene, toluene, xylenes and
heavier aromatics. The majority of toluene
and heavier aromatics from reformate is
converted to benzene and xylenes and is
mainly used for p-xylene production. The
remaining supply of aromatics is produced
from pyrolysis gasoline and from coke oven
light oil.	
Benzene, which has the highest production
rate beside xylenes and toluene, is mainly
produced from pyrolysis gasoline, followed
by reformate. A significant percentage of
Benzene, i.e. 15%, is also obtained from
the hydrodealkylation (HDA) of heavier aro-
matics and from toluene disproportionation
(TDP). The smallest percentage of about
5% of benzene is obtained from coke oven
light oil (Fig. 3-02).
World Aromatics Sources World Benzene Sources
Fig. 3-01 Source: HPP Science Fig. 3-02 Source: HPP Science
HDA: Hydrodealkylation of heavier aromatics
TDP: Toluene disproportionation
Aromatics (benzene, toluene and xylenes) rank amongst
the most important intermediate products in the chemical
industry and have a wide range of applications.
Ethylbenzene
Cumene
Cyclohexane
Nitrobenzene
Alkylbenzene
Chlorobenzenes
Nitrotoluenes
Solvents
o-Xylene
m-Xylene
p-Xylene
Styrene
Phenol
α-Methylstyrene
Caprolactam
Adipic Acid
Cyclohexanone
Aniline
LAB
Toluene Diisocyanate
Explosives, Dyes
Phthalic Anhydride
Isophthalic Acid
Terephthalic Acid/
Dimethylterephthalate
Polystyrene, ABS Resins, SBR
Aniline, Phenolic Resins, Epoxy
Resins, Surfactants
Adhesives, ABS Resins, Waxes
Polyamide 6
Polyamide 66
Polyurethane Foams
Alkyd Resins, Methylacrylate
Polyesters, Alkyd Resins
Polyesters
Benzene
Toluene
Xylenes
7
2005
0
10
20
30
40
50
2007
2009
Benzene
Toluene
Xylenes
(Million metric tons/year)
World Aromatics Demand
Fig. 3-03
Source: HPP Science
Fig. 3-04
Main Applications of BTX Aromatics
Demand	
Worldwide, approx. 110 million tonnes of
BTX aromatics are currently produced per
year. An increase in demand of almost
4% p.a. is predicted for benzene due to the
growth of end-use markets such as poly-
styrene, polycarbonate, phenolic resins
and nylon (Fig. 3-03).
In the case of xylenes the increase in de-
mand is determined by p-xylene, the big-
gest isomer in terms of quantity. Growth
in consumption of this isomer is expected
to well exceed 5% p.a. in the near future.
Para-xylene is used almost exclusively for
the production of polyester via purified
terephthalic acid.
The estimated growth in overall toluene
consumption is less than 3% p.a. Its major
direct chemical use is toluene diisocyanate
(TDI), a raw material for the production of
polyurethane. Toluene extraction will in-
crease as toluene is converted into benzene
and xylenes via disproportionation.
Applications	
The wide range of applications involving
the main aromatics, benzene, toluene and
xylenes (Fig. 3-04), illustrates the impor-
tance of these intermediate products to the
chemical industry.
Typical Composition [wt.%]
Component
Benzene
Toluene
Xylenes
Ethylbenzene
C9+ Aromatics
Total Aromatics
Naphthenes
Olefins
Paraffins
Sulphur
Pyrolysis Gasoline
30
20
4
3
3
60
High
High
Low
Up to 1000 ppm wt.
Reformate
3
13
18
5
16
55
Low
High
High
 1ppm wt.
Light Reformate
24
46
 0.5
 0.5
0
70
Low
Low
High
Low
Coke Oven Light Oil
65
18
6
2
7
98
High
High
Low
Up to 1 wt.%
Fig. 4-01
Off-Gas
to Steamcracker
Selective
Hydrogenation
H2
C5- Fraction
to Gasoline Pool
Full
Hydrogenation
H2
Depentanizer
Stabilizer
Benzene
Toluene
Non-Aromatics
to Steamcracker
C8+ Fraction
to Gasoline Pool
Extractive
Distillation
B/TColumn
Deheptanizer
Crude Pyrolysis
Gasoline from
Steamcracker
8
4.	 Process Configuration
	 Aromatics from Pyrolysis Gasoline,
	 Reformate  Coke Oven Light Oil
Aromatics (benzene, toluene, xylenes) are
mainly recovered from the following three
feedstocks:
•	Pyrolysis gasoline from steamcrackers
•	Reformate from catalytic reformers
•	Light reformate from aromatics production
•	Coke oven light oil from coke oven plants
The type of aromatics recovered and the
process configuration are dictated by the
feedstock used, as the composition of these
feedstocks differs with regard to the content
of paraffins, olefins, naphthenes and aro-
matics (Fig. 4-01) and the amount of im-
purities, such as chlorine, oxygen, nitrogen
and sulphur components.
Fig. 4-02
Aromatics from Pyrolysis Gasoline
Off-Gas
to Steamcracker
Selective
Hydrogenation
H2
Benzene
Non-Aromatics
to Steamcracker
C5- Fraction
to Gasoline Pool
Full
Hydrogenation
Extractive
Distillation
H2
Depentanizer
C9+ Fraction
to Gasoline
Pool
Heavy AromaticsH2
Hydro-
dealkylation
Off-Gas
Aromatics
B/TColumn
Stabilizer
Deheptanizer
Deoctanizer
Crude Pyrolysis
Gasoline from
Steamcracker
9
4.1 Aromatics from Pyrolysis Gasoline
Pyrolysis gasoline is mainly used to recover
benzene as well as benzene and toluene
together. Producing mixed xylenes from
pyrolysis gasoline is uneconomical due to
the low xylene content and the high ethyl-
benzene content in the pyrolysis gasoline.
A typical process route for recovering
benzene and toluene, starting from crude
pyrolysis gasoline, is illustrated in Fig. 4-02.
In the first step, the selective hydrogena-
tion, diolefins are saturated at a relatively
low temperature to avoid polymerisation.
The C5-
fraction is usually separated from
the selectively hydrogenated pyrolysis gaso-
line in a depentaniser upstream of the full
hydrogenation stage and sent to the gaso-
line pool as an octane-blending component.
Thereby, hydrogen consumption is mini-
mised and the size of the full hydrogenation
unit can be reduced.
If, however, the C5-
fraction is sent back to
the steamcracker as feedstock, it should
be fully hydrogenated and separated with
the non-aromatics downstream of the full
hydrogenation unit in a combined depen-
taniser/stabiliser or an extractive distillation
stage. This dispenses with the need for a
complete depentaniser system.
Olefins as well as impurities, such as nitro-
gen, sulphur and other components, are
completely hydrogenated in the full hydro-
genation unit. The off-gas containing H2
S
is separated in the stabiliser and then re-
turned to the steamcracker.
In order to extract the required aromatics, a
specific aromatics cut has to be separated
from the pretreated pyrolysis gasoline. In
the case of benzene recovery, a C6-
cut is
separated, in case of benzene and toluene
recovery, a C7-
cut is separated in a predis-
tillation column and sent to the extractive
distillation. The C7+
or C8+
fraction is sent to
the gasoline pool as feedstock.
Benzene or benzene and toluene are sepa-
rated from the non-aromatics in the extrac-
tive distillation unit which comprises a simple
two column system. The non-aromatics are
sent back to the steamcracker as feedstock.
In the case of combined benzene and tolu-
ene recovery, both products have to be sepa-
rated downstream in a benzene/toluene col-
umn system.
In some cases it can be more economical
to convert the C7+
aromatics into benzene
to maximise the benzene output. In this
case, a thermal hydrodealkylation unit is
integrated in such a way that the extracted
toluene and xylenes from the predistillation
stage are dealkylated to form benzene
(Fig. 4-03).
Fig. 4-03
Maximum Benzene Recovery
from Pyrolysis Gasoline
10
Aromatics	complex	for	
BASF	in	Mannheim/Germany.
Capacities: 405,000mtpy aromatics extraction,
340,000mtpy hydrodealkylation
The full range:
Consisting of pyrolysis gasoline full hydrogenation,
pyrolysis gasoline separation, reformate separation,
benzene extractive distillation, toluene/xylene
extractive distillation and hydrodealkylation.
1111
H2 Light Ends
H2
Xylenes
Isomerisation
Benzene
Non-Aromatics
to Gasoline Pool
p-Xylene
Adsorption
Extractive
Distillation
ReformateSplitter
C9+ Aromatics
to Gasoline Pool
Toluene Dis-
proportionation
p-Xylene
XyleneColumn
BenzeneColumn
TolueneColumn
Reformate from
Catalytic Reformer
o-Xylene
Light Ends
o-XyleneColumn
C8+
C7–
12
The off-gas produced can then be used
as fuel gas. The toluene does not necessar-
ily have to be extracted before being fed to
the hydrodealkylation stage. However, if the
toluene fraction is fed directly from the pre-
distillation stage, more hydrogen has to be
consumed to crack the C7
non-aromatics
and consequently more off-gas is pro-
duced.
Depending on the feedstock available and
the products required, individual process
configurations and heat integration of the
individual units can be optimised whilst tak-
ing into account local conditions such as
specific utility availability and costs. Uhde
finds the most cost-effective solutions with
regard to investment and operating costs
for its customers.
4.2 Aromatics from Reformate
As a result of its relatively low benzene con-
tent and relatively high toluene and xylenes
content, reformate is mainly used to pro-
duce p-xylene. Another application for aro-
matics recovery is the reduction of benzene
in motor gasoline by extracting benzene from
the catalytic reformate.
P-Xylene Production
The typical process route for the production
of p-xylene from reformate is illustrated in
Fig. 4-04.
In this case catalytic reformate is split into
a C7-
fraction and a C8+
fraction. The C7-
frac-
tion is then sent to the extractive distillation
stage, where benzene and toluene are sepa-
rated from the C7-
non-aromatics.
Fig. 4-04
Aromatics from Reformate
13
The C8+
fraction is sent directly to the
p-xylene loop without the xylenes being ex-
tracted. The non-aromatics content in this
fraction is very low and can therefore be
easily handled in the p-xylene loop. Conse-
quently only benzene and toluene have to
be extracted and not full-range BTX.
The toluene is fed to the toluene dispropor-
tionation stage where it is converted into
benzene and xylenes.
The benzene produced is separated as a
high-purity product together with the ex-
tracted benzene, whilst the unconverted
toluene is recycled back to the dispropor-
tionation.
After separation, the mixed xylenes fraction
from the disproportionation, the xylenes
fraction from the reformate splitter and the
recycled xylenes from the isomerisation are
sent to the p-xylene adsorption, where
p-xylene is separated from the xylenes. The
remaining xylenes (m-xylene, o-xylene and
ethylbenzene) are sent to the isomerisation
to be converted into p-xylene.
If o-xylene is also to be obtained as a prod-
uct, it must be removed as a pure product
by distillation in a separate column system
before the xylenes enter the p-xylene isom-
erisation loop.
If maximum p-xylene production is required,
a toluene and C9+
aromatics transalkylation
is integrated into the process configuration
(not illustrated). With respect to an opti-
mised heat integration, vapours from the
xylenes separation can be used to heat the
benzene and toluene columns and other
consumers.
Half a million tonnes of benzene from reformate for
Chevron Phillips Chemical Company,
Pascagoula, MS, USA
14
Reformate
from Catalytic
Reformer
Selective
Hydrogenation
H2 Off-Gas
ReformateSplitter
Non-Aromatics
to Gasoline Pool
Extractive
Distillation
Benzene
C7+ Fraction
to Gasoline Pool
Benzene Reduction in Motor Gasoline
In order to comply with the latest regula-
tions limiting the benzene content in motor
gasoline, the refining industry has to adjust
its operations to either convert or recover
benzene and other aromatics.
Uhde has developed an optimised Mor-
phylane®
extractive destillation process
for recovering benzene from reformate with
lower investment and operating costs (Fig.
4-05) compared to aromatics saturation,
liquid-liquid extraction and other processes.
The reformate from the catalytic reformer
is fed to the selective hydrogenation stage
to saturate the diolefins which influence
the acid wash colour (AWC) of the benzene
product.
The selective hydrogenation unit consists
of a small reactor which is operated at low
temperatures and pressure in a trickle phase.
The small amount of off-gas is separated
in the reactor using only phase separation.
This upstream hydrogenation of diolefins
eliminates the necessity for a downstream
clay treating and subsequent product distil-
lation thus saving considerably on invest-
ment and operating costs.	
The pretreated reformate is fractionated
and the C6-
fraction is sent to the extrac-
tive distillation where high purity benzene
is removed from the non-aromatics in a
simple two column system. One of the
advantages of the Morphylane®
extractive
distillation process is that both dissolved
hydrogen and light hydrocarbons can be
easily removed with the overhead prod-
uct thereby saving on investment for an
upstream depentaniser system.
Another advantage of the process is the ex-
cellent benzene purity. A very low benzene
content in the non-aromatics ( 0.1 wt%)
can be achieved in the optimised extractive
distillation configuration.	
Determined by the specific requirements of
the refiners, Uhde also provides other pro-
cess configurations, e.g. a combination of
reformate fractionation (producing several
blending cuts) and benzene extractive distil-
lation or a combined benzene and toluene
extraction.
Fig. 4-05
Benzene from Reformate
(Benzene Removal from Motor Gasoline)
Deheptanizer
Coke Oven
Light Oil
C8+
Hydrorefining
Extractive
Distillation
C7-
C9+
Non-Aromatics
Tar
Toluene
Benzene
H2 Off-Gas
Xylenes
B/TColumn
C8Column
Stabilizer
C8-
15
4.3 Aromatics from Coke Oven Light Oil
Coke oven light oil is generally used as a
feedstock for recovering benzene, toluene,
xylenes and higher aromatics as it has a
very high aromatics content. The general
process line for recovering aromatics from
coke oven light oil is illustrated in Fig. 4-06.
In a first step, the feedstock, which has a
high content of impurities and a high con-
tent of olefins and diolefins, is hydrogen-
ated. A special hydrorefining process with
a specific heating/evaporation system and
a two stage reaction system is used for this
purpose.
The hydrogenated coke oven light oil is sent
to the stabiliser where the off-gas, which
contains for instance H2
S, is separated.
The stabilised coke oven light oil is then sent
to a deheptaniser. The overhead C7-
fraction
is sent to the extractive distillation in which
benzene and toluene are separated from the
relatively small amount of non-aromatics in
a single extractive distillation before being
split into high-purity benzene and toluene.
The C8+
fraction leaving wthe bottom of the
deheptaniser is usually sent to another frac-
tionation system where xylenes and higher
aromatics are recovered by distillation.
Fig. 4-06
Aromatics from Coke Oven Light Oil
Uhde engineered the entire aromatics
recovery complex for ARSOL Aromatics
in Gelsenkirchen/Germany, consisting of
hydrorefining, benzene extractive distillation
and distillation of the benzene homologues
(Toluene, Xylenes and C9+
aromatics)
from coke oven light oil.
H2
Selectively
Hydrogenated
Pyrolysis Gasoline
Liquid Recycle
H2 Off-Gas
Separator
Reactor
Crude Pyrolysis
Gasoline from
Steamcracker
16
5.1			Hydrogenation	Technology
If pure aromatics are to be obtained, the
feed must undergo a pretreatment before
the non-aromatics and aromatics can be
separated by extractive distillation. Catalytic
hydrogenation processes have become the
most appropriate technologies for eliminat-
ing impurities such as diolefins, olefins,
sulphur, nitrogen and oxygen components.
