steam cracking of renewable naphtha
DESCRIPTION
Tests show that olefin plants (steam crackers) can diversify to biorenewable feeds without modifying their facilities or operations. And by doing this, they will help "sequester" CO2 into plastics.TRANSCRIPT
1http://www.lct.ugent.be
1 Laboratory for Chemical Technology, Universiteit Gent2 Syntroleum Corp., Tulsa, OK, [email protected]
Steam Cracking of Renewable Naphtha
Kevin M. Van Geem 1, Ramin Abhari 2, Steven P. Pyl
1, Marie-Françoise Reyniers 1 and Guy B. Marin 1
Ethylene Producers ConferenceMarch 22-25, 2010, San Antonio, TX, USA
1st dimension retention time (min)0 5025
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
2
1st dimension retention time (min)0 105
sign
al in
tens
ity (m
V)
modulatednotmodulated
paraffins
(a) (b)
methane
propene
1.3-butadiene
ethene
indene
naphthalene
benzene
methyl-naphthalenes
styrene
toluene
• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Commercialization Status
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
2
• Biomass to hydrocarbons– Gasification+FT (“BTL”) and enzyme routes not commercial– Hydrotreated Vegetable Oil (e.g. Bio-Synfining™)
commercialized• Economics based on diesel and jet fuel• Naphtha co-product tested as feedstock for conventional
steam crackers
Feedstock
ProcessDiesel, Jet, Naphtha
IntroductionEPC, San Atonio, TX, 22/03/2010
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Brown grease
Seed oils
Yellow grease
Waste animal fats
Seaweed oils
Tall oil fatty acid
Algal oils
Bio-Synfining™ Feedstocks
U.S. sources ~ 360,000 BPD (16 million tonne/y) hydrocarbon equivalent …and increasing
EPC, San Atonio, TX, 22/03/2010
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• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
5
ChemistryO
O
O
O
O
OHC
+ 6 H2O + C3H8
+ 15 H2
3 (1a)
(n-octadecane)
(typical triglyceride with linoleic, oleic, and stearic acids)
H2C
H2C
HO
O
+ 4 H2
+ 2 H2O (1b)
NiMo cat
(isoparaffinic hydrocarbons)
NiMo cat
Bi-functionalcatalyst
(2)(typical)
+ + H2
Paraffinic hydrocarbons from bio oils via hydrodeoxygenation (Eqs 1a-b) and hydrocracking (Eq 2)
EPC, San Atonio, TX, 22/03/2010
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Process
FEED
JET
Hydro-deoxygenator
Hydrocracker
Water
C5-C9
C10-C15
C15-C18+
C3-C18+
RecycleCompressor
LPG
Naphtha
C3-C4
Fractionation
HydrogenMakeup
Simple, low capital cost process
EPC, San Atonio, TX, 22/03/2010
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Feed pretreatment
FG
FG
ISO Container #1 ISO Container #2
50 psig N2 Supply
Backwash Pulse Tank
Water/Acid Soln Tote
Filter Cartridge
Backwash Collection
Drum
Sample Port
Sample Port
PG PG
PG
DP
Check valve
Makeup of Bio Oil for Renewable Naphtha Test Component Amount (wt %)
Poultry Fat 46 Yellow Grease 18 Brown Grease 18 Floatation Grease 9 Grease from Prepared Foods 9
EPC, San Atonio, TX, 22/03/2010
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Acid wash removes 95% of solubilized metals and phosphorus
Contaminants in Bio Oil Blend Before and After Pretreatment
Before After
Ash (ppm wt) 1675 67.2 Nitrogen (ppm wt) 920 1006 Sulfur (ppm wt) 69 111 Acid Value (mg KOH/g) 94.7 129 ICP-AES Analysis Calcium (ppm wt) 285 14.5 Iron (ppm wt) 67.3 6.57 Potassium (ppm wt) 117 3 Magnesium (ppm wt) 7.6 0.532 Sodium (ppm wt) 123 6.79 Phosphorus (ppm wt) 144 8.28
Feed pretreatmentEPC, San Atonio, TX, 22/03/2010
