ED-PR/WeD, 200 7-05 6th Petch em Feedstock Co nf Seite 1

ID149

Uhde GmbH
Division Edeleanu Refining Technologies

Pure Aromatics
Recovery from Coke
Oven Light Oil
(COLO)
Dorothe Weimer
6th Petchem Feedstock Asia/China Markets Conference,
May 2007, Shenzhen, China
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Aromatics
World aromatics demand

(Million Metric Tons/Year) 40 (Million Metric Tons/Year)

50
45 35
B enz ene le n es
40 30 Mixed Xy
35
25
30
25 20
Toluene nes
20 15 p-Xyle
15 10
10
5
5
0
0
97

99

01

03

05

07

09
97

99

01

05

07

09

19

19

20

20

20

20

20
00
19

19

20

20

20

20
2
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AROMATICS
Aromatics Supply by Sources

Coke HDA/TDP Reformate

Oven 22 % 33 %
Pyrolysis Light
Gasoline Oil
24 % 4% Coke
Oven
Light
Oil
6%
Reformate Pyrolysis
72 % Gasoline
39 %

World aromatics supply by source World benzene supply by source

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Aromatics
Feedstocks for Aromatics Recovery

% Hydrotreated Hydrotreated Reformate

coke oven light oil pyrolysis gasoline
Benzene 65 40 3
Toluene 18 20 13
Xylenes 6 4 18
Ethylbenzene 2 3 5
Higher aromatics 7 3 16
Total aromatics 98 70 55
Non aromatics 2 30 45
100 100 100
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Aromatics
Uhdes Market Share

Erected Plants 1992-2005

Uhde
55%
Lummus 2%
Axens 3%
Lurgi 3%

Others
4%

UOP
33%
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Uhde GmbH
Division Edeleanu Refining Technologies

Pure Aromatics
Recovery from Coke
Oven Light Oil
(COLO)
 ED-PR/WeD, 200 7-05 6th Petch em Feedstock Co nf Seite 7
ID14
9

Aromatics
Aromatics Recovery from Coke Oven Light Oil (COLO)
Non-Aromatics

Off-Gas (H2S, NH3, CH4, etc.) Benzene

Predistillation

B/T Splitter
COLO Feed Hydro- Extractive
Refining Unit Distillation
Unit

Hydrogen

Residue
Toluene
Xylenes Fract.

C8 Fraction

Mixed Xylenes

C9+ Fraction
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Uhde GmbH
Division Edeleanu Refining Technologies

Hydrorefining of
Coke Oven Light Oil
(COLO)
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Hydrotreating
Hydrorefining of Coke Oven Light Oil
Off-gas

Stage
evaporator
Pre-
reactor

Stabilizer
Main- column
reactor

HP
Separator
Make-up Coke oven Residue BTXS Fraction
hydrogen light oil
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Hydrotreating
Hydrorefining Proprietary Feed Evaporation Raw Benzole
Vapor + Hydrogen

Raw Benzole ~10%

8
~90%

Pre-Evaporator
Vaporizer
1

Mixing
Jet
Reactor-
Product

Hydrogen

Reactor-
Product Residue
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Hydrotreating
BASF Hydrorefining Catalyst
M8
M8- -21
21S3
S3
Application:
Application: Mainly
Mainlypre-treatment,
pre-treatment,i.e.
i.e.hydrogenation
hydrogenationofofunsaturated
unsaturatedcompounds
compounds
(diolefins,
(diolefins,styrene)
styrene)ofof cuts
cutsrich
richininaromatic
aromaticcompounds
compoundsoriginated
originated
from
fromcoke
cokeoven
ovenprocesses
processes
Composition:
Composition: NiO
NiO/ /MoO
MoO3 on
onalumina
aluminaoxide
oxidecarrier
carrier 3
Form
Form/ /Size:
Size: Extrudates,
Extrudates,approx.
approx.33mm
mmdiameter
diameter
Bulk
BulkDensity:
Density: approx.
approx.750
750kg/m
kg/m