5.1.1		Hydrogenation	
of	Pyrolysis	Gasoline
Due to its high diolefin content, crude pyro-
lysis gasoline from steamcrackers has a
tendency to polymerise and to form gum
even when stored in tanks under nitrogen
blanketing. In view of the fact that polymer-
isation is encouraged at higher tempera-
tures, the diolefins have to be hydrogenated
at relatively low temperatures by highly ac-
tive catalysts in the so-called selective hydro-
genation process. Once the diolefins have
been subjected to selective hydrogenation,
other impurities can be hydrogenated in the
full hydrogenation stage at high tempera-
tures.
Selective	Hydrogenation	
(see Fig. 5-01)
In this process step, crude pyrolysis gas-
oline is sent to the hydrogenation reactor
after having been mixed with hydrogen. The
reaction takes place in the trickle phase or
in the liquid phase on nobel metal catalysts
(palladium on aluminium oxide carrier) or
on nickel catalysts.
The selectively hydrogenated pyrolysis
gasoline leaves the reactor and is sent to a
separator where the remaining hydrogen is
separated from the liquid phase. Depending
on the catalyst selected, the gas phase is
sent either to the fuel gas unit or to the full
hydrogenation stage in which the remaining
hydrogen is utilised as a make-up agent.
After cooling, part of the liquid phase is re-
cycled to the reactor to control the reactor
temperature. The selectively hydrotreated
product is fed to a fractionation column or
is sent directly to the full hydrogenation.
Fig. 5-01
Selective Hydrogenation of
Pyrolysis Gasoline
5. Technology
Hydrogenation Technology
Selectively Hydrogenated
Pyrolysis Gasoline
Recycle H2
Reactor Separator
Fully Hydrogenated
Pyrolysis Gasoline
High Pressure
Separator
Make-up H2 Off-Gas
17
Full	Hydrogenation	
(see Fig. 5-02)
Impurities such as sulphur, nitrogen and
oxygen components and olefins are hydro-
genated in the full hydrogenation stage. The
reactions take place in the gaseous phase
on nickel/molybdenum and/or cobalt/molyb-
denum catalysts at reactor inlet tempera-
tures of between 240°C and 320°C.
To this end, the selectively hydrogenated
pyrolysis is fed to the reactor via feed/efflu-
ent heat exchangers and a process heater
after having been mixed with recycled hydro-
gen. After cooling, the reactor product is
sent to a high pressure separator where the
hydrogen, which has not been consumed,
is separated from the liquid phase.
The remaining hydrogen is mixed with
fresh make-up hydrogen and fed back to
the reactor.
The liquid reactor product, fully hydrogen-
ated pyrolysis gasoline, is sent to a stabiliser
system in which the off-gas containing H2
S
is separated from the product. The off-gas
is normally recycled back to the steam
cracker, whilst the stabilised reactor product
is sent either to a fractionation column or
directly to the aromatics recovery unit.
Various optimised process designs are
provided depending on the specific criteria,
such as feedstock specification, hydrogen
quality, etc. In this respect some of the
most cost-effective solutions with regard
to investment and operating costs include
reactor-side intermediate quenching by
cooled liquid product recycle, steam gen-
eration and additional reactive catalyst
layers for difficult feedstocks.
Fig. 5-02
Full Hydrogenation of
Pyrolysis Gasoline
Reformate Fraction
H2
Reformate Fraction
Off-Gas
Reactor
18
5.1.2		Hydrogenation	of	Reformate
Although high quality benzene containing
less than 30ppm non-aromatics is pro-
duced by extractive distillation, even a small
quantity of diolefins (around 5ppm) can
result in an acid wash colour (AWC) speci-
fication higher than that which is actually
required. If diolefins are present, especially
those of a naphthenic nature the reformate
must be subjected to an additional treat-
ment stage.
As the most common unsaturated com-
ponents, such as olefins and diolefins, are
mostly removed by clay treating combined
with a conventional liquid-liquid extraction
plant. One alternative is to install a selec-
tive hydrogenation stage for the olefins and
diolefins upstream of the extractive distil-
lation process. The catalyst used for the
selective hydrogenation of reformate has a
long service life and can usually be regen-
erated several times. The maintenance
savings are thus quite remarkable. In addi-
tion, disposing of clay has become more
and more difficult due to the enforcement
of environmental protection laws in an in-
creasing number of countries.
The essential features of the catalyst can
be summarised as follows:
• high conversion rate with regard
to diolefins
• reduction of olefins
• low benzene losses
(as compared to clay treating)
• long cycle length between regeneration
• long service life
• mild operating conditions
The typical process scheme is illustrated
in Fig. 5-03.
The benzene-rich cut upstream of the ex-
tractive distillation stage is passed to the
selective hydrogenation reactor once the
required inlet temperature has been reached.
Hydrogen is added to the benzene-rich cut.
Selective hydrogenation takes place in the
trickle bed of the reactor at low tempera-
tures and pressures. The product, which is
free of diolefins, is then passed directly to
the extractive distillation stage. Separation
of the gas phase takes place in the reactor
bottom. Additional stripping of the product
is not necessary.
Fig. 5-03
Reformate Selective
Hydrogenation
Coke Oven
Light Oil
Recycle
Compressor
Stage
Evaporator
H2
Tardistillation
Column
Tar
Pre-Reactor Main Reactor
Hydrogenated
Coke Oven Light Oil
High Pressure
Separator
Off-Gas
19
5.1.3		Hydrogenation	
of	Coke	Oven	Light	Oil
In a similar way to crude pyrolysis gasoline,
coke oven light oil also has to be hydrogen-
ated. Impurities, such as organic sulphur,
nitrogen and oxygen components, have to be
removed and diolefins and olefins have to be
saturated to stabilise the coke oven light oil
and to assure high-quality final products.
The “BASF-Scholven” process meets all the
above requirements. The reactions take place
in the gas phase on a nickel/molybdenum
catalyst in the prereactor and on a cobalt/
molybdenum catalyst in the main reactor.
Special emphasis is placed on the evapo-
ration of the coke oven light oil feed. Uhde
has developed a proprietary system which
permits smooth evaporation in a special-
multistage evaporator thereby minimising
fouling whilst achieving high on-stream
factors without the addition of fouling in-
hibitors.
The coke oven light oil is mixed with make-
up hydrogen and recycle hydrogen and
passed through a system of feed/effluent
exchangers which are combined with the
stage evaporator (Fig. 5-04). With the ex-
ception of a small quantity of heavy hydro-
carbons which are withdrawn at the bottom
of the multi-stage evaporator, almost all
the feedstock is evaporated.
After being subjected to additional heating,
this material is fed to the prereactor where
most of the diolefins are converted. The
effluent from the prereactor is then heated
further by a process heater. In the main
reactor the olefins are saturated and the
remaining sulphur, nitrogen and oxygen
compounds are hydrogenated. After cool-
ing, the effluent from the main reactor is
sent to the high pressure separator to dis-
engage the hydrogen from the liquid phase.
The separated hydrogen is mixed with
make-up hydrogen, recompressed and
returned to the coke oven light oil feed.
The fully hydrogenated raffinate from the
high pressure separator is sent to a conven-
tional stabiliser system. Off-gas containing
H2
S and NH3
is separated from the raffinate
product. The stabilised raffinate is sent to a
fractionation and aromatics recovery unit.
Uhde offers a variety of process configura-
tions adapted to the feedstock conditions and
customer requirements. The heavy hydrocar-
bon residue can, for example, be subjected
to further treatment in a tar distillation unit
to enhance BTX aromatics recovery or to
produce valuable tar-derived products.
Fig. 5-04
Hydrorefining of
Coke Oven Light Oil
20
5.2 Fractionation Technology
For many decades, distillation has been one
of Uhde's key areas. From hydrocarbon C2
and C3
distillation to C9
and C10
distillation,
from crude distillation to pure component
distillation, Uhde can provide fractionation
technology for virtually any hydrocarbon
system.
Our extensive experience is very efficiently
backed up by our laboratory and pilot plant
facilities. Hydrocarbon equilibrium data can
be measured in our laboratories and then
implemented in conventional standard pro-
cess simulators.
Pilot testing may also be used to confirm or
demonstrate these adapted models. Special
feedstocks can be tested in our pilot plants
allowing distillation processes to be opti-
mised to meet customer requirements.
5.2.1 Conventional Distillation
Uhde’s expertise includes distillation sys-
tems which use conventional tray tech-
nology as well as random and structured
packing technologies. We have designed
columns up to 10 metres in diameter and
as high as 100 metres.
5.2.2 Divided Wall
Column Distillation
Whenever more than two fractions have to
be separated by distillation, the question
arises as to which is the most efficient con-
figuration (Fig. 5-05).
Configurations involving columns which
are fully thermodynamically coupled have
certain energetic advantages over conven-
tional fractionation technologies. Latest
technological developments have, however,
laid the foundation for adequate calcula-
tion techniques and established the generic
guidelines for thermodynamic simulations.
This has resulted in the development of en-
gineering tools which permit the application
of the divided wall technology and which
make use of the thermodynamic advan-
tages.
These advantages are reflected in:
•	up to 20% less investment costs
•	up to 35% less energy costs
•	up to 40% less plant space
requirements
Uhde successfully introduced this tech-
nology to aromatics applications. Two com-
mercial-scale divided wall columns have
recently been commissioned for aromatics
recovery. In addition, Uhde has installed
divided wall column test facilities in its own
laboratories to work on further improve-
ments.
The divided wall column technology is an
excellent tool for revamping plants, enhanc-
ing their capacity and improving product
qualities and yields. Existing hardware can
be modified within one week resulting in a
short shut-down time and low production
losses.
Plant converted to the divided wall tech-
nology in just five days.
The Uhde team at the Ruhr Oel GmbH re-
finery in Münchsmünster in Bavaria had just
five days to convert a distillation column to
a divided wall column using one of Uhde’s
new developments. The Uhde team man-
aged to complete the task in the allotted
time despite inclement weather. The divided
wall column saved Ruhr Oel having to build
a second column for removal of benzene so
that the more stringent benzene specifica-
tions in gasoline could be met.
Fractionation Technology
Old section of the existing column
Reformate or
Pyrolysis Gasoline
C8+ Fraction
C5 Fraction
C6/C7 Fraction
21
Fig. 5-05
Divided Wall Column
New divided wall section before
installation of packings
22
5.3 Morphylane®
Extractive Distillation
Due to lower capital cost and utilities con-
sumption, the Uhde Morphylane®
extractive
distillation process has replaced the former
liquid-liquid extraction technology.
5.3.1 Conventional
Morphylane®
Process
In the extractive distillation (ED) process
(see Fig. 5-06), the solvent alters the va-
pour pressure of the components to be
separated. The vapour pressure of the
aromatics is lowered more than that of the
less soluble non-aromatics. The ED process
is relatively simple. The solvent is supplied
to the head of a distillation column via a
central feed inlet. The non-aromatic vapours
leave the ED column with some of the sol-
vent vapours. The internal reflux is con-
trolled by the solvent feed temperature.
The solvent is recovered from the overhead
product in a small column with sectional
reflux, which can be either mounted on
the main column or installed separately.
The bottom product from the ED column is
fed to a distillation stage, i.e. the stripper,
to separate the pure aromatics and the
solvent. After intensive heat exchange, the
lean solvent is recycled to the ED column.
The product purity is affected by a number
of different parameters including solvent
selectivity, the number of separation stages,
the solvent/feedstock ratio and the internal
reflux ratio in the ED column. The solvent
properties needed for this process include
high selectivity, thermal stability and a suit-
able boiling point. The solvent used in the
Morphylane®
process is a single compound,
namely N-formylmorpholine (NFM). No
agents or promoters are added to the sol-
vent. The salient features of NFM are sum-
marised in Fig. 5-07.
5.3.2 Nitrogen Guard Bed
The Morphylane®
process withholds the sol-
vent in the unit almost completely. The con-
centration of NFM in the extract is typically
less than 1 wt.-ppm, which corresponds to
0.15 wt.-ppm basic nitrogen. Therefore
losses are of no importance to the eco-
nomics of the process. However, market
demands have increased: Due to the inven-
tion and spread of zeolithe catalysts for
alkylation processes the requirements for
the extract of the Morphylane®
process have
become stricter. The nitrogen concentration
is required to be as low as possible. Uhde’s
answer to this market demand is the Nitro-
gen Guard Bed. This adsorption bed is able
to capture even traces of basic nitrogen,
such that the product concentration is in the
ppb-range, below the detection limit. There-
fore aromatics from the Morphylane®
units
can safely be fed to zeolithe-catalysts reac-
tors, producing alkyl-aromatics in world-scale.
Aromatics
Extractive
Distillation
Column
Stripper
Column
Solvent + Aromatics
Solvent
Non-Aromatics
Aromatics
Fraction
Fig. 5-06
Morphylane®
Extractive Distillation
Morphylane®
Extractive Distillation
Solvent:
N-formylmorpholine (NFM)
23
5.3.3 Single-Column Morphylane®
Extractive Distillation
Uhde’s new Single-Column Morphylane®
extractive distillation process uses a single-
column configuration which integrates the
extractive distillation (ED) column and the
stripper column of the conventional Mor-
phylane®
design. It represents a superior
process option in terms of investment and
operation (Fig. 5-08).
In the Single-Column ED process, the aro-
matics are removed from the vaporised feed
by the solvent (NFM) in packing 2. Residual
non-aromatics are stripped off by aromatics
vapours in packing 3. Solvent traces in the
column head are washed back with the non-
aromatics reflux in packing 1, while solvent
traces in the aromatics vapours are removed
by aromatics reflux in packing 4.
Packings 3 and 4 are separated by a divid-
ing wall forming two chambers. The cham-
ber containing packing 4 is closed at the
top side.
The aromatics-solvent mixture draining from
the two chambers is fed to the stripping sec-
tion (packing 5) where the aromatics are
stripped off from the solvent. The lean sol-
vent is returned to the top of the column. In-
tensive stripping is crucial to the aromatics
yield.
The first industrial realisation of the new con-
cept has been a toluene recovery plant for
ARSOL Aromatics GmbH in Gelsenkirchen,
Germany, commissioned in October 2004.
Based on the Single-Column Uhde Morphy-
lane®
process described above, the plant
produces pure toluene from fully hydrogen-
ated coke oven light oil.
The plant has a toluene capacity of 30,000
tonnes/year and it achieves purities of over
99.99%. The column has proved easy to
operate, even under varying feed conditions
and product specifications.
Uhde supplied the licence for the plant,
provided engineering services and was on
hand in a consulting capacity during com-
missioning.
In 2005, Uhde was presented with the
'Kirkpatrick Honor Award for Chemical En-
gineering Achievement', a biennial award
for innovative products or processes by the
journal Chemical Engineering. A vital pre-
requisite for submission of an innovation is
that its first-time industrial-scale implemen-
tation was within the past two years. Our
technology met this condition with the suc-
cessful commissioning of the aromatics plant
based on the innovative single-column con-
cept for ARSOL Aromatics GmbH in 2004.
An international team of experts ranked the
process among the five best process inno-
vations of the last two years.
Non-Aromatics
Aromatics
Solvent
Feed
3
2
1
4
5
Fig. 5-08
Single-Column Morphylane®
Extractive Distillation
Fig. 5-07
Main Features of the Morphylane
®
Extractive Distillation Process
Process features:
Simple plant arrangement
Low number of equipment (2 columns)
Little space required
No raffinate wash system required
Low solvent filling
Low investment
Low energy consumption
Easy to operate
No chemical agents required
High on-stream time
N-formylmorpholine solvent features:
High selectivity
High solvent efficiency
High purity products even from
Feedstocks with high paraffinic contents
High permanent thermal stability
High heat transfer rate
No corrosive effect
High chemical stability
Negligible solvent consumption
Low solvent regeneration cost
No toxicity
Low price
24
525,000mtpy of pyrolysis
gasoline extractive distillation for
Rayong Olefins Corp., Thailand
5.4		Hydrodealkylation	Technology
Hydrodealkylation, commonly known as
HDA, is a well-established process for con-
verting C7
and C8
(even up to C9+
) alkylben-
zenes to high purity benzene. Very few new
plants are being built, however, as the huge
hydrogen consumption makes the benzene
quite expensive.