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Stable catalyst: activity/selectivity
HydrodeoxygenationEPC, San Atonio, TX, 22/03/2010
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Hydrocracker distillate consistent – jet fuel flash point dictates naphtha end point
Hydrocracker product yields: JETEPC, San Atonio, TX, 22/03/2010
11
• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Commercialization Status
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
12
Feedstock analysis
GCGC set-upEPC, San Atonio, TX, 22/03/2010
13
OVEN
FID
tof-MS
He
Rtx-1 PONA
BPX-50
BPX-50
injector
modulator
4-port 2-way valve
Liq. CO2 in
valves
jets
2nd dim. column1st dim. column
2nd dim. column1st dim. column
coolingcarrier gas
cooling
cooling
Tof-MS
FID
1st dimension retention time (min)10 5030
2nd
dim
ensi
on re
tent
ion
time
(s)
0
4
C9
C16
Di-aromatics
naphthenesDi-naphthenes
Mono-aromatics
Naphtheno-aromatics
paraffins
GCGC analysis renewable naphthaEPC, San Atonio, TX, 22/03/2010
14Separation based on boiling point
Sepa
ratio
n ba
sed
on p
olar
ity
Offline renewable naphtha analysis: Tof-MS
EPC, San Atonio, TX, 22/03/2010
15
Group type separationEPC, San Atonio, TX, 22/03/2010
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C9
e: di-naphthenesf: (iso)paraffinsg: mono-naphthenes
n and isoparaffins
aromatics
naphthenes
Group type separation by selecting specific ions in the Tof-MS chromatogram
Visualusation of ppb amounts of components
1st dimension retention time (min)10 5030
2nd
dim
ensi
on re
tent
ion
time
(s)
0
4
C9
C16
Di-aromatics
naphthenesDi-naphthenes
Mono-aromatics
Naphtheno-aromatics
paraffins
Group type separation: no oxygenatesEPC, San Atonio, TX, 22/03/2010
17Separation based on boiling point
Sepa
ratio
n ba
sed
on p
olar
ity
Detailed PIONAEPC, San Atonio, TX, 22/03/2010
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C9
Identification of over 300 different individual components Quantification in to 300 components
P I O N A SUM3 0.17 0.00 0.00 0.00 0.00 0.174 1.45 0.93 0.00 0.00 0.00 2.385 4.41 4.77 0.00 0.00 0.00 9.186 7.49 9.57 0.00 1.02 0.00 18.077 7.66 12.38 0.00 1.34 0.10 21.498 5.39 10.72 0.02 1.64 0.29 18.069 3.13 10.34 0.25 1.64 0.32 15.67
10 1.19 6.27 0.06 0.60 0.09 8.2111 0.24 2.09 0.00 0.04 0.00 2.3812 0.06 0.56 0.00 0.00 0.00 0.6213 0.04 0.17 0.00 0.00 0.00 0.2014 0.03 0.07 0.00 0.00 0.00 0.1115 0.69 0.14 0.00 0.00 0.00 0.8316 0.68 0.31 0.00 0.00 0.00 0.9917 0.34 0.55 0.00 0.00 0.00 0.8918 0.17 0.60 0.00 0.00 0.00 0.77
SUM 33.14 59.46 0.33 6.28 0.80 100.00
• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Commercialization Status
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
19
Pilot plant test
Pilot plant set-upEPC, San Atonio, TX, 22/03/2010
20
Pilot plant set-upEPC, San Atonio, TX, 22/03/2010
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cell 1 cell 2 cell 3 cell 4 cell 5 cell 6 cell 7
air
oil
N2
flare
DHA
FURNACE & REACTOR TLE ANALYSIS
H2O
hydr
ocar
bons
FEED
IR-GA
preheating & mixing reactor zone
P P P PP
condensate
cool
er
GC×GC
RGAPGA
water
oven
Nitrogen is used as internal standard
Methane functions as a second internal standard
Pilot plant set-upEPC, San Atonio, TX, 22/03/2010
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RGA (TCD)
RGA (FID)
PGA (TCD)
DHA (FID)
GC×GC (FID)
H2 CO2 C2H4 C2H6 C2H2 CH4 CON2
C2 C3 C4CH4
CO2 C2H4 C2H6 C2H2 CO CH4
C2 C3 C4CH4 C5 C6 ...