M8
M8--12
12S3
S3
Application:
Application: Mainly
Mainlyhydro-refining,
hydro-refining,i.e.
i.e.desulphurization,
desulphurization,denitrification
denitrificationand
and
olefin
olefinsaturation
saturationofofaromatic
aromaticrich
richcuts
cutsfrom
fromcoke
cokeoven
ovenprocesses
processes
Composition:
Composition: CoO
CoO/ /MoO
MoO3 on
onalumina
aluminaoxide
oxidecarrier
carrier
3
Form
Form/ /Size:
Size: Extrudates,
Extrudates,approx.
approx.33mm
mmdiameter
diameter
Bulk
BulkDensity:
Density: approx.
approx.700
700kg/m
kg/m
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Hydrotreating
Hydrorefining Typical Plot Arrangement
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Aromatics
Hydrorefining: Summary of process features

High quality,
High quality, desulfurized
desulfurized products
products BTX
BTX andand C9
C9
Simple plant
Simple plant arrangement
arrangement at at minimum
minimum space
space
High on-stream
High on-stream time time due
due to
to good
good operability
operability
No additional
No additional chemicals
chemicals needed
needed (anti
(anti polymer,
polymer,
anti corrosion,
anti corrosion, anti
anti foam)
foam)
Limited utilities
Limited utilities (e.g.
(e.g. no
no chilled
chilled water)
water)
Lowinvestment
Low investment and and low
low operating
operating costs
costs
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Uhde GmbH
Division Edeleanu Refining Technologies

MORPHYLANE
Extractive Distillation
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Aromatics
MORPHYLANE Extractive Distillation

Non-aromatics

Aromatics fraction Extractive

distillation Pure Aromatics
column

Stripper
column
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Aromatics
Properties of the MORPHYLANE Solvent NFM
N-Formylmorpholine CH2 CH2 H
4-Formylmorpholine O N C
4-Morpholinecarboxyaldehyde CH2 CH2 O
Formylmorpholid
Structure

Spec. heat:
at 20 C = 0.42 cal/g C Mol. wt.: 115
at 50 C = 0.44 cal/g C Bp.: 243 C at 14.7 psi
at 100 C = 0.48 cal/g C Melt point: 23 C
at 150 C = 0.53 cal/g C Density at 20 C: 1153 kg/m3
Vaporisation heat at Bp. Flash point (Pensky-Martens): 125 C
14.7 psi: 106 kcal/kg Ignition point: 370 C

Refractive index n25

D : 1.484
pH-Value when mixed with water 1:1 = 8.6
Viscosity at 30 C: 6.68 cP; 5.85 cSt

Miscible with benzene at any ratio

Miscible with water at any ratio

No azeotropes with C 6 - C 9 - hydrocarbons

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Aromatics
Boiling Temperature at 1 bar

Pure Component 15mol% Component

+ 85mol% Solvent
C C
Aromatics
Benzene C6H6 80.15 135.46
Toluene C7H8 110.64 160.70

Naphthenes
Cyclohexane C6H12 80.74 88.04
Methylcyclohexane C7H14 100.95 107.51
Tr-1, 2 Dimethylcyclopentane C7H14 91.85 98.60
Cis-1, 4 Dimethylcyclohexane C8H16 124.33 130.27
Paraffines
n-Heptane C7H16 98.45 103.69
n-Octane C8H18 125.65 132.46
2-Methylheptane C8H18 117.65 124.48
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Aromatics
MORPHYLANE Solvent Features

High solvent
High solvent selectivity
selectivity and
and efficiency
efficiency
High thermal
High thermal and
and chemical
chemical stability
stability
No corrosive
No corrosive effect
effect
No fouling
No fouling and
and foaming
foaming effect
effect
Minimal solvent
Minimal solvent losses
losses
Negligible solvent
Negligible solvent regeneration
regeneration expenditure
expenditure
No chemical
No chemical agents
agents required
required
Lowsolvent
Low solvent inventory
inventory
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Aromatics
MORPHYLANE Process Features (I)