The preferred technology uses non-catalytic
thermal reactor systems which have a high
benzene yield, extremely high on-stream
factors and lower operating costs as com-
pared with catalytic systems. A typical pro-
cess configuration is shown in Fig. 5-09.
Several options, e.g. to enhance benzene
yield or to minimise hydrogen consump-
tion are available, depending on the qual-
ity of the feedstock treated in the HDA.
Co-processing C8
and even C9+
aromatics
will enhance benzene output but will also
increase hydrogen consumption consider-
ably. An upstream extraction stage reduces
the content of non-aromatics to such an
extent that the amount of hydrogen con-
sumed in the cracking reaction is minimised.
5.5		Toluene	Disproportionation	
Technology
Toluene Disproportionation Technology
(TDP) converts toluene to benzene and
mixed xylenes in approximately equimolar
quantities. The reaction is carried out in the
vapour phase on a variety of acidic zeolite
catalysts. Conventional TDP produces a
xylenes fraction in which the xylene-isomer
equilibrium is reached. The para-xylene
concentration is therefore limited to 24%.
Further processing is required to increase
the para-xylene yield.
This involves separating the para-xylene
isomer by selectively adsorbing or by
crystallising and isomerising the remaining
meta-xylenes and ortho-xylenes (optionally)
to form para-xylene. Since the para-xylene
concentration in isomerisation is only 24%
as well, a large recycle loop is required to
completely convert the undesired isomers
to para-xylene.
Fresh
Toluene
BenzeneColumn
XyleneRevovery
Column
Deheptanizer
Separator
TDPReactor
Stabilizer
Make-up
Hydrogen
Light Ends
to Fuel
Mixed Xylenes to
Para-xylene Recovery
Benzene
C9+ Aromatics
to Gasoline Pool
B/T Aromatics
from Extraction
Vent
Benzene
Heavy Aromatics Purge
HDAReactor
C8+ Aromatics
from Predistillation
BenzeneColumn
RecycleColumn
Make-up
Hydrogen
Stabilizer
Separator
25
Fig. 5-10
Toluene Disproportionation Unit
Fig. 5-09
Hydrodealkylation (HDA) Unit
Hydrodealkylation and Toluene
Disproportionation Technology
A major technological break-through was
achieved when the zeolite catalyst geometry
was developed to maximise para-xylene
selectivity. The TDP with improved selectiv-
ity produces a xylene fraction which con-
tains up to 90% para-xylene. Consequently,
the downstream para-xylene recovery and
xylene isomerisation stages are smaller and
more efficient.
Fig. 5-10 shows a typical process
configuration for a TDP.
26
5.6  Toluene/C9+
Transalkylation
Technology
In contrast to the TDP, toluene and C9+
aro-
matics are converted to mixed xylenes in
the transalkylation technology. The xylenes-
to-benzene ratio increases if more C9+
aro-
matics are mixed with the toluene feed and
if the transalkylation reaction rate increases.
Similar catalysts to those used in TDP units
are used.
5.7  Para-Xylene
Adsorption Technology
Para-xylene can practically not be sepa-
rated from meta-xylene by conventional
distillation due to the closeness of their
boiling points. In contrast, ortho-xylene can
be recovered by conventional distillation
because its boiling point is considerably
higher than that of the other isomers.
The most common para-xylene separation
technology used today involves adsorption
using molecular sieves.
Crystallisation technology is also widely
used, especially in North America and in
Western Europe. However, one of the main
advantages of adsorption over crystallisa-
tion is its high recovery rate per pass (up to
97%). In contrast, crystallisation units have
a eutectic limitation of 65%. All commer-
cialised para-xylene adsorption processes
use isothermal, liquid phase adsorption.
The adsorbent’s selectivity, capacity and
reversibility are the key properties relevant
to desorption.
At the heart of the adsorption process are
the adsorption columns in which the fol-
lowing steps occur in a sophisticated semi-
continuous operation:
•	 feeding in mixed xylenes
•	diluting out extract (para-xylene)
with a desorbent
•	diluting out raffinate (ethylbenzene,
meta-xylene and ortho-xylene)
with a desor bent
•	feeding in recycled desorbent
The diluted extract and raffinate streams
are fractionated in an extraction column and
a raffinate column to recover the desorbent
which is recycled back to the adsorbers.
Any residual toluene contained in the mixed
xylenes feed and carried over with the para-
xylene extracted is separated in a finishing
column. The concentrated raffinate, meta-,
ortho-xylene and ethylbenzene, is sent to
the isomerisation stage. A simplified pro-
cess configuration is shown in Fig. 5-11.
Mixed Xylenes from
Xylene Splitter
RaffinateColumnExtractColumn
FinishingColumn
Block scheme of the
Adsorption System
Desorbent
Light Ends
Para-Xylene
(Extract)
C8 -Aromatics
to Isomerisation
(Raffinate)
Fig. 5-11
Para-Xylene Adsorption Unit
Toluene/C9+
Transalkylation and
Para-Xylene Adsorption Technology
27
5.8			Xylenes	Isomerisation	
Technology
Once the C8
aromatics stream has been
depleted of para-xylene (and optionally of
ortho-xylene as well), the stream is sent
to an isomerisation unit to re-establish the
equilibrium of the xylene mixture. This oc-
curs by converting the meta-xylene (and
ortho-xylene, if present) and the ethyl-
benzene (EB) to para-xylene by isomerisa-
tion until the equilibrium is reached. The
isomerisate is then returned to the xylene
fractionation section in which valuable par-
axylene, and optionally ortho-xylene, are
recovered. Meta-xylene and EB are returned
to the recycle loop.
Alternatively, EB can be dealkylated to
form benzene and ethane.
The method of EB conversion is influenced
by the catalyst type. Xylene isomerisation
catalysts can be categorised according to
their ability to isomerise EB into additional
xylenes or their ability to dealkylate EB. Both
types of catalyst isomerise the xylenes to
form a close equilibrium xylene isomerisate
mixture.
EB isomerisation catalysts result in the
highest para-xylene yield from a given feed-
stock due to the conversion of EB to addi-
tional xylenes. EB isomerisation is more
difficult than xylene isomerisation and re-
quires a bifunctional acid-metal catalyst.
EB isomerisation occurs using C8
-naphthene
intermediates. This type of catalyst must be
operated with a substantial concentration of
C8
-naphthenes in the reactor recycle loop to
allow efficient conversion of EB to xylenes.
Xylene feedstocks containing high EB con-
centrations, such as pyrolysis gasoline feed-
stocks, are particularly suitable as the EB is
converted to naphthenes thereby producing
the naphthene concentration required. The
EB isomerisation conversion rate typically
amounts to 30-35%.
EB dealkylation is not limited to equilibrium
conditions and permits EB conversion rates
of up to 65%. EB dealkylation catalysts gen-
erally contain a shape-specific molecular
sieve with a given pore size, which minimises
xylene loss caused by xylene disproportion-
ation, transalkylation or hydrocracking.
3CH
CH3
CH
CH3
CH3
3
CH3
meta-Xylene para-Xylene ortho-Xylene
Xylene Isomers
Xylenes Isomerisation Technology
28
6.	Operating Results
of Extractive Distillation Plants
ED column and stripper, aromatics complex
at the Kashima refinery, Japan
Table 7-01
Reformate feed with
high aromatics content
Typically, reformates which con-
tain large quantities of aromat-
ics are processed in aromatics
complexes in which a high
aromatics yield reformer is in-
stalled. The C6
 core cut contains
aromatics levels which well in
excess of 50%. The operating
results of four plants are sum-
marised in Tables 7-01 and 7-02.
Reformate feed with high aromatics content
Plant for
Year of commissioning
Benzene in ED-feed
Toluene in ED-feed
Benzene production
Toluene production
Benzene quality
Toluene quality
Solvent loss
Steam consumption
Yield
Japan Energy, Kashima
2007
30%
49%
136,000 mtpy
223,000 mtpy
max. 400 wt.-ppm non-aromatics
99.0 wt.-%
max. 0.007 kg/t aromatics
480 kg/t ED-feed
Benzene: 99.92%
Repsol, Spain
2007
75%
0%
221,000 mtpy
-
400 wt.-ppm non-aromatics
-
max. 0.010 kg/t aromatics
470 kg/t ED-feed
Benzene: 99.7%
Table 7-04
Table 7-02 *) including the benzene/toluene splitter
Table 7-03
29
Reformate feed with low
aromatics content
Reformates processed in gas-
oline-based refineries generally
contain smaller quantities of
benzene. Reformers are often
operated at lower severity levels.
If the benzene content of gaso-
line is to be reduced, the ben-
zene content of the C6
core cut
fed to the extractive distillation
stage needs to be well below
50 wt%. In this type of applica-
tion, the energy consumption of
extractive distillation processes
is lower than that of reformate
streams with a higher aromatics
(benzene) content. Table 7-03
shows the operating results of
two plants recently commis-
sioned for benzene reduction.
Pyrolysis gasoline feed
Pyrolysis gasoline from steam-
crackers has a relatively high
aromatics content which is dic-
tated by the cracker feedstock
and the severity of the cracker.
The results obtained from an
aromatics distillation process
in a typical naphtha-based
steam-cracker are shown in
Table 7-04. The two examples
are based on a benzene ED,
which was started up in the
Netherlands at the end of 2002,
and a benzene/toluene ED,
which went into operation in
Poland in 2005.
Reformate and pyrolysis gasoline feed with high aromatics content
Plant for
Year of commissioning
Benzene in ED-feed
Toluene in ED-feed
Benzene production
Toluene production
Benzene quality
Toluene quality
Solvent loss
Steam consumption
Yield
PKN Orlen, Poland
2006
33%
41%
178,000 mtpy
222,000 mtpy
70 wt.-ppm non-aromatics
470 wt.-ppm non-aromatics
0.006 kg/t aromatics
540 kg/t ED-feed
Benzene: 99.9; Toluol: 98.2 %
Shell Moerdijk, The Netherlands
2002
65 wt.-%
-
550,000 mtpy
-
max. 200 wt.-ppm non-aromatics
-
max. 0.003 kg/t benzene
400 kg / t ED-feed
-
Reformate feed with low aromatics content
Plant for
Year of commissioning
Benzene in ED-feed
Benzene production
Benzene quality
Solvent loss
Steam consumption
Holborn Refinery, Germany
2003
~ 27 wt.%
66,000 mtpy
max. 10 ppm wt. non-aromatics
max. 0.002 kg/t benzene
450 kg/t ED-feed
Tonen, Kawasaki, Japan
1999
~ 30 wt.%
100,000 mtpy
max. 50 ppm wt. non-aromatics
max. 0.001 kg/t benzene
380 kg/t ED-feed
Reformate feed with high aromatics content
Plant for
Year of commissioning
Benzene in ED-feed
Toluene in ED-feed
Benzene production
Toluene production
Benzene quality
Toluene quality
Solvent loss
Steam consumption
BASF Antwerp, Belgium
2000
~ 65 wt.%
-
258,000 mtpy
-
max. 100 ppm wt. non-aromatics
-
max. 0.005 kg/t benzene
450 kg/t ED-feed
SPC, PR China
1999
~ 75 wt.%
~ 85 wt.%
135,000 mtpy
65,000 mtpy
max. 80 ppm wt. non-aromatics
max. 600 ppm wt. non-aromatics
max. 0.08 kg/t aromatics
680 kg/t ED-feed *)
30
Uhde operates laboratory and pilot plant
facilities in Ennigerloh, Germany. The facili-
ties are used for ongoing developments to
new processes and for optimising estab-
lished processes. In conjunction with their
colleagues in the central RD division, a
highly qualified team of 30 employees is
committed to providing RD services for
our customers. This team includes:
•	12 chemists and chemical engineers
•	10 chemical technicians and mechanics
•	4 administrative staff is committed to
providing RD services for our customers.
Using the latest state-of-the-art equipment,
our RD staff is dedicated to:
•	improving Uhde processes
•	searching for new processes
and process opportunities
•	improving analytical methods and
preparing analytical instructions and
manuals
•	providing a wide range of analyses for
feedstocks and products
•	providing analytical support during the
commissioning 	of our plants
Our process engineers in Dortmund and
Bad Soden work closely with the laboratory
staff and are able to support operations
whenever needed. The laboratory and pilot
facilities are certified in accordance with ISO
9001 to ensure consistently high standards.
7.1 Analytical facilities
The laboratory consists of 5 working sections:
•	laboratory for inorganic
chemistry/physical analyses
•	gas chromatography
•	laboratory for fuel and coal analysis
•	laboratory for oil and wax analysis
•	test laboratory
The analytical facilities permit standard
DIN/ISO or ASTM analyses of virtually any
type of fuel and refinery/petrochemical
feedstock, as well as a variety of inorganic
analytical methods and water analysis
methods. Some of the main methods are
summarised below.
7.1.1 Gas chromatography
Our laboratory uses gas chromatographs
to categorise all types of hydrocarbon feed-
stocks, products and intermediate products.
The samples are separated analytically
in capillary, widebore or packed columns
of suitable polarity. Standard analytical
methods using flame ionisation detectors
(FID) and thermal conductivity detectors
(TCD), are enhanced by special detection
methods which use selective sulphur detec-
tors (S-CLD) or nitrogen detectors (NPD and
N-CLD). Additionally, a powerful GC-MSD sys-
tem enables us not only to identify unknown
components in a complex matrix, but also to
quantify components of special interest even
when present as trace amounts.
7.1.2 Physical and chemical methods
Hydrocarbon components are completely
broken down and other properties and im-
purities are also of interest. We use various
analytical methods to analyse these prop-
erties and impurities, including elemental
analyses (CHNS), chloride content, bromine
index/number, acid wash colour, specific
gravity, molecular weight, acidity, refraction
index and many more. The methods used
include:
•	UV-Vis spectroscopy
•	ion chromatography
•	atom absorption spectroscopy
•	potentiometry
•	coulometry
•	viscosimetry (Hoeppler, Ubbelhohe, Engler)
•	ignition point determination
(Abel-Pensky, Pensky-Martens)
•	surface tension (DeNouy)
•	hydrogen/oxygen combustion
•	water determination (Karl Fischer)
•	solidification point acc. to ASTM D 852
•	boiling range acc. to
ASTM D 850 and D 1160
•	total sulphur acc. to ASTM
D 5453 and D 7183
•	total nitrogen acc. to ASTM
D 6069 and D 7184
7.1.3 Other analytical methods
In addition to the standard analytical meth-
ods mentioned above, our laboratory is
able to develop other analytical methods to
cater to special customer requirements, or
to support troubleshooting in our customers’
plants. This means that we can measure:
•	thermal stability of chemicals
•	corrosion of materials in chemicals
•	2-liquid phase separation abilities
•	polymer content in solvents
•	foaming tendencies
•	chemical stability
7.2 Determination of thermo-physical
properties
Simulation models must be constantly
enhanced using data gained during plant
operation or in laboratory tests to ensure
the continuous improvement of process
simulation and equipment design.
Uhde has continuously developed and
increased its thermo-physical property
data banks which are used for process
simulation of its separation technologies.