N2
...CH4
chec
k
C16
C25
Pilot plant set-upEPC, San Atonio, TX, 22/03/2010
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Heated transfer lineto GCGC
Online GCGC Tof-MS chromatogram EPC, San Atonio, TX, 22/03/2010
24
1st dimension retention time (min)0 5025
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
2
1st dimension retention time (min)0 105
sign
al in
tens
ity (m
V)
modulatednotmodulated
paraffins
(a) (b)
methane
propene
1.3-butadiene
ethene
indene
naphthalene
benzene
methyl-naphthalenes
styrene
toluene
Division of GCGC chromatogram in a 1-dimensional and 2-dimensional part
Online GCGC Tof-MS chromatogram EPC, San Atonio, TX, 22/03/2010
251st dimension retention time (min)40 6050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
1st dimension retention time (min)60 8070
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
(c) (d)
1st dimension retention time (min)20 8050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
1st dimension retention time (min)20 5035
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
indene
naphthalene
acenapthylene
phenanthrene/anthracene
(a) (b)
pyrene
benzene
toluene
C2-BzC3-Bz C4-Bz C5-Bz
styrenevinyltolune
vinylstyrene
phenanthrene
anthracene
C1-triaroC2-triaro
naphthalene
2-methyl-naphthalene
1-methyl-naphthalene
C2-Nph C3-Nph
ethylbenzenen-propylbenzene
toluenealkyl-benzenes
benzene
biphenyl
methyl-biphenyl
ethenyl-naphthalene
(iso)-propenyl-
Nph
1st dimension retention time (min)40 6050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
1st dimension retention time (min)60 8070
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
(c) (d)
1st dimension retention time (min)20 8050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
1st dimension retention time (min)20 5035
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
indene
naphthalene
acenapthylene
phenanthrene/anthracene
(a) (b)
pyrene
benzene
toluene
C2-BzC3-Bz C4-Bz C5-Bz
styrenevinyltolune
vinylstyrene
phenanthrene
anthracene
C1-triaroC2-triaro
naphthalene
2-methyl-naphthalene
1-methyl-naphthalene
C2-Nph C3-Nph
ethylbenzenen-propylbenzene
toluenealkyl-benzenes
benzene
biphenyl
methyl-biphenyl
ethenyl-naphthalene
(iso)-propenyl-
Nph
Online GCGC FID chromatogram EPC, San Atonio, TX, 22/03/2010
26
1st dimension retention time (min)20 8050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
1st dimension retention time (min)20 8050
2nd
dim
ensi
on re
tent
ion
time
(s)
0
5
(a) (b)
indene
naphthalene
acenapthylene
phenanthrene
pyrenetoluenealkyl-benzenes
benzene
indene
naphthalene
acenapthylene
phenanthrene
pyrenetoluenealkyl-benzenes
benzeneethyl-Bz ethyl-Bz
nC14nC10
Reduced peak overlap when using GCGC allows more accurate quantification
COT = 820°C COT = 865°C
Detailed effluent with GCGC FIDEPC, San Atonio, TX, 22/03/2010
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Over 100 components are identified and quantified each run Product Yield (wt%) COT = 820°C COT = 835°C COT = 850°C COT = 865°C