Lownumber
Low number ofof equipment,
equipment, all all carbon
carbon steel
steel
Simple plant
Simple plant arrangement
arrangement at at minimum
minimum space
space
High on-stream
High on-stream time
time
Proven technology
Proven technology forfor all
all feedstocks
feedstocks
Highest aromatics
Highest aromatics purity
purity and
and yield
yield
Lowinvestment
Low investment and
and low
low operating
operating costs
costs
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Aromatics
MORPHYLANE Process Features (II)

Benzene purity
Benzene purity of
of >> 99.95
99.95 wt.-%
wt.-% possible
possible
Toluene purity
Toluene purity TDI
TDI grade
grade possible
possible
Aromatics yield
Aromatics yield usually
usually between
between 98 98 -- 99
99 wt.-%
wt.-%
Solvent consumption
Solvent consumption << 10 10 gram/ton
gram/ton ED ED feed
feed
Lowenergy
Low energy consumption
consumption
Basic nitrogen
Basic nitrogen guaranteed
guaranteed in in pure
pure aromatics
aromatics
On-stream time
On-stream time 8,600 hours/year 1)1)possible
8,600 hours/year possible
Hydro-Refining plants
Hydro-Refining plants usually
usually with
with 8000
8000 hours/year
hours/year
1)Calculation
1) Calculationbased
basedon
onMORPHYLANE
MORPHYLANEplant plantevaluation
evaluationat
atBASF
BASFAG,
AG,
DOWChemical,
DOW Chemical,Chevron-Phillips
Chevron-Phillipsand
andShell
Shell&&DEA
DEAOil
Oil
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Aromatics
MORPHYLANE typical Plot Arrangement
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Aromatics
Economics of Plant Capacity for COLO Processing

Typical
Typicalcapacities
capacitiesfor
forCoke
CokeOven
OvenLight
LightOil
Oil(COLO)
(COLO)plants
plants
between
between30.000
30.000tpa
tpaand
and200.000
200.000tpa
tpa

For
Forthis
thiskind
kindof
ofplant,
plant,economics
economicsof
ofplant
plantcapacity
capacityis
isof
ofmajor
major
impact
impact

Advantages
Advantagesin:
in: specific
specificTIC
TIC higher
higherNPV
NPV
specific
specificProduct
Productcost
cost shorter
shorterpay
payout
out
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Aromatics
Economics of Plant Capacity for COLO Processing

120%

Specific Product Cost per ton

Conversion
Conversioncost costincluding
including
depreciation 100%
depreciation


Identical
Identicalfeed feedcomposition
composition 80%
assumed
assumed 60%


Comparable
Comparableplant plantconcept
concept
(COLO 40%
(COLOHydrogenation
Hydrogenationand and
BTX
BTXRecovery)
Recovery) 20%


TIC
TICincludes
includesall allequipment,
equipment, 0%
first
firstfill
fillof
ofcatalyst
catalyst&&solvent,
solvent, 80,000 150,000 200,000
licence
licence&&engineering
engineeringfee,fee, Feed [tpa]
civil,
civil,steel
steelstructure
structureandand
construction
construction Consumption Materials Labour Cost
Utilty cost Maintenance
Depreciation
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Aromatics
Economics of Plant Capacity for COLO Processing

CONCLUSION:
CONCLUSION:


Requirements
Requirementsfor
forequity
equityis
isminimized
minimized

Cost
Costadvantages
advantagesfor
forend
endproducts
productsBenzene,
Benzene,Toluene
Tolueneand
and
Xylenes
Xylenesup
upto
to30%
30%

even
evenunder
underconsideration
considerationofoftransportation
transportationcost
costaa
centralised
centralisedlarge
largeplant
plantfor
forprocessing
processingCOLO
COLOis ismore
moreviable
viable
compared
comparedto toseveral
severalsmaller
smallerplants
plants