Vapour-liquid equilibrium (VLE) or liquid-
7. 	 Laboratory, Analytical
	 and RD Services 	
Gas-phase chromatographs used in
the separation and quantitative ana-
lysis of liquid and gaseous samples
i-Butan
n-Butan
i-Pentan
n-Pentan
2.2-Dimethylbutan
2.3-Dimethylbutan
Cyclopentan
n-Hexan
2.2-Dimethylpentan
2.4-Dimethylpentan
2.2.1-Trimethylpentan
Methylcyclopentan
3.3-Dimethylpentan
2-Methylhexan
2.3-Dimethylpentan
Cyclohexan
2.2.3-Trimethylpentan
3-Ethylpentan
cis1.3-DMCP
tr1.3-DMCP
tr1.2-DMCP
n-Heptan
2.2.3.3-Teramethylbutan
Benzol
Methylcyclohexan
2.2-Dimethylhexan
1.1.3-Trimethylhexan
3-Methylhexan
31
liquid equilibrium (LLE) data for specific
solvent/hydrocarbon systems (used in ED
and LLE) is measured in our laboratories,
evaluated and linked to our process simula-
tors. Simulation results can later be verified
or checked in our pilot plant facilities under
real operating conditions. This procedure
allows us to develop tailor-made separation
processes for our customers.
Uhde’s laboratory includes equipment to:
•	determine the VLE dataof binary and
tertiary systems at temperatures of
20°C-160°C and pressures of 0-40 bar
•	determine the LLE data of binary, ter-
tiary, and quaternary systems at tem-
peratures of -40°C to 95°C for 1 bar, and
temperatures of 20°C-160°C for pres-
sures ranging from 0-5 bar
•	measure crystallisation equilibria
•	measure the solubility of gases in liquids
•	determine mass transfer coefficients
7.3 Pilot Plant Tests
The Uhde pilot plant tower is a three-storey
building situated next to the laboratory. The
3 platforms cover an overall height of 12 m.
Larger pilot plant facilities can be erected
on various other ThyssenKrupp sites if re-
quired.
The pilot plant is completely surrounded by
scaffolding made from Mero cuboid struc-
tural components (edge length 1 m) and
can be accessed every 2 m to permit simple
and fast installation of equipment and bulk.
Most modern DCS and instrumentation ele-
ments are used for measuring and control-
ling the pilot plant.
A 2-channel gas chromatograph with FID
is used for online liquid analysis. The chro-
matograph is equipped with 2 completely
separated systems of recycle pumps and
automatic liquid injectors. Time-controlled
processing and analytical operations are
performed using a computer.
7.3.1 Separation techniques
A variety of fractionation utilities is
available:
•	conventional distillation with up to 160
theoretical stages. Modules with an ID
of 100 mm, 72 mm, and 50 mm made of
stainless steel or glass for laboratorytype
structured packings (Sulzer DX/EX) and
bubble cap trays
•	extractive distillation with up to 70 theo-
retical stages. Modules with an ID of
72mm in stainless steel equipped with
structured packings
•	liquid-liquid extractors with up to 50
theoretical stages. Modules with an ID of
40 mm in glass equipped with structured
packings (Sulzer BX)
•	divided wall columns with up to 40 theo-
retical stages in the partition section.
The operating range can be varied from a
high vacuum to 6 bar.
Several types of tubular reactors, some of
which are jacketed, and agitated autoclaves
(CSTR) can be used for catalyst and absor-
bents testing, and for measuring reaction
kinetics. Pressures of up to 200 bar and
temperatures of up to 600°C can be applied
to test catalytic reactions and catalyst for-
mulations.
7.3.2  Absorption/adsorption techniques
The specially designed equipment in our
pilot plant facilities allows us to test or meas-
ure static and dynamic absorption equilibria
and mass transfer for gas scrubbers. This
equipment includes autoclaves, falling-film
adsorbers and scrubbers fitted with a variety
of random or structured packings.
The Uhde
research centre
Research facility with PC-based process control
system for process development in the fields of
distillation, extraction and extractive distillation
32
ThyssenKrupp Uhde is dedicated to providing its cus-
tomers with a wide range of services and to supporting
them in their efforts to succeed in their line of business.
With our worldwide network of local organisations and
experienced local representatives, as well as first-class
backing from our head office, ThyssenKrupp Uhde has
the ideal qualifications to achieve this goal.
We at ThyssenKrupp Uhde place particular importance
on interacting with our customers at an early stage to
combine their ambition and expertise with our experi-
ence.
Whenever we can, we give potential customers the
opportunity to visit operating plants and to personally
evaluate such matters as process operability, main-
tenance and on-stream time. We aim to build our future
business on the confidence our customers place in us.
ThyssenKrupp Uhde provides the entire spectrum of
services associated with an EPC contractor, from the
initial feasibility study, through financing concepts and
project management right up to the commissioning of
units and grass-roots plants.
Our impressive portfolio of services includes:
•	 Feasibility studies / technology selection
•	 Project management
•	 Arrangement of financing schemes
•	 Financial guidance based on an intimate
	 knowledge of local laws, regulations and
	 tax procedures
•	 Environmental studies
•	 Licensing incl. basic / detail engineering
•	 Utilities / offsites / infrastructure
•	 Procurement / inspection / transportation services
•	 Civil works and erection
•	 Commissioning
•	 Training of operating personnel using operator
	 training simulator
•	 Plant operation support / plant maintenance
•	 Remote Performance Management (Teleservice)
ThyssenKrupp Uhde’s policy is to ensure utmost quality
in the implementation of its projects. We work worldwide
to the same quality standard, certified according to:
DIN / ISO 9001 / EN29001.
We remain in contact with our customers even after pro-
ject completion. Partnering is our byword.
By organising and supporting technical symposia, we
promote active communication between customers, li-
censors, partners, operators and our specialists. This
enables our customers to benefit from the development
of new technologies and the exchange of experience as
well as troubleshooting information.
We like to cultivate our business relationships and learn
more about the future goals of our customers. Our after-
sales services include regular consultancy visits which
keep the owner informed about the latest developments
or revamping options.
ThyssenKrupp Uhde stands for tailor-made concepts and
international competence. For more information contact
one of the ThyssenKrupp Uhde offices near you or visit
our website:
www.uhde.eu
Further information on this subject can be found
in the following brochures:
•	 Oil  Gas
•	 Polymers
8.	 Services for our customers
33
34
Completion	 Customer	 Process	 Prod. Capacity	 Licensor or
	 Plant Site	 Plant	 mtpy	 Know-how
Morphylane®
Extractive Distillation
2014	 Refineria Del Pacifico	 Benzene	 143,000	 Uhde
	 Manabi, Ecuador	 from Reformate
2014	 Petrobras S.A.	 Benzene/Toluene	 940,000	 Uhde		
	 Rio de Janeiro, Brazil	 from Reformate
2013	 Atyrau Refinery	 Benzene/Toluene	 289,000	 Uhde	
	 Kazakhstan	 from Reformate
2012	 Sasol Technology	 Benzene from	 106,000	 Uhde	
	 Secunda, South Africa	 Coal tar nawphthta SCC Gasoline
2012	 Rabigh Refining and Petrochemical Co.	 Benzene/Toluene	 881,000	 Uhde		
	 Rabigh, Saudi Arabia	 from Reformate
2012	 Total Jerp	 Benzene	 140,000	 Uhde		
	 Al-Jubail, Saudi Arabia	 from Reformate
2011	 Tianjin Binhai Tiansheng Coal Chemical Co.	 Benzene/Toluene/Xylenes	 87,300	 Uhde		
	 Tianjin, China	 from Coke Oven Light Oil
2011	 S-Oil Corporation	 Benzene/Toluene	 680,000	 Uhde		
	 Ulsan, South Korea	 from Reformate
2011	 Tabriz Oil Refining Co.	 Benzene	 33,600	 Uhde		
	 Tabriz, Iran	 from Reformate
2010	 Xingtai Risun CoalChemical Company	 Benzene/Toluene/Xylenes	 88,000	 Uhde		
	 Xingtai, China	 from Coke Oven Light Oil
2010	 Baosteel Chemical Co.	 Benzene/Toluene	 80,800	 Uhde		
	 Baoshan, China	 from Coke Oven Light Oil
2010	 Tangshan Risun Chemical Company	 Benzene/Toluene/Xylenes	 173,000	 Uhde		
	 Tangshan, China	 from Coke Oven Light Oil
2010	 Qatar Petroleum	 Benzene/Toluene	 762,000	 Uhde		
	 Qatar	 from Reformate
2010	 Yunnan Dawei Group Co. Ltd.	 Benzene/Toluene/Xylenes	 89,000	 Uhde		
	 Yunwei, China	 from Coke Oven Light Oil
2010	 Shell Eastern Petroleum Ltd.	 Benzene	 210,000	 Uhde		
	 Singapore	 from Pyrolysis Gasoline
2009	 China Steel Chemical Corporation	 Benzene/Toluene	 27,000	 Uhde		
	 Kaohsiung, Taiwan	 from Coke Oven Light Oil
2009	 Wuhan Iron and Steel Co. Ltd.	 Benzene/Toluene/Xylenes	 94,000	 Uhde		
	 Wuhan, China	 from Coke Oven Light Oil
2009	 Xingtai Risun Coal  Chemical Company	 Benzene/Toluene/Xylenes	 88,000	 Uhde		
	 Xingtai, China	 from Coke Oven Light Oil
2009	 GCW Anshan IS Group Co.	 Benzene/Toluene/Xylenes	 128,000	 Uhde		
	 Anshan, China	 from Coke Oven Light Oil
2009	 Oman Oil Company	 Benzene/Toluene	 350,000	 Uhde		
	 Sohar, Oman	 from Reformate
2008	 Jiantao Chemical Co. Ltd.	 Benzene/Toluene/Xylenes	 45,000	 Uhde		
	 Hebei, China	 from Coke Oven Light Oil
2008	 Yunnan Kungang IT Co. Ltd.	 Benzene/Toluene/Xylenes	 44,000	 Uhde		
	 Kunming, China	 from Coke Oven Light Oil
2007	 Shanxi Sanwei Group Co. Ltd.	 Benzene/Toluene/Xylenes	 178,000	 Uhde		
	 Zhahocheng, China	 from Coke Oven Light Oil
2007	Sasol	 Benzene	 100,000	 Uhde
	 Secunda, South Africa	 from Pyrolysis Gasoline
2007	 Hood Oil	 Benzene	 110,000	 Uhde
	 Sanaa, Yemen	 from Reformate
2007	 Japan Energy Co.	 Benzene/Toluene	 310,000	 Uhde		
	 Kashima, Japan	 from Reformate
9.	 Main references
	 Just a few of more than 100 reference 		
	 plants in the last ten years
35
Completion	 Customer	 Process	 Feed Capacity	 Licensor or
	 Plant Site	 Plant	 mtpy	 Know-how
Reformate Hydrogenation
2002	 Shell Nederland Chemie B.V.	 Selective Hydrogenation	 850,000	 Axens
	 Moerdijk, Netherlands
2000	 Tonen Corporation	 Selective Hydrogenation	 320,000	 BASF
	 Kawasaki, Japan
2000	 Saudi Chevron Petrochemical	 Selective Hydrogenation	 860,000	 BASF		
	 Al Jubail, Saudi Arabia	
Pyrolysis Gasoline Hydrogenation
2010	 Shell Eastern Petroleum Ltd.	 First and Second Stage Hydrogenation	 733,000	 Axens	
	Singapore
2005	 CNOOC / Shell Petrochemicals Co. Ltd.	 Hydrogenation	 800,000	 Axens	
	 Huizhou, China
2005	 BASF / Yangzi Petrochemical Co.	 Hydrogenation	 600,000	 BASF		
	 Nanjing, China	 of Pyrolysis Gasoline
2004	 Bouali Sina Petrochemical Co.	 First Stage Hydrogenation	 139,000	 Axens	
	 Bandar Imam, Iran	 Second Stage Hydrogenation	 106,000
2001	 BASF/FINA	 First Stage Hydrogenation	 795,000	 BASF		
	 Port Arthur, Texas, USA	 Second Stage Hydrogenation	 563,000
Coke Oven Light Oil Hydrorefining
2010	 Xingtai Risun CoalChemical Company	 Hydrorefining	 100,000	 Uhde/BASF
	 Xingtai, China
2010	 Baosteel Chemical Co.	 Hydrorefining	 100,000	 Uhde/BASF
	 Baoshan, China
2010	 Tangshan Risun Chemical Co.	 Hydrorefining	 200,000	 Uhde/BASF
	 Tangshan, China
2009	 Yunnan Dawei Group Co. Ltd.	 Hydrorefining	 100,000	 Uhde/BASF
	 Yunwei, China
2009	 Wuhan Iron and Steel Co. Ltd.	 Hydrorefining	 100,000	 Uhde/BASF
	 Wuhan, China
2009	 Xingtai Risun Coal  Chemical Co. 	 Hydrorefining	 100,000	 Uhde/BASF
	 Xingtai, China
2009	 GCW Anshan IS Group Co.	 Hydrorefining	 150,000	 Uhde/BASF
	 Anshan, China
2008	 Jiantao Chemical Co. Ltd.	 Hydrorefining	 50,000	 Uhde/BASF
	 Hebei, China
2008	 Yunnan Kungang IT Co. Ltd.	 Hydrorefining	 50,000	 Uhde/BASF
	 Kunming, China			
2007	 Shanxi Sanwei Group co. Ltd.	 Hydrorefining	 200,000	 Uhde/BASF
	 Zhahocheng, China	
Divided Wall Column Distillation and Single-Column Morphylane®
2000	 Saudi Chevron Petrochemical	 Divided Wall Column Distillation	 140,000	 BASF/Uhde
	 Al Jubail, Saudi Arabia			
1999	 VEBA OEL AG	 Divided Wall Column Distillation	 170,000	 BASF/Uhde
	 Münchsmünster, Germany			
2004	 Aral Aromatics GmbH	 Single-Column Morphylane®
	 28,000	Uhde
	 Gelsenkirchen, Germany	 Toluene from Coke Oven Light Oil
Isomerisation, Transalkylation, Adsorption
2004	 Bouali Sina Petrochemical Co.	 p-Xylene Adsorption	 428,000	 Axens
	 Bandar Imam, Iran			
2004	 Bouali Sina Petrochemical Co.	 Xylenes Isomerisation	 1 970,000	 Axens
	 Bandar Imam, Iran			
2004	 Bouali Sina Petrochemical Co.	 Transalkylation	 883,000	 Sinopec
	 Bandar Imam, Iran
Thyssen Krupp Uhde GmbH
Friedrich-Uhde-Strasse 15 · 44141 Dortmund · Germany
Phone +49 231 547-0 · Fax +49 231 547-3032
www.uhde.eu
RT645/150002/2012ThyssenKruppUhde/TKprintmedia/PrintedinGermany

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ThyssenKrupp's Long History in Aromatics Production and Technology

  • 1. ThyssenKrupp Uhde Aromatics Our new name is ThyssenKrupp Industrial Solutions www.thyssenkrupp-industrial-solutions.com
  • 2. Table of contents 22 1. Company profile 3 2. Uhde and Aromatics 5 3. Aromatics – Sources, Demand and Applications 6 4. Process Configuration 8 4.1 Aromatics from Pyrolysis Gasoline 9 4.2 Aromatics from Reformate 12 4.3 Aromatics from Coke Oven Light Oil 15 5. Technology 16 5.1 Hydrogenation Technology 16 5.1.1 Hydrogenation of Pyrolysis Gasoline 16 5.1.2 Hydrogenation of Reformate 18 5.1.3 Hydrogenation of Coke Oven Light Oil 19 5.2 Fractionation Technology 20 5.2.1 Conventional Distillation 20 5.2.2 Divided Wall Column Distillation 20 5.3 Morphylane® Extractive Distillation 22 5.3.1 Conventional Morphylane® Process 22 5.3.2 Nitrogen Guard Bed 22 5.3.3 Single-Column Morphylane® Extractive Distillation 23 5.4 Hydrodealkylation Technology 25 5.5 Toluene Disproportionation Technology 25 5.6 Toluene/C9+ Transalkylation Technology 26 5.7 Para-Xylene Adsorption Technology 26 5.8 Xylenes Isomerisation Technology 27 6. Operating Results of Extractive Distillation Plants 28 7. Laboratory, Analytical and R&D Services 30 7.1 Analytical Facilities 30 7.1.1 Gas chromatography 30 7.1.2 Physical and chemical methods 30 7.1.3 Other analytical methods 30 7.2 Determination of thermohysical properties 30 7.3 Pilot Plant Tests 31 7.3.1 Separation techniques 31 7.3.2 Absorption/adsorption techniques 31 8. Services for our customers 32 9. Main references 34
  • 3. Uhde’s head office Dortmund, Germany 33 1. Company profile With its highly specialised workforce of more than 5,600 employees and its international network of subsidiaries and branch offices, Uhde, a Dortmund-based engineering contractor, has to date successfully completed over 2,000 projects throughout the world. Uhde’s international reputation has been built on the successful application of its motto Engineering with ideas to yield cost-effective high-tech solutions for its customers. The ever-increasing demands placed upon process and application technology in the fields of chemical processing, energy and environmental protection are met through a combination of specialist know-how, comprehensive service packages, top-quality engineering and impeccable punctuality.
  • 4. 4 Erection of the 60 meter high benzene extractive distillation column for Titan Petrochemicals, Pasir Gudang, Malaysia. Capacity: 168,000 mtpy benzene and toluene from pyrolysis gasoline.
  • 5. 5 Uhde’s extensive knowledge in extractive distillation technology and its excellent labora- tory facilities have led it to develop the most advanced process configurations for recover- ing aromatics and other products, such as butenes, a-olefins, cumene, isoprene and phenols, from different feedstocks. Uhde’s history in aromatics goes back to the first decades of the 20th century when Heinrich Koppers developed the Koppers coke oven technology for the production of coke for the steel industry. Right up to the fifties, coke oven light oil, which is recov- ered as a by-product of crude coke oven gas in coke oven plants, was the world’s main aromatics source. Due to the large quantity of impurities (diolefins, olefins, nitrogen, oxygen and sulphur compounds) the coke oven light oil had to be purified before the aromatics could be recovered. In those days, the lower benzene quality requirements could be met by sulphuric acid treatment and convention- al distillation processes. However, the large quantity of aromatics lost during sulphona- tion and the relatively high sulphur content in the benzene product were the driving force in the development of a hydrogena- tion process which was worked on together with BASF AG, Ludwigshafen, Germany and which solved the problems caused by unsaturated and inorganic impurities in the feedstock. The final purification of aromat- ics continued to be achieved by distillation only. At the beginning of the fifties, high-purity aromatics recovered by liquid-liquid extrac- tion in refineries came on to the market. The superior quality of these aromatics made it impossible for the aromatics distilled from coke oven light oil to compete. In addition, the improved purification process using azeotropic distillation was linked with high investment costs and inefficient energy util- isation. The liquid-liquid extraction process could not be used for coke oven light oil with an aro- matics content of 95% as separable phases are not able to form when the aromatics content is this high. At the request of the German coal and steel industry, Uhde initi- ated intensive R&D activities and developed a new process for coke oven light oil to ob- tain aromatics of a similar or better quality than those from refineries. The process developed by Uhde was based on a new solvent called N-formylmorpholine and used a different separation principle in- volving extractive distillation. The process was able to produce all the product purities required whilst reducing utilities consump- tion considerably as compared to liquid- liquid extraction processes. The first commercial plant based on this extractive distillation process (Morphylane® process) went on-stream in 1968 and pro- duced excellent results with regard to prod- uct quality and utility consumption figures. Based on the outstanding performance of this plant, the Morphylane® process was subsequently adapted to other feedstocks, such as pyrolysis gasoline and reformate. The process has undergone continuous im- provements and optimisation and its cost- effectiveness has led it to replace liquid- liquid extraction in all applications. Further- more, by optimising the combination of all the processes involved, such as hydrogena- tion, fractionation and aromatics extractive distillation, the complete process line for recovering aromatics from all possible feed- stocks was able to be improved to such an extent that competitive processes were left standing. Up to now, Uhde has been awarded con- tracts for more than 60 Morphylane® plants worldwide for recovering aromatics from pyrolysis gasoline, reformate and coke oven light oil. Leading aromatics producers, such as Chevron Phillips, Dow, BASF, Total, Shell and SK Corp., selected the Morphylane® pro- cess on the strength of its outstanding per- formance figures and its optimised process configuration after comparing it with com- petitive technologies. Uhde provides its customers with the fol- lowing services in the field of aromatics production: • Consulting services • Analytical services • Licensing • Engineering • Procurement • Construction • Plant operation • Maintenance services • Plant optimisation services Benzene Toluene Para-Xylene 5 2. Uhde and Aromatics Remarkably long experience
  • 6. Pyrolysis Gasoline 47% Reformate 33% HDA/TDP 15% Coke Oven Light Oil 5% Reformate 68% Pyrolysis Gasoline 29% Coke Oven Light Oil 3% Pyrolysis Gasoline 47% Reformate 33% HDA/TDP 15% Coke Oven Light Oil 5% Reformate 68% Pyrolysis Gasoline 29% Coke Oven Light Oil 3% 6 3. Aromatics – Sources, Demand and Applications Sources The main sources of aromatics (benzene, toluene, xylenes) are reformate from cata- lytic reforming, pyrolysis gasoline from steam-crackers and coke oven light oil from coke oven plants (Fig. 3-01). The reformate from catalytic reforming provides the basic supply of benzene, toluene, xylenes and heavier aromatics. The majority of toluene and heavier aromatics from reformate is converted to benzene and xylenes and is mainly used for p-xylene production. The remaining supply of aromatics is produced from pyrolysis gasoline and from coke oven light oil. Benzene, which has the highest production rate beside xylenes and toluene, is mainly produced from pyrolysis gasoline, followed by reformate. A significant percentage of Benzene, i.e. 15%, is also obtained from the hydrodealkylation (HDA) of heavier aro- matics and from toluene disproportionation (TDP). The smallest percentage of about 5% of benzene is obtained from coke oven light oil (Fig. 3-02). World Aromatics Sources World Benzene Sources Fig. 3-01 Source: HPP Science Fig. 3-02 Source: HPP Science HDA: Hydrodealkylation of heavier aromatics TDP: Toluene disproportionation Aromatics (benzene, toluene and xylenes) rank amongst the most important intermediate products in the chemical industry and have a wide range of applications.
  • 7. Ethylbenzene Cumene Cyclohexane Nitrobenzene Alkylbenzene Chlorobenzenes Nitrotoluenes Solvents o-Xylene m-Xylene p-Xylene Styrene Phenol α-Methylstyrene Caprolactam Adipic Acid Cyclohexanone Aniline LAB Toluene Diisocyanate Explosives, Dyes Phthalic Anhydride Isophthalic Acid Terephthalic Acid/ Dimethylterephthalate Polystyrene, ABS Resins, SBR Aniline, Phenolic Resins, Epoxy Resins, Surfactants Adhesives, ABS Resins, Waxes Polyamide 6 Polyamide 66 Polyurethane Foams Alkyd Resins, Methylacrylate Polyesters, Alkyd Resins Polyesters Benzene Toluene Xylenes 7 2005 0 10 20 30 40 50 2007 2009 Benzene Toluene Xylenes (Million metric tons/year) World Aromatics Demand Fig. 3-03 Source: HPP Science Fig. 3-04 Main Applications of BTX Aromatics Demand Worldwide, approx. 110 million tonnes of BTX aromatics are currently produced per year. An increase in demand of almost 4% p.a. is predicted for benzene due to the growth of end-use markets such as poly- styrene, polycarbonate, phenolic resins and nylon (Fig. 3-03). In the case of xylenes the increase in de- mand is determined by p-xylene, the big- gest isomer in terms of quantity. Growth in consumption of this isomer is expected to well exceed 5% p.a. in the near future. Para-xylene is used almost exclusively for the production of polyester via purified terephthalic acid. The estimated growth in overall toluene consumption is less than 3% p.a. Its major direct chemical use is toluene diisocyanate (TDI), a raw material for the production of polyurethane. Toluene extraction will in- crease as toluene is converted into benzene and xylenes via disproportionation. Applications The wide range of applications involving the main aromatics, benzene, toluene and xylenes (Fig. 3-04), illustrates the impor- tance of these intermediate products to the chemical industry.
  • 8. Typical Composition [wt.%] Component Benzene Toluene Xylenes Ethylbenzene C9+ Aromatics Total Aromatics Naphthenes Olefins Paraffins Sulphur Pyrolysis Gasoline 30 20 4 3 3 60 High High Low Up to 1000 ppm wt. Reformate 3 13 18 5 16 55 Low High High 1ppm wt. Light Reformate 24 46 0.5 0.5 0 70 Low Low High Low Coke Oven Light Oil 65 18 6 2 7 98 High High Low Up to 1 wt.% Fig. 4-01 Off-Gas to Steamcracker Selective Hydrogenation H2 C5- Fraction to Gasoline Pool Full Hydrogenation H2 Depentanizer Stabilizer Benzene Toluene Non-Aromatics to Steamcracker C8+ Fraction to Gasoline Pool Extractive Distillation B/TColumn Deheptanizer Crude Pyrolysis Gasoline from Steamcracker 8 4. Process Configuration Aromatics from Pyrolysis Gasoline, Reformate Coke Oven Light Oil Aromatics (benzene, toluene, xylenes) are mainly recovered from the following three feedstocks: • Pyrolysis gasoline from steamcrackers • Reformate from catalytic reformers • Light reformate from aromatics production • Coke oven light oil from coke oven plants The type of aromatics recovered and the process configuration are dictated by the feedstock used, as the composition of these feedstocks differs with regard to the content of paraffins, olefins, naphthenes and aro- matics (Fig. 4-01) and the amount of im- purities, such as chlorine, oxygen, nitrogen and sulphur components. Fig. 4-02 Aromatics from Pyrolysis Gasoline
  • 9. Off-Gas to Steamcracker Selective Hydrogenation H2 Benzene Non-Aromatics to Steamcracker C5- Fraction to Gasoline Pool Full Hydrogenation Extractive Distillation H2 Depentanizer C9+ Fraction to Gasoline Pool Heavy AromaticsH2 Hydro- dealkylation Off-Gas Aromatics B/TColumn Stabilizer Deheptanizer Deoctanizer Crude Pyrolysis Gasoline from Steamcracker 9 4.1 Aromatics from Pyrolysis Gasoline Pyrolysis gasoline is mainly used to recover benzene as well as benzene and toluene together. Producing mixed xylenes from pyrolysis gasoline is uneconomical due to the low xylene content and the high ethyl- benzene content in the pyrolysis gasoline. A typical process route for recovering benzene and toluene, starting from crude pyrolysis gasoline, is illustrated in Fig. 4-02. In the first step, the selective hydrogena- tion, diolefins are saturated at a relatively low temperature to avoid polymerisation. The C5- fraction is usually separated from the selectively hydrogenated pyrolysis gaso- line in a depentaniser upstream of the full hydrogenation stage and sent to the gaso- line pool as an octane-blending component. Thereby, hydrogen consumption is mini- mised and the size of the full hydrogenation unit can be reduced. If, however, the C5- fraction is sent back to the steamcracker as feedstock, it should be fully hydrogenated and separated with the non-aromatics downstream of the full hydrogenation unit in a combined depen- taniser/stabiliser or an extractive distillation stage. This dispenses with the need for a complete depentaniser system. Olefins as well as impurities, such as nitro- gen, sulphur and other components, are completely hydrogenated in the full hydro- genation unit. The off-gas containing H2 S is separated in the stabiliser and then re- turned to the steamcracker. In order to extract the required aromatics, a specific aromatics cut has to be separated from the pretreated pyrolysis gasoline. In the case of benzene recovery, a C6- cut is separated, in case of benzene and toluene recovery, a C7- cut is separated in a predis- tillation column and sent to the extractive distillation. The C7+ or C8+ fraction is sent to the gasoline pool as feedstock. Benzene or benzene and toluene are sepa- rated from the non-aromatics in the extrac- tive distillation unit which comprises a simple two column system. The non-aromatics are sent back to the steamcracker as feedstock. In the case of combined benzene and tolu- ene recovery, both products have to be sepa- rated downstream in a benzene/toluene col- umn system. In some cases it can be more economical to convert the C7+ aromatics into benzene to maximise the benzene output. In this case, a thermal hydrodealkylation unit is integrated in such a way that the extracted toluene and xylenes from the predistillation stage are dealkylated to form benzene (Fig. 4-03). Fig. 4-03 Maximum Benzene Recovery from Pyrolysis Gasoline
  • 10. 10 Aromatics complex for BASF in Mannheim/Germany. Capacities: 405,000mtpy aromatics extraction, 340,000mtpy hydrodealkylation The full range: Consisting of pyrolysis gasoline full hydrogenation, pyrolysis gasoline separation, reformate separation, benzene extractive distillation, toluene/xylene extractive distillation and hydrodealkylation.