TIC
TICfor
foreach
eachparty
partyinvolved
involvedis
isreduced
reducedfor
forone
onelarger
largerplant
plant
compared
comparedwith
withthe
theTIC
TICto
tobe
bespent
spentfor
forseparately
separatelyowned
owned
smaller
smallerplants
plants
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Uhde GmbH
Division Edeleanu Refining Technologies

References
 ED-PR/WeD, 200 7-05 6th Petch em Feedstock Co nf Seite 26

Aromatics
MORPHYLANE References (last 10 years)
Start- Company Feed Process Aromatics Licensor Contract
Up Plant Site Process Data Capacity [t/y] Project Notes
2009 JERP - Reformate Benzene 140,300 Uhde E (in cooperation
Jubail Export Refinery Project MORPHYLANE with Axens)
Jubail (Saudi Arabia)
2009 Xingtai Risun Coke Oven Light Oil Benzene 74,400 Uhde E, P
Coal&Chemical LTD MORPHYLANE Toluene 11,200
Yanjiatun (Xingtai), Xylenes 1,800
P.R. China
2009 Jiantao Chemical Co., Ltd. Coke Oven Light Oil Benzene 38,500 Uhde E, P
Jiantao (Hebei), MORPHYLANE Toluene 5,800
P.R. China Xylenes 1,100
2008 Yunnan Kungang IT Co., Ltd. Coke Oven Light Oil Benzene 35,000 Uhde E, P
Kunming, P.R. China MORPHYLANE Toluene 7,000
Xylenes 2,000
2008 GCW Anshan I&S Group Co. Coke Oven Light Oil Benzene 100,000 Uhde E, P
Anshan, P.R. China MORPHYLANE Toluene 20,000
Xylenes 8,000
2007 Sasol Pyrolysis Gasoline Benzene 100,000 Uhde E
South Africa MORPHYLANE
2007 HoodOil Reformate Benzene 110,000 Uhde E (in cooperation
Yemen MORPHYLANE with Axens)
2007 Shell Eastern Pyrolysis Gasoline Benzene 210,000 Uhde E (in cooperation
Singapore MORPHYLANE with Axens)
2007 Japan Energy Corporation Reformate Benzene/ 310,000 Uhde E (in cooperation
Japan MORPHYLANE Toluene with Axens)
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Aromatics
MORPHYLANE References (last 10 years)
Start- Company Feed Process Aromatics Licensor Contract
Up Plant Site Process Data Capacity [t/y] Project Notes
2007 Oman Oil Company Reformate Benzene/ 350,000 Uhde E (in cooperation
Sohar, Oman MORPHYLANE Toluene with Axens)
2006 Baosteel International Coke Oven Light Oil Benzene 56,000 Uhde E
Taiyuan, P.R. China MORPHYLANE Toluene 12,000
2006 Repsol S.A. Reformate and Benzene 221,000 Uhde E (in cooperation
Tarragona, Spain Pyrolysis Gasoline with Axens)
MORPHYLANE
2005 Copesul Companhia Petro- Pyrolysis Gasoline Benzene 140,000 Uhde E (Expansion)
quimica do Sul MORPHYLANE
Triunfo. Brazil
2006 Shanxi Sanwei Group Co., Ltd. Coke Oven Light Oil Benzene 129,000 Uhde E, P
Zhaocheng, P.R. China MORPHYLANE Toluene 35,000
Xylenes 14,000
2006 CEPSA S.A. Reformate Benzene 352,000 Uhde E
Huelva, Spain MORPHYLANE Toluene 79,000
2006 SK Corp. Reformate Benzene 95,000 Uhde E (in cooperation
Ulsan, Korea MORPHYLANE Toluene 374,000 with Axens)
2005 CNOOC / Shell Petrochemicals Pyrolysis Gasoline Benzene 250,000 Uhde E
Company Ltd. MORPHYLANE
Huizhou, P.R. China