  • 11. 1111
  • 12. H2 Light Ends H2 Xylenes Isomerisation Benzene Non-Aromatics to Gasoline Pool p-Xylene Adsorption Extractive Distillation ReformateSplitter C9+ Aromatics to Gasoline Pool Toluene Dis- proportionation p-Xylene XyleneColumn BenzeneColumn TolueneColumn Reformate from Catalytic Reformer o-Xylene Light Ends o-XyleneColumn C8+ C7– 12 The off-gas produced can then be used as fuel gas. The toluene does not necessar- ily have to be extracted before being fed to the hydrodealkylation stage. However, if the toluene fraction is fed directly from the pre- distillation stage, more hydrogen has to be consumed to crack the C7 non-aromatics and consequently more off-gas is pro- duced. Depending on the feedstock available and the products required, individual process configurations and heat integration of the individual units can be optimised whilst tak- ing into account local conditions such as specific utility availability and costs. Uhde finds the most cost-effective solutions with regard to investment and operating costs for its customers. 4.2 Aromatics from Reformate As a result of its relatively low benzene con- tent and relatively high toluene and xylenes content, reformate is mainly used to pro- duce p-xylene. Another application for aro- matics recovery is the reduction of benzene in motor gasoline by extracting benzene from the catalytic reformate. P-Xylene Production The typical process route for the production of p-xylene from reformate is illustrated in Fig. 4-04. In this case catalytic reformate is split into a C7- fraction and a C8+ fraction. The C7- frac- tion is then sent to the extractive distillation stage, where benzene and toluene are sepa- rated from the C7- non-aromatics. Fig. 4-04 Aromatics from Reformate
  • 13. 13 The C8+ fraction is sent directly to the p-xylene loop without the xylenes being ex- tracted. The non-aromatics content in this fraction is very low and can therefore be easily handled in the p-xylene loop. Conse- quently only benzene and toluene have to be extracted and not full-range BTX. The toluene is fed to the toluene dispropor- tionation stage where it is converted into benzene and xylenes. The benzene produced is separated as a high-purity product together with the ex- tracted benzene, whilst the unconverted toluene is recycled back to the dispropor- tionation. After separation, the mixed xylenes fraction from the disproportionation, the xylenes fraction from the reformate splitter and the recycled xylenes from the isomerisation are sent to the p-xylene adsorption, where p-xylene is separated from the xylenes. The remaining xylenes (m-xylene, o-xylene and ethylbenzene) are sent to the isomerisation to be converted into p-xylene. If o-xylene is also to be obtained as a prod- uct, it must be removed as a pure product by distillation in a separate column system before the xylenes enter the p-xylene isom- erisation loop. If maximum p-xylene production is required, a toluene and C9+ aromatics transalkylation is integrated into the process configuration (not illustrated). With respect to an opti- mised heat integration, vapours from the xylenes separation can be used to heat the benzene and toluene columns and other consumers. Half a million tonnes of benzene from reformate for Chevron Phillips Chemical Company, Pascagoula, MS, USA
  • 14. 14 Reformate from Catalytic Reformer Selective Hydrogenation H2 Off-Gas ReformateSplitter Non-Aromatics to Gasoline Pool Extractive Distillation Benzene C7+ Fraction to Gasoline Pool Benzene Reduction in Motor Gasoline In order to comply with the latest regula- tions limiting the benzene content in motor gasoline, the refining industry has to adjust its operations to either convert or recover benzene and other aromatics. Uhde has developed an optimised Mor- phylane® extractive destillation process for recovering benzene from reformate with lower investment and operating costs (Fig. 4-05) compared to aromatics saturation, liquid-liquid extraction and other processes. The reformate from the catalytic reformer is fed to the selective hydrogenation stage to saturate the diolefins which influence the acid wash colour (AWC) of the benzene product. The selective hydrogenation unit consists of a small reactor which is operated at low temperatures and pressure in a trickle phase. The small amount of off-gas is separated in the reactor using only phase separation. This upstream hydrogenation of diolefins eliminates the necessity for a downstream clay treating and subsequent product distil- lation thus saving considerably on invest- ment and operating costs. The pretreated reformate is fractionated and the C6- fraction is sent to the extrac- tive distillation where high purity benzene is removed from the non-aromatics in a simple two column system. One of the advantages of the Morphylane® extractive distillation process is that both dissolved hydrogen and light hydrocarbons can be easily removed with the overhead prod- uct thereby saving on investment for an upstream depentaniser system. Another advantage of the process is the ex- cellent benzene purity. A very low benzene content in the non-aromatics ( 0.1 wt%) can be achieved in the optimised extractive distillation configuration. Determined by the specific requirements of the refiners, Uhde also provides other pro- cess configurations, e.g. a combination of reformate fractionation (producing several blending cuts) and benzene extractive distil- lation or a combined benzene and toluene extraction. Fig. 4-05 Benzene from Reformate (Benzene Removal from Motor Gasoline)
  • 15. Deheptanizer Coke Oven Light Oil C8+ Hydrorefining Extractive Distillation C7- C9+ Non-Aromatics Tar Toluene Benzene H2 Off-Gas Xylenes B/TColumn C8Column Stabilizer C8- 15 4.3 Aromatics from Coke Oven Light Oil Coke oven light oil is generally used as a feedstock for recovering benzene, toluene, xylenes and higher aromatics as it has a very high aromatics content. The general process line for recovering aromatics from coke oven light oil is illustrated in Fig. 4-06. In a first step, the feedstock, which has a high content of impurities and a high con- tent of olefins and diolefins, is hydrogen- ated. A special hydrorefining process with a specific heating/evaporation system and a two stage reaction system is used for this purpose. The hydrogenated coke oven light oil is sent to the stabiliser where the off-gas, which contains for instance H2 S, is separated. The stabilised coke oven light oil is then sent to a deheptaniser. The overhead C7- fraction is sent to the extractive distillation in which benzene and toluene are separated from the relatively small amount of non-aromatics in a single extractive distillation before being split into high-purity benzene and toluene. The C8+ fraction leaving wthe bottom of the deheptaniser is usually sent to another frac- tionation system where xylenes and higher aromatics are recovered by distillation. Fig. 4-06 Aromatics from Coke Oven Light Oil Uhde engineered the entire aromatics recovery complex for ARSOL Aromatics in Gelsenkirchen/Germany, consisting of hydrorefining, benzene extractive distillation and distillation of the benzene homologues (Toluene, Xylenes and C9+ aromatics) from coke oven light oil.
  • 16. H2 Selectively Hydrogenated Pyrolysis Gasoline Liquid Recycle H2 Off-Gas Separator Reactor Crude Pyrolysis Gasoline from Steamcracker 16 5.1 Hydrogenation Technology If pure aromatics are to be obtained, the feed must undergo a pretreatment before the non-aromatics and aromatics can be separated by extractive distillation. Catalytic hydrogenation processes have become the most appropriate technologies for eliminat- ing impurities such as diolefins, olefins, sulphur, nitrogen and oxygen components. 5.1.1 Hydrogenation of Pyrolysis Gasoline Due to its high diolefin content, crude pyro- lysis gasoline from steamcrackers has a tendency to polymerise and to form gum even when stored in tanks under nitrogen blanketing. In view of the fact that polymer- isation is encouraged at higher tempera- tures, the diolefins have to be hydrogenated at relatively low temperatures by highly ac- tive catalysts in the so-called selective hydro- genation process. Once the diolefins have been subjected to selective hydrogenation, other impurities can be hydrogenated in the full hydrogenation stage at high tempera- tures. Selective Hydrogenation (see Fig. 5-01) In this process step, crude pyrolysis gas- oline is sent to the hydrogenation reactor after having been mixed with hydrogen. The reaction takes place in the trickle phase or in the liquid phase on nobel metal catalysts (palladium on aluminium oxide carrier) or on nickel catalysts. The selectively hydrogenated pyrolysis gasoline leaves the reactor and is sent to a separator where the remaining hydrogen is separated from the liquid phase. Depending on the catalyst selected, the gas phase is sent either to the fuel gas unit or to the full hydrogenation stage in which the remaining hydrogen is utilised as a make-up agent. After cooling, part of the liquid phase is re- cycled to the reactor to control the reactor temperature. The selectively hydrotreated product is fed to a fractionation column or is sent directly to the full hydrogenation. Fig. 5-01 Selective Hydrogenation of Pyrolysis Gasoline 5. Technology Hydrogenation Technology
  • 17. Selectively Hydrogenated Pyrolysis Gasoline Recycle H2 Reactor Separator Fully Hydrogenated Pyrolysis Gasoline High Pressure Separator Make-up H2 Off-Gas 17 Full Hydrogenation (see Fig. 5-02) Impurities such as sulphur, nitrogen and oxygen components and olefins are hydro- genated in the full hydrogenation stage. The reactions take place in the gaseous phase on nickel/molybdenum and/or cobalt/molyb- denum catalysts at reactor inlet tempera- tures of between 240°C and 320°C. To this end, the selectively hydrogenated pyrolysis is fed to the reactor via feed/efflu- ent heat exchangers and a process heater after having been mixed with recycled hydro- gen. After cooling, the reactor product is sent to a high pressure separator where the hydrogen, which has not been consumed, is separated from the liquid phase. The remaining hydrogen is mixed with fresh make-up hydrogen and fed back to the reactor. The liquid reactor product, fully hydrogen- ated pyrolysis gasoline, is sent to a stabiliser system in which the off-gas containing H2 S is separated from the product. The off-gas is normally recycled back to the steam cracker, whilst the stabilised reactor product is sent either to a fractionation column or directly to the aromatics recovery unit. Various optimised process designs are provided depending on the specific criteria, such as feedstock specification, hydrogen quality, etc. In this respect some of the most cost-effective solutions with regard to investment and operating costs include reactor-side intermediate quenching by cooled liquid product recycle, steam gen- eration and additional reactive catalyst layers for difficult feedstocks. Fig. 5-02 Full Hydrogenation of Pyrolysis Gasoline
  • 18. Reformate Fraction H2 Reformate Fraction Off-Gas Reactor 18 5.1.2 Hydrogenation of Reformate Although high quality benzene containing less than 30ppm non-aromatics is pro- duced by extractive distillation, even a small quantity of diolefins (around 5ppm) can result in an acid wash colour (AWC) speci- fication higher than that which is actually required. If diolefins are present, especially those of a naphthenic nature the reformate must be subjected to an additional treat- ment stage. As the most common unsaturated com- ponents, such as olefins and diolefins, are mostly removed by clay treating combined with a conventional liquid-liquid extraction plant. One alternative is to install a selec- tive hydrogenation stage for the olefins and diolefins upstream of the extractive distil- lation process. The catalyst used for the selective hydrogenation of reformate has a long service life and can usually be regen- erated several times. The maintenance savings are thus quite remarkable. In addi- tion, disposing of clay has become more and more difficult due to the enforcement of environmental protection laws in an in- creasing number of countries. The essential features of the catalyst can be summarised as follows: • high conversion rate with regard to diolefins • reduction of olefins • low benzene losses (as compared to clay treating) • long cycle length between regeneration • long service life • mild operating conditions The typical process scheme is illustrated in Fig. 5-03. The benzene-rich cut upstream of the ex- tractive distillation stage is passed to the selective hydrogenation reactor once the required inlet temperature has been reached. Hydrogen is added to the benzene-rich cut. Selective hydrogenation takes place in the trickle bed of the reactor at low tempera- tures and pressures. The product, which is free of diolefins, is then passed directly to the extractive distillation stage. Separation of the gas phase takes place in the reactor bottom. Additional stripping of the product is not necessary. Fig. 5-03 Reformate Selective Hydrogenation
  • 19. Coke Oven Light Oil Recycle Compressor Stage Evaporator H2 Tardistillation Column Tar Pre-Reactor Main Reactor Hydrogenated Coke Oven Light Oil High Pressure Separator Off-Gas 19 5.1.3 Hydrogenation of Coke Oven Light Oil In a similar way to crude pyrolysis gasoline, coke oven light oil also has to be hydrogen- ated. Impurities, such as organic sulphur, nitrogen and oxygen components, have to be removed and diolefins and olefins have to be saturated to stabilise the coke oven light oil and to assure high-quality final products. The “BASF-Scholven” process meets all the above requirements. The reactions take place in the gas phase on a nickel/molybdenum catalyst in the prereactor and on a cobalt/ molybdenum catalyst in the main reactor. Special emphasis is placed on the evapo- ration of the coke oven light oil feed. Uhde has developed a proprietary system which permits smooth evaporation in a special- multistage evaporator thereby minimising fouling whilst achieving high on-stream factors without the addition of fouling in- hibitors. The coke oven light oil is mixed with make- up hydrogen and recycle hydrogen and passed through a system of feed/effluent exchangers which are combined with the stage evaporator (Fig. 5-04). With the ex- ception of a small quantity of heavy hydro- carbons which are withdrawn at the bottom of the multi-stage evaporator, almost all the feedstock is evaporated. After being subjected to additional heating, this material is fed to the prereactor where most of the diolefins are converted. The effluent from the prereactor is then heated further by a process heater. In the main reactor the olefins are saturated and the remaining sulphur, nitrogen and oxygen compounds are hydrogenated. After cool- ing, the effluent from the main reactor is sent to the high pressure separator to dis- engage the hydrogen from the liquid phase. The separated hydrogen is mixed with make-up hydrogen, recompressed and returned to the coke oven light oil feed. The fully hydrogenated raffinate from the high pressure separator is sent to a conven- tional stabiliser system. Off-gas containing H2 S and NH3 is separated from the raffinate product. The stabilised raffinate is sent to a fractionation and aromatics recovery unit. Uhde offers a variety of process configura- tions adapted to the feedstock conditions and customer requirements. The heavy hydrocar- bon residue can, for example, be subjected to further treatment in a tar distillation unit to enhance BTX aromatics recovery or to produce valuable tar-derived products. Fig. 5-04 Hydrorefining of Coke Oven Light Oil
  • 20. 20 5.2 Fractionation Technology For many decades, distillation has been one of Uhde's key areas. From hydrocarbon C2 and C3 distillation to C9 and C10 distillation, from crude distillation to pure component distillation, Uhde can provide fractionation technology for virtually any hydrocarbon system. Our extensive experience is very efficiently backed up by our laboratory and pilot plant facilities. Hydrocarbon equilibrium data can be measured in our laboratories and then implemented in conventional standard pro- cess simulators. Pilot testing may also be used to confirm or demonstrate these adapted models. Special feedstocks can be tested in our pilot plants allowing distillation processes to be opti- mised to meet customer requirements. 5.2.1 Conventional Distillation Uhde’s expertise includes distillation sys- tems which use conventional tray tech- nology as well as random and structured packing technologies. We have designed columns up to 10 metres in diameter and as high as 100 metres. 5.2.2 Divided Wall Column Distillation Whenever more than two fractions have to be separated by distillation, the question arises as to which is the most efficient con- figuration (Fig. 5-05). Configurations involving columns which are fully thermodynamically coupled have certain energetic advantages over conven- tional fractionation technologies. Latest technological developments have, however, laid the foundation for adequate calcula- tion techniques and established the generic guidelines for thermodynamic simulations. This has resulted in the development of en- gineering tools which permit the application of the divided wall technology and which make use of the thermodynamic advan- tages. These advantages are reflected in: • up to 20% less investment costs • up to 35% less energy costs • up to 40% less plant space requirements Uhde successfully introduced this tech- nology to aromatics applications. Two com- mercial-scale divided wall columns have recently been commissioned for aromatics recovery. In addition, Uhde has installed divided wall column test facilities in its own laboratories to work on further improve- ments. The divided wall column technology is an excellent tool for revamping plants, enhanc- ing their capacity and improving product qualities and yields. Existing hardware can be modified within one week resulting in a short shut-down time and low production losses. Plant converted to the divided wall tech- nology in just five days. The Uhde team at the Ruhr Oel GmbH re- finery in Münchsmünster in Bavaria had just five days to convert a distillation column to a divided wall column using one of Uhde’s new developments. The Uhde team man- aged to complete the task in the allotted time despite inclement weather. The divided wall column saved Ruhr Oel having to build a second column for removal of benzene so that the more stringent benzene specifica- tions in gasoline could be met. Fractionation Technology Old section of the existing column
  • 21. Reformate or Pyrolysis Gasoline C8+ Fraction C5 Fraction C6/C7 Fraction 21 Fig. 5-05 Divided Wall Column New divided wall section before installation of packings
  • 22. 22 5.3 Morphylane® Extractive Distillation Due to lower capital cost and utilities con- sumption, the Uhde Morphylane® extractive distillation process has replaced the former liquid-liquid extraction technology. 5.3.1 Conventional Morphylane® Process In the extractive distillation (ED) process (see Fig. 5-06), the solvent alters the va- pour pressure of the components to be separated. The vapour pressure of the aromatics is lowered more than that of the less soluble non-aromatics. The ED process is relatively simple. The solvent is supplied to the head of a distillation column via a central feed inlet. The non-aromatic vapours leave the ED column with some of the sol- vent vapours. The internal reflux is con- trolled by the solvent feed temperature. The solvent is recovered from the overhead product in a small column with sectional reflux, which can be either mounted on the main column or installed separately. The bottom product from the ED column is fed to a distillation stage, i.e. the stripper, to separate the pure aromatics and the solvent. After intensive heat exchange, the lean solvent is recycled to the ED column. The product purity is affected by a number of different parameters including solvent selectivity, the number of separation stages, the solvent/feedstock ratio and the internal reflux ratio in the ED column. The solvent properties needed for this process include high selectivity, thermal stability and a suit- able boiling point. The solvent used in the Morphylane® process is a single compound, namely N-formylmorpholine (NFM). No agents or promoters are added to the sol- vent. The salient features of NFM are sum- marised in Fig. 5-07. 5.3.2 Nitrogen Guard Bed The Morphylane® process withholds the sol- vent in the unit almost completely. The con- centration of NFM in the extract is typically less than 1 wt.-ppm, which corresponds to 0.15 wt.-ppm basic nitrogen. Therefore losses are of no importance to the eco- nomics of the process. However, market demands have increased: Due to the inven- tion and spread of zeolithe catalysts for alkylation processes the requirements for the extract of the Morphylane® process have become stricter. The nitrogen concentration is required to be as low as possible. Uhde’s answer to this market demand is the Nitro- gen Guard Bed. This adsorption bed is able to capture even traces of basic nitrogen, such that the product concentration is in the ppb-range, below the detection limit. There- fore aromatics from the Morphylane® units can safely be fed to zeolithe-catalysts reac- tors, producing alkyl-aromatics in world-scale. Aromatics Extractive Distillation Column Stripper Column Solvent + Aromatics Solvent Non-Aromatics Aromatics Fraction Fig. 5-06 Morphylane® Extractive Distillation Morphylane® Extractive Distillation Solvent: N-formylmorpholine (NFM)
  • 23. 23 5.3.3 Single-Column Morphylane® Extractive Distillation Uhde’s new Single-Column Morphylane® extractive distillation process uses a single- column configuration which integrates the extractive distillation (ED) column and the stripper column of the conventional Mor- phylane® design. It represents a superior process option in terms of investment and operation (Fig. 5-08). In the Single-Column ED process, the aro- matics are removed from the vaporised feed by the solvent (NFM) in packing 2. Residual non-aromatics are stripped off by aromatics vapours in packing 3. Solvent traces in the column head are washed back with the non- aromatics reflux in packing 1, while solvent traces in the aromatics vapours are removed by aromatics reflux in packing 4. Packings 3 and 4 are separated by a divid- ing wall forming two chambers. The cham- ber containing packing 4 is closed at the top side. The aromatics-solvent mixture draining from the two chambers is fed to the stripping sec- tion (packing 5) where the aromatics are stripped off from the solvent. The lean sol- vent is returned to the top of the column. In- tensive stripping is crucial to the aromatics yield. The first industrial realisation of the new con- cept has been a toluene recovery plant for ARSOL Aromatics GmbH in Gelsenkirchen, Germany, commissioned in October 2004. Based on the Single-Column Uhde Morphy- lane® process described above, the plant produces pure toluene from fully hydrogen- ated coke oven light oil. The plant has a toluene capacity of 30,000 tonnes/year and it achieves purities of over 99.99%. The column has proved easy to operate, even under varying feed conditions and product specifications. Uhde supplied the licence for the plant, provided engineering services and was on hand in a consulting capacity during com- missioning. In 2005, Uhde was presented with the 'Kirkpatrick Honor Award for Chemical En- gineering Achievement', a biennial award for innovative products or processes by the journal Chemical Engineering. A vital pre- requisite for submission of an innovation is that its first-time industrial-scale implemen- tation was within the past two years. Our technology met this condition with the suc- cessful commissioning of the aromatics plant based on the innovative single-column con- cept for ARSOL Aromatics GmbH in 2004. An international team of experts ranked the process among the five best process inno- vations of the last two years. Non-Aromatics Aromatics Solvent Feed 3 2 1 4 5 Fig. 5-08 Single-Column Morphylane® Extractive Distillation Fig. 5-07 Main Features of the Morphylane ® Extractive Distillation Process Process features: Simple plant arrangement Low number of equipment (2 columns) Little space required No raffinate wash system required Low solvent filling Low investment Low energy consumption Easy to operate No chemical agents required High on-stream time N-formylmorpholine solvent features: High selectivity High solvent efficiency High purity products even from Feedstocks with high paraffinic contents High permanent thermal stability High heat transfer rate No corrosive effect High chemical stability Negligible solvent consumption Low solvent regeneration cost No toxicity Low price
  • 24. 24 525,000mtpy of pyrolysis gasoline extractive distillation for Rayong Olefins Corp., Thailand
  • 25. 5.4 Hydrodealkylation Technology Hydrodealkylation, commonly known as HDA, is a well-established process for con- verting C7 and C8 (even up to C9+ ) alkylben- zenes to high purity benzene. Very few new plants are being built, however, as the huge hydrogen consumption makes the benzene quite expensive. The preferred technology uses non-catalytic thermal reactor systems which have a high benzene yield, extremely high on-stream factors and lower operating costs as com- pared with catalytic systems. A typical pro- cess configuration is shown in Fig. 5-09. Several options, e.g. to enhance benzene yield or to minimise hydrogen consump- tion are available, depending on the qual- ity of the feedstock treated in the HDA. Co-processing C8 and even C9+ aromatics will enhance benzene output but will also increase hydrogen consumption consider- ably. An upstream extraction stage reduces the content of non-aromatics to such an extent that the amount of hydrogen con- sumed in the cracking reaction is minimised. 5.5 Toluene Disproportionation Technology Toluene Disproportionation Technology (TDP) converts toluene to benzene and mixed xylenes in approximately equimolar quantities. The reaction is carried out in the vapour phase on a variety of acidic zeolite catalysts. Conventional TDP produces a xylenes fraction in which the xylene-isomer equilibrium is reached. The para-xylene concentration is therefore limited to 24%. Further processing is required to increase the para-xylene yield. This involves separating the para-xylene isomer by selectively adsorbing or by crystallising and isomerising the remaining meta-xylenes and ortho-xylenes (optionally) to form para-xylene. Since the para-xylene concentration in isomerisation is only 24% as well, a large recycle loop is required to completely convert the undesired isomers to para-xylene. Fresh Toluene BenzeneColumn XyleneRevovery Column Deheptanizer Separator TDPReactor Stabilizer Make-up Hydrogen Light Ends to Fuel Mixed Xylenes to Para-xylene Recovery Benzene C9+ Aromatics to Gasoline Pool B/T Aromatics from Extraction Vent Benzene Heavy Aromatics Purge HDAReactor C8+ Aromatics from Predistillation BenzeneColumn RecycleColumn Make-up Hydrogen Stabilizer Separator 25 Fig. 5-10 Toluene Disproportionation Unit Fig. 5-09 Hydrodealkylation (HDA) Unit Hydrodealkylation and Toluene Disproportionation Technology A major technological break-through was achieved when the zeolite catalyst geometry was developed to maximise para-xylene selectivity. The TDP with improved selectiv- ity produces a xylene fraction which con- tains up to 90% para-xylene. Consequently, the downstream para-xylene recovery and xylene isomerisation stages are smaller and more efficient. Fig. 5-10 shows a typical process configuration for a TDP.
  • 26. 26 5.6 Toluene/C9+ Transalkylation Technology In contrast to the TDP, toluene and C9+ aro- matics are converted to mixed xylenes in the transalkylation technology. The xylenes- to-benzene ratio increases if more C9+ aro- matics are mixed with the toluene feed and if the transalkylation reaction rate increases. Similar catalysts to those used in TDP units are used. 5.7 Para-Xylene Adsorption Technology Para-xylene can practically not be sepa- rated from meta-xylene by conventional distillation due to the closeness of their boiling points. In contrast, ortho-xylene can be recovered by conventional distillation because its boiling point is considerably higher than that of the other isomers. The most common para-xylene separation technology used today involves adsorption using molecular sieves. Crystallisation technology is also widely used, especially in North America and in Western Europe. However, one of the main advantages of adsorption over crystallisa- tion is its high recovery rate per pass (up to 97%). In contrast, crystallisation units have a eutectic limitation of 65%. All commer- cialised para-xylene adsorption processes use isothermal, liquid phase adsorption. The adsorbent’s selectivity, capacity and reversibility are the key properties relevant to desorption. At the heart of the adsorption process are the adsorption columns in which the fol- lowing steps occur in a sophisticated semi- continuous operation: • feeding in mixed xylenes • diluting out extract (para-xylene) with a desorbent • diluting out raffinate (ethylbenzene, meta-xylene and ortho-xylene) with a desor bent • feeding in recycled desorbent The diluted extract and raffinate streams are fractionated in an extraction column and a raffinate column to recover the desorbent which is recycled back to the adsorbers. Any residual toluene contained in the mixed xylenes feed and carried over with the para- xylene extracted is separated in a finishing column. The concentrated raffinate, meta-, ortho-xylene and ethylbenzene, is sent to the isomerisation stage. A simplified pro- cess configuration is shown in Fig. 5-11. Mixed Xylenes from Xylene Splitter RaffinateColumnExtractColumn FinishingColumn Block scheme of the Adsorption System Desorbent Light Ends Para-Xylene (Extract) C8 -Aromatics to Isomerisation (Raffinate) Fig. 5-11 Para-Xylene Adsorption Unit Toluene/C9+ Transalkylation and Para-Xylene Adsorption Technology
  • 27. 27 5.8 Xylenes Isomerisation Technology Once the C8 aromatics stream has been depleted of para-xylene (and optionally of ortho-xylene as well), the stream is sent to an isomerisation unit to re-establish the equilibrium of the xylene mixture. This oc- curs by converting the meta-xylene (and ortho-xylene, if present) and the ethyl- benzene (EB) to para-xylene by isomerisa- tion until the equilibrium is reached. The isomerisate is then returned to the xylene fractionation section in which valuable par- axylene, and optionally ortho-xylene, are recovered. Meta-xylene and EB are returned to the recycle loop. Alternatively, EB can be dealkylated to form benzene and ethane. The method of EB conversion is influenced by the catalyst type. Xylene isomerisation catalysts can be categorised according to their ability to isomerise EB into additional xylenes or their ability to dealkylate EB. Both types of catalyst isomerise the xylenes to form a close equilibrium xylene isomerisate mixture. EB isomerisation catalysts result in the highest para-xylene yield from a given feed- stock due to the conversion of EB to addi- tional xylenes. EB isomerisation is more difficult than xylene isomerisation and re- quires a bifunctional acid-metal catalyst. EB isomerisation occurs using C8 -naphthene intermediates. This type of catalyst must be operated with a substantial concentration of C8 -naphthenes in the reactor recycle loop to allow efficient conversion of EB to xylenes. Xylene feedstocks containing high EB con- centrations, such as pyrolysis gasoline feed- stocks, are particularly suitable as the EB is converted to naphthenes thereby producing the naphthene concentration required. The EB isomerisation conversion rate typically amounts to 30-35%. EB dealkylation is not limited to equilibrium conditions and permits EB conversion rates of up to 65%. EB dealkylation catalysts gen- erally contain a shape-specific molecular sieve with a given pore size, which minimises xylene loss caused by xylene disproportion- ation, transalkylation or hydrocracking. 3CH CH3 CH CH3 CH3 3 CH3 meta-Xylene para-Xylene ortho-Xylene Xylene Isomers Xylenes Isomerisation Technology
  • 28. 28 6. Operating Results of Extractive Distillation Plants ED column and stripper, aromatics complex at the Kashima refinery, Japan Table 7-01 Reformate feed with high aromatics content Typically, reformates which con- tain large quantities of aromat- ics are processed in aromatics complexes in which a high aromatics yield reformer is in- stalled. The C6  core cut contains aromatics levels which well in excess of 50%. The operating results of four plants are sum- marised in Tables 7-01 and 7-02. Reformate feed with high aromatics content Plant for Year of commissioning Benzene in ED-feed Toluene in ED-feed Benzene production Toluene production Benzene quality Toluene quality Solvent loss Steam consumption Yield Japan Energy, Kashima 2007 30% 49% 136,000 mtpy 223,000 mtpy max. 400 wt.-ppm non-aromatics 99.0 wt.-% max. 0.007 kg/t aromatics 480 kg/t ED-feed Benzene: 99.92% Repsol, Spain 2007 75% 0% 221,000 mtpy - 400 wt.-ppm non-aromatics - max. 0.010 kg/t aromatics 470 kg/t ED-feed Benzene: 99.7%
  • 29. Table 7-04 Table 7-02 *) including the benzene/toluene splitter Table 7-03 29 Reformate feed with low aromatics content Reformates processed in gas- oline-based refineries generally contain smaller quantities of benzene. Reformers are often operated at lower severity levels. If the benzene content of gaso- line is to be reduced, the ben- zene content of the C6 core cut fed to the extractive distillation stage needs to be well below 50 wt%. In this type of applica- tion, the energy consumption of extractive distillation processes is lower than that of reformate streams with a higher aromatics (benzene) content. Table 7-03 shows the operating results of two plants recently commis- sioned for benzene reduction. Pyrolysis gasoline feed Pyrolysis gasoline from steam- crackers has a relatively high aromatics content which is dic- tated by the cracker feedstock and the severity of the cracker. The results obtained from an aromatics distillation process in a typical naphtha-based steam-cracker are shown in Table 7-04. The two examples are based on a benzene ED, which was started up in the Netherlands at the end of 2002, and a benzene/toluene ED, which went into operation in Poland in 2005. Reformate and pyrolysis gasoline feed with high aromatics content Plant for Year of commissioning Benzene in ED-feed Toluene in ED-feed Benzene production Toluene production Benzene quality Toluene quality Solvent loss Steam consumption Yield PKN Orlen, Poland 2006 33% 41% 178,000 mtpy 222,000 mtpy 70 wt.-ppm non-aromatics 470 wt.-ppm non-aromatics 0.006 kg/t aromatics 540 kg/t ED-feed Benzene: 99.9; Toluol: 98.2 % Shell Moerdijk, The Netherlands 2002 65 wt.-% - 550,000 mtpy - max. 200 wt.-ppm non-aromatics - max. 0.003 kg/t benzene 400 kg / t ED-feed - Reformate feed with low aromatics content Plant for Year of commissioning Benzene in ED-feed Benzene production Benzene quality Solvent loss Steam consumption Holborn Refinery, Germany 2003 ~ 27 wt.% 66,000 mtpy max. 10 ppm wt. non-aromatics max. 0.002 kg/t benzene 450 kg/t ED-feed Tonen, Kawasaki, Japan 1999 ~ 30 wt.% 100,000 mtpy max. 50 ppm wt. non-aromatics max. 0.001 kg/t benzene 380 kg/t ED-feed Reformate feed with high aromatics content Plant for Year of commissioning Benzene in ED-feed Toluene in ED-feed Benzene production Toluene production Benzene quality Toluene quality Solvent loss Steam consumption BASF Antwerp, Belgium 2000 ~ 65 wt.% - 258,000 mtpy - max. 100 ppm wt. non-aromatics - max. 0.005 kg/t benzene 450 kg/t ED-feed SPC, PR China 1999 ~ 75 wt.% ~ 85 wt.% 135,000 mtpy 65,000 mtpy max. 80 ppm wt. non-aromatics max. 600 ppm wt. non-aromatics max. 0.08 kg/t aromatics 680 kg/t ED-feed *)