2005 Borzouyeh Petrochemical Reformate Benzene/ 630,000 Uhde E (in cooperation
Company MORPHYLANE Toluene
Bandar Assaluyeh, Iran
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Aromatics
MORPHYLANE References (last 10 years)
Start- Company Feed Process Aromatics Licensor Contract
Up Plant Site Process Data Capacity [t/y] Project Notes
2005 PKN Orlen Reformate and Benzene/ 400,000 Uhde E
Plock, Poland Pyrolysis Gasoline Toluene
MORPHYLANE
2004 Aral Aromatics Coke Oven Light Oil Toluene 28,000 Uhde E
Gelsenkirchen, Germany MORPHYLANE
2003 Bouali Sina Petrochemical Reformate and Benzene/ 320,000 Uhde E (in cooperation
Company
Bandar Imam, Iran Pyrolysis Gasoline Toluene with Axens)
MORPHYLANE
2003 Holborn Erdoel Raffinerie Reformate Benzene 67,000 Uhde E (in cooperation
Hamburg, Germany MORPHYLANE with Axens)
2002 Shanghai Petrochemical Pyrolysis gasoline Benzene/ 320,000 Uhde E (Expansion in
Company MORPHYLANE Toluene cooperation with
SJEC)
Jinshanwei, P.R. China Expansion
2002 Shell Nederland Chemie Reformate Benzene 550,000 Uhde E
Moerdijk, Netherlands MORPHYLANE
2001 BASF/FINA Pyrolysis Gasoline Benzene/ 280,000 Uhde E
Port Arthur, TX, USA MORPHYLANE Toluene
2000 BASF Antwerpen N.V. Pyrolysis Gasoline Benzene 258,000 Uhde Turn-key
Antwerp, Belgium MORPHYLANE
2000 Tonen Corp. Reformate Benzene 100,000 Uhde E
Kawasaki, Japan MORPHYLANE
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Aromatics
MORPHYLANE References (last 10 years)
Start- Company Feed Process Aromatics Licensor Contract
Up Plant Site Process Data Capacity [t/y] Project Notes
2000 Saudi Chevron Petrochemical Reformate Benzene/ 697,000 Uhde E
Al Jubail. Saudi Arabia MORPHYLANE Toluene
2000 Titan Petrochemicals Pyrolysis Gasoline Benzene/ 168,000 Uhde Turn-key
Pasir Gudang, Malaysia MORPHYLANE Toluene
1999 DEA Mineraloel AG Reformate Benzene 43,200 Uhde E
Wesseling, Germany MORPHYLANE
1999 Thai Petrochemical Industries Pyrolysis Gasoline Benzene 168,000 Uhde E
MORPHYLANE
Rayong, Thailand
1999 Rayong Olefins Co. Pyrolysis Gasoline Benzene 124,500 Uhde E, P
Rayong, Thailand MORPHYLANE Toluene 12,000
1999 Copesul Companhia Petro- Pyrolysis Gasoline Benzene 88,500 Uhde E
quimica do Sul MORPHYLANE
Triunfo, Brazil
1999 Fina Raffinaderij Antwerp Pyrolysis Gasoline Benzene 250,000 Uhde E
Antwerp, Belgium MORPHYLANE
1999 VFT n. V. Coke oven light oil Benzene 64,000 Uhde E
Zelzate, Belgium MORPHYLANE
1999 Shanghai Petrochemical Pyrolysis gasoline Benzene/ 227,000 Uhde E
Company MORPHYLANE Toluene
Shanghai, P.R. China
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Aromatics
MORPHYLANE References

Customer:
Customer: BASF
BASF
Location:
Location: Antwerp
Antwerp // Belgium
Belgium
Capacity:
Capacity: 258,000
258,000 t/year of
t/year of benzene
benzene
Process:
Process: BASF SELOP + MORPHYLANE
BASF SELOP + MORPHYLANE
Commissioning:
Commissioning: 2000
2000
Speciality:
Speciality: Turnkey
Turnkey