  • 30. 30 Uhde operates laboratory and pilot plant facilities in Ennigerloh, Germany. The facili- ties are used for ongoing developments to new processes and for optimising estab- lished processes. In conjunction with their colleagues in the central RD division, a highly qualified team of 30 employees is committed to providing RD services for our customers. This team includes: • 12 chemists and chemical engineers • 10 chemical technicians and mechanics • 4 administrative staff is committed to providing RD services for our customers. Using the latest state-of-the-art equipment, our RD staff is dedicated to: • improving Uhde processes • searching for new processes and process opportunities • improving analytical methods and preparing analytical instructions and manuals • providing a wide range of analyses for feedstocks and products • providing analytical support during the commissioning of our plants Our process engineers in Dortmund and Bad Soden work closely with the laboratory staff and are able to support operations whenever needed. The laboratory and pilot facilities are certified in accordance with ISO 9001 to ensure consistently high standards. 7.1 Analytical facilities The laboratory consists of 5 working sections: • laboratory for inorganic chemistry/physical analyses • gas chromatography • laboratory for fuel and coal analysis • laboratory for oil and wax analysis • test laboratory The analytical facilities permit standard DIN/ISO or ASTM analyses of virtually any type of fuel and refinery/petrochemical feedstock, as well as a variety of inorganic analytical methods and water analysis methods. Some of the main methods are summarised below. 7.1.1 Gas chromatography Our laboratory uses gas chromatographs to categorise all types of hydrocarbon feed- stocks, products and intermediate products. The samples are separated analytically in capillary, widebore or packed columns of suitable polarity. Standard analytical methods using flame ionisation detectors (FID) and thermal conductivity detectors (TCD), are enhanced by special detection methods which use selective sulphur detec- tors (S-CLD) or nitrogen detectors (NPD and N-CLD). Additionally, a powerful GC-MSD sys- tem enables us not only to identify unknown components in a complex matrix, but also to quantify components of special interest even when present as trace amounts. 7.1.2 Physical and chemical methods Hydrocarbon components are completely broken down and other properties and im- purities are also of interest. We use various analytical methods to analyse these prop- erties and impurities, including elemental analyses (CHNS), chloride content, bromine index/number, acid wash colour, specific gravity, molecular weight, acidity, refraction index and many more. The methods used include: • UV-Vis spectroscopy • ion chromatography • atom absorption spectroscopy • potentiometry • coulometry • viscosimetry (Hoeppler, Ubbelhohe, Engler) • ignition point determination (Abel-Pensky, Pensky-Martens) • surface tension (DeNouy) • hydrogen/oxygen combustion • water determination (Karl Fischer) • solidification point acc. to ASTM D 852 • boiling range acc. to ASTM D 850 and D 1160 • total sulphur acc. to ASTM D 5453 and D 7183 • total nitrogen acc. to ASTM D 6069 and D 7184 7.1.3 Other analytical methods In addition to the standard analytical meth- ods mentioned above, our laboratory is able to develop other analytical methods to cater to special customer requirements, or to support troubleshooting in our customers’ plants. This means that we can measure: • thermal stability of chemicals • corrosion of materials in chemicals • 2-liquid phase separation abilities • polymer content in solvents • foaming tendencies • chemical stability 7.2 Determination of thermo-physical properties Simulation models must be constantly enhanced using data gained during plant operation or in laboratory tests to ensure the continuous improvement of process simulation and equipment design. Uhde has continuously developed and increased its thermo-physical property data banks which are used for process simulation of its separation technologies. Vapour-liquid equilibrium (VLE) or liquid- 7. Laboratory, Analytical and RD Services Gas-phase chromatographs used in the separation and quantitative ana- lysis of liquid and gaseous samples
  • 31. i-Butan n-Butan i-Pentan n-Pentan 2.2-Dimethylbutan 2.3-Dimethylbutan Cyclopentan n-Hexan 2.2-Dimethylpentan 2.4-Dimethylpentan 2.2.1-Trimethylpentan Methylcyclopentan 3.3-Dimethylpentan 2-Methylhexan 2.3-Dimethylpentan Cyclohexan 2.2.3-Trimethylpentan 3-Ethylpentan cis1.3-DMCP tr1.3-DMCP tr1.2-DMCP n-Heptan 2.2.3.3-Teramethylbutan Benzol Methylcyclohexan 2.2-Dimethylhexan 1.1.3-Trimethylhexan 3-Methylhexan 31 liquid equilibrium (LLE) data for specific solvent/hydrocarbon systems (used in ED and LLE) is measured in our laboratories, evaluated and linked to our process simula- tors. Simulation results can later be verified or checked in our pilot plant facilities under real operating conditions. This procedure allows us to develop tailor-made separation processes for our customers. Uhde’s laboratory includes equipment to: • determine the VLE dataof binary and tertiary systems at temperatures of 20°C-160°C and pressures of 0-40 bar • determine the LLE data of binary, ter- tiary, and quaternary systems at tem- peratures of -40°C to 95°C for 1 bar, and temperatures of 20°C-160°C for pres- sures ranging from 0-5 bar • measure crystallisation equilibria • measure the solubility of gases in liquids • determine mass transfer coefficients 7.3 Pilot Plant Tests The Uhde pilot plant tower is a three-storey building situated next to the laboratory. The 3 platforms cover an overall height of 12 m. Larger pilot plant facilities can be erected on various other ThyssenKrupp sites if re- quired. The pilot plant is completely surrounded by scaffolding made from Mero cuboid struc- tural components (edge length 1 m) and can be accessed every 2 m to permit simple and fast installation of equipment and bulk. Most modern DCS and instrumentation ele- ments are used for measuring and control- ling the pilot plant. A 2-channel gas chromatograph with FID is used for online liquid analysis. The chro- matograph is equipped with 2 completely separated systems of recycle pumps and automatic liquid injectors. Time-controlled processing and analytical operations are performed using a computer. 7.3.1 Separation techniques A variety of fractionation utilities is available: • conventional distillation with up to 160 theoretical stages. Modules with an ID of 100 mm, 72 mm, and 50 mm made of stainless steel or glass for laboratorytype structured packings (Sulzer DX/EX) and bubble cap trays • extractive distillation with up to 70 theo- retical stages. Modules with an ID of 72mm in stainless steel equipped with structured packings • liquid-liquid extractors with up to 50 theoretical stages. Modules with an ID of 40 mm in glass equipped with structured packings (Sulzer BX) • divided wall columns with up to 40 theo- retical stages in the partition section. The operating range can be varied from a high vacuum to 6 bar. Several types of tubular reactors, some of which are jacketed, and agitated autoclaves (CSTR) can be used for catalyst and absor- bents testing, and for measuring reaction kinetics. Pressures of up to 200 bar and temperatures of up to 600°C can be applied to test catalytic reactions and catalyst for- mulations. 7.3.2 Absorption/adsorption techniques The specially designed equipment in our pilot plant facilities allows us to test or meas- ure static and dynamic absorption equilibria and mass transfer for gas scrubbers. This equipment includes autoclaves, falling-film adsorbers and scrubbers fitted with a variety of random or structured packings. The Uhde research centre Research facility with PC-based process control system for process development in the fields of distillation, extraction and extractive distillation
  • 32. 32 ThyssenKrupp Uhde is dedicated to providing its cus- tomers with a wide range of services and to supporting them in their efforts to succeed in their line of business. With our worldwide network of local organisations and experienced local representatives, as well as first-class backing from our head office, ThyssenKrupp Uhde has the ideal qualifications to achieve this goal. We at ThyssenKrupp Uhde place particular importance on interacting with our customers at an early stage to combine their ambition and expertise with our experi- ence. Whenever we can, we give potential customers the opportunity to visit operating plants and to personally evaluate such matters as process operability, main- tenance and on-stream time. We aim to build our future business on the confidence our customers place in us. ThyssenKrupp Uhde provides the entire spectrum of services associated with an EPC contractor, from the initial feasibility study, through financing concepts and project management right up to the commissioning of units and grass-roots plants. Our impressive portfolio of services includes: • Feasibility studies / technology selection • Project management • Arrangement of financing schemes • Financial guidance based on an intimate knowledge of local laws, regulations and tax procedures • Environmental studies • Licensing incl. basic / detail engineering • Utilities / offsites / infrastructure • Procurement / inspection / transportation services • Civil works and erection • Commissioning • Training of operating personnel using operator training simulator • Plant operation support / plant maintenance • Remote Performance Management (Teleservice) ThyssenKrupp Uhde’s policy is to ensure utmost quality in the implementation of its projects. We work worldwide to the same quality standard, certified according to: DIN / ISO 9001 / EN29001. We remain in contact with our customers even after pro- ject completion. Partnering is our byword. By organising and supporting technical symposia, we promote active communication between customers, li- censors, partners, operators and our specialists. This enables our customers to benefit from the development of new technologies and the exchange of experience as well as troubleshooting information. We like to cultivate our business relationships and learn more about the future goals of our customers. Our after- sales services include regular consultancy visits which keep the owner informed about the latest developments or revamping options. ThyssenKrupp Uhde stands for tailor-made concepts and international competence. For more information contact one of the ThyssenKrupp Uhde offices near you or visit our website: www.uhde.eu Further information on this subject can be found in the following brochures: • Oil Gas • Polymers 8. Services for our customers
  • 33. 33
  • 34. 34 Completion Customer Process Prod. Capacity Licensor or Plant Site Plant mtpy Know-how Morphylane® Extractive Distillation 2014 Refineria Del Pacifico Benzene 143,000 Uhde Manabi, Ecuador from Reformate 2014 Petrobras S.A. Benzene/Toluene 940,000 Uhde Rio de Janeiro, Brazil from Reformate 2013 Atyrau Refinery Benzene/Toluene 289,000 Uhde Kazakhstan from Reformate 2012 Sasol Technology Benzene from 106,000 Uhde Secunda, South Africa Coal tar nawphthta SCC Gasoline 2012 Rabigh Refining and Petrochemical Co. Benzene/Toluene 881,000 Uhde Rabigh, Saudi Arabia from Reformate 2012 Total Jerp Benzene 140,000 Uhde Al-Jubail, Saudi Arabia from Reformate 2011 Tianjin Binhai Tiansheng Coal Chemical Co. Benzene/Toluene/Xylenes 87,300 Uhde Tianjin, China from Coke Oven Light Oil 2011 S-Oil Corporation Benzene/Toluene 680,000 Uhde Ulsan, South Korea from Reformate 2011 Tabriz Oil Refining Co. Benzene 33,600 Uhde Tabriz, Iran from Reformate 2010 Xingtai Risun CoalChemical Company Benzene/Toluene/Xylenes 88,000 Uhde Xingtai, China from Coke Oven Light Oil 2010 Baosteel Chemical Co. Benzene/Toluene 80,800 Uhde Baoshan, China from Coke Oven Light Oil 2010 Tangshan Risun Chemical Company Benzene/Toluene/Xylenes 173,000 Uhde Tangshan, China from Coke Oven Light Oil 2010 Qatar Petroleum Benzene/Toluene 762,000 Uhde Qatar from Reformate 2010 Yunnan Dawei Group Co. Ltd. Benzene/Toluene/Xylenes 89,000 Uhde Yunwei, China from Coke Oven Light Oil 2010 Shell Eastern Petroleum Ltd. Benzene 210,000 Uhde Singapore from Pyrolysis Gasoline 2009 China Steel Chemical Corporation Benzene/Toluene 27,000 Uhde Kaohsiung, Taiwan from Coke Oven Light Oil 2009 Wuhan Iron and Steel Co. Ltd. Benzene/Toluene/Xylenes 94,000 Uhde Wuhan, China from Coke Oven Light Oil 2009 Xingtai Risun Coal Chemical Company Benzene/Toluene/Xylenes 88,000 Uhde Xingtai, China from Coke Oven Light Oil 2009 GCW Anshan IS Group Co. Benzene/Toluene/Xylenes 128,000 Uhde Anshan, China from Coke Oven Light Oil 2009 Oman Oil Company Benzene/Toluene 350,000 Uhde Sohar, Oman from Reformate 2008 Jiantao Chemical Co. Ltd. Benzene/Toluene/Xylenes 45,000 Uhde Hebei, China from Coke Oven Light Oil 2008 Yunnan Kungang IT Co. Ltd. Benzene/Toluene/Xylenes 44,000 Uhde Kunming, China from Coke Oven Light Oil 2007 Shanxi Sanwei Group Co. Ltd. Benzene/Toluene/Xylenes 178,000 Uhde Zhahocheng, China from Coke Oven Light Oil 2007 Sasol Benzene 100,000 Uhde Secunda, South Africa from Pyrolysis Gasoline 2007 Hood Oil Benzene 110,000 Uhde Sanaa, Yemen from Reformate 2007 Japan Energy Co. Benzene/Toluene 310,000 Uhde Kashima, Japan from Reformate 9. Main references Just a few of more than 100 reference plants in the last ten years
  • 35. 35 Completion Customer Process Feed Capacity Licensor or Plant Site Plant mtpy Know-how Reformate Hydrogenation 2002 Shell Nederland Chemie B.V. Selective Hydrogenation 850,000 Axens Moerdijk, Netherlands 2000 Tonen Corporation Selective Hydrogenation 320,000 BASF Kawasaki, Japan 2000 Saudi Chevron Petrochemical Selective Hydrogenation 860,000 BASF Al Jubail, Saudi Arabia Pyrolysis Gasoline Hydrogenation 2010 Shell Eastern Petroleum Ltd. First and Second Stage Hydrogenation 733,000 Axens Singapore 2005 CNOOC / Shell Petrochemicals Co. Ltd. Hydrogenation 800,000 Axens Huizhou, China 2005 BASF / Yangzi Petrochemical Co. Hydrogenation 600,000 BASF Nanjing, China of Pyrolysis Gasoline 2004 Bouali Sina Petrochemical Co. First Stage Hydrogenation 139,000 Axens Bandar Imam, Iran Second Stage Hydrogenation 106,000 2001 BASF/FINA First Stage Hydrogenation 795,000 BASF Port Arthur, Texas, USA Second Stage Hydrogenation 563,000 Coke Oven Light Oil Hydrorefining 2010 Xingtai Risun CoalChemical Company Hydrorefining 100,000 Uhde/BASF Xingtai, China 2010 Baosteel Chemical Co. Hydrorefining 100,000 Uhde/BASF Baoshan, China 2010 Tangshan Risun Chemical Co. Hydrorefining 200,000 Uhde/BASF Tangshan, China 2009 Yunnan Dawei Group Co. Ltd. Hydrorefining 100,000 Uhde/BASF Yunwei, China 2009 Wuhan Iron and Steel Co. Ltd. Hydrorefining 100,000 Uhde/BASF Wuhan, China 2009 Xingtai Risun Coal Chemical Co. Hydrorefining 100,000 Uhde/BASF Xingtai, China 2009 GCW Anshan IS Group Co. Hydrorefining 150,000 Uhde/BASF Anshan, China 2008 Jiantao Chemical Co. Ltd. Hydrorefining 50,000 Uhde/BASF Hebei, China 2008 Yunnan Kungang IT Co. Ltd. Hydrorefining 50,000 Uhde/BASF Kunming, China 2007 Shanxi Sanwei Group co. Ltd. Hydrorefining 200,000 Uhde/BASF Zhahocheng, China Divided Wall Column Distillation and Single-Column Morphylane® 2000 Saudi Chevron Petrochemical Divided Wall Column Distillation 140,000 BASF/Uhde Al Jubail, Saudi Arabia 1999 VEBA OEL AG Divided Wall Column Distillation 170,000 BASF/Uhde Münchsmünster, Germany 2004 Aral Aromatics GmbH Single-Column Morphylane® 28,000 Uhde Gelsenkirchen, Germany Toluene from Coke Oven Light Oil Isomerisation, Transalkylation, Adsorption 2004 Bouali Sina Petrochemical Co. p-Xylene Adsorption 428,000 Axens Bandar Imam, Iran 2004 Bouali Sina Petrochemical Co. Xylenes Isomerisation 1 970,000 Axens Bandar Imam, Iran 2004 Bouali Sina Petrochemical Co. Transalkylation 883,000 Sinopec Bandar Imam, Iran
  • 36. Thyssen Krupp Uhde GmbH Friedrich-Uhde-Strasse 15 · 44141 Dortmund · Germany Phone +49 231 547-0 · Fax +49 231 547-3032 www.uhde.eu RT645/150002/2012ThyssenKruppUhde/TKprintmedia/PrintedinGermany