hydrogen 0.71 0.80 0.88 0.96 CO 0.32 0.32 0.23 0.18 CO2 0.15 0.03 0.07 0.03 methane 13.55 15.28 16.28 17.67 ethylene 27.26 29.87 30.85 32.02 ethane 4.22 4.19 4.16 4.09 propylene 19.51 18.85 17.59 16.39 propane 0.72 0.66 0.60 0.54 isobutene 3.96 3.60 3.09 2.60 Trans 2-butene 3.16 2.40 1.73 1.13 Cis 2-butene 0.85 0.65 0.53 0.41 1-butene 0.61 0.50 0.57 0.47 1,3-butadiene 5.80 5.33 5.42 5.13 n-butane 0.49 0.34 0.27 0.18 benzene 3.18 4.42 5.58 6.02 toluene 1.62 2.05 2.08 2.46 Et-benzene 0.18 0.21 0.20 0.18 m-xylene 0.24 0.26 0.24 0.26 p-xylene 0.10 0.10 0.05 0.13 styrene 0.30 0.46 0.59 0.73 o-xylene 0.11 0.12 0.12 0.13 indene 0.11 0.21 0.25 0.31 naphthalene 0.15 0.23 0.32 0.43
Simulated trends with COILSIM1DEPC, San Atonio, TX, 22/03/2010
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0
5
10
15
20
25
30
35
10 11 12 13 14 15 16 17 18
Yie
ld (
wt%
)
Methane Yield (wt%)
ethylene propylene 1,3-butadiene 1-butene benzene pygas fuel oil
Pilot plant coking runEPC, San Atonio, TX, 22/03/2010
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FeedRenewable Naphtha
+ 100 ppm DMDSRenewable Naphtha
Time on stream 1h 5h 1h 5hConditions
HC-flow (kg/hr) 4.008 3.990 4.008 3.996H2O-flow (kg/hr) 1.764 1.812 1.728 1.800Dilution (kg/kg) 0.440 0.454 0.431 0.450COT (°C) 850 850 850 850COP (bar abs) 1.64 1.69 1.67 1.66
hydrogen 0.88 0.87 0.93 0.89CO 0.05 0.06 0.30 0.12CO2 0.00 0.00 0.04 0.01methane 15.99 16.10 16.39 16.48ethylene 31.21 31.20 30.90 31.13ethane 4.11 4.29 4.23 4.21propylene 18.27 18.34 17.52 17.631-butene 1.78 1.76 1.66 1.591,3-butadiene 5.70 5.61 5.13 5.35benzene 5.38 5.46 5.58 5.60toluene 2.18 2.28 2.38 2.24styrene 0.64 0.61 0.56 0.45naphthalene 0.38 0.39 0.29 0.40
Measured coke yieldsEPC, San Atonio, TX, 22/03/2010
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0
1
2
3
4
5
6
7
8
RenewableNaphtha
Renewable Naphtha + 100ppm DMDS
Ethane Petroleum
Naphtha
Condensate
g c
oke/
3600
s
Run length simulationEPC, San Atonio, TX, 22/03/2010
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TLEinlet inlet
Reactor coil Type Number of reactors Number of passes Reactor length Internal reactor diameter (passes 1-4) External reactor diameter (passes 1-4) Internal reactor diameter (passes 5-6) External reactor diameter (passes 5-6) Wall thickness Naphtha flow rate per reactor coil Steam dilution CIT (a) COP (b)
GK I Split coil 8 6 53.89 m 0.080 m 0.096 m 0.114 m 0.130 m 0.008 m 2785 kg h-1
0.70 kg/kg 620 °C 1.45 105 Pa
Feedstock characteristics PINA analysis (wt%) n-praffins isoparaffins naphthenes aromatics ASTM D86 BP (wt%) IBP 50% FBP Specific density
37.0 wt% 33.0 wt% 18.0 wt% 12.0 wt%
36.0 94.5 161.0 0.706
Outlet specification Ethylene yield 28.6 wt%
Simulated run length with COILSIM1D
EPC, San Atonio, TX, 22/03/2010
32
740
790
840
890
940
990
1040
1090
1140
0 10 20 30 40 50 60
Exte
rnal
wal
l tem
pera
ture
(°C)
Axial Position (m)
0 h
1000 h
2000 h
3000 h
3800 h
Simulated Run length : Renewable Naphtha 158 days Fossil based Naphtha 83 days (Industrial 85 days)
• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Commercialization Status
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
33
Commercialization statusEPC, San Atonio, TX, 22/03/2010
• 75 million gal/y plant in Geismar, LA• Renewable naphtha 10% of output
34
• Introduction
• Bio-Synfining process
• Steam cracking of renewable naphtha
• Commercialization Status
• Conclusions
OutlineEPC, San Atonio, TX, 22/03/2010
35
Process to convert bio oils to hydrocarbons commercialized
Renewable naphtha major co-product
Excellent feedstock for conventional steam crackers
High ethylene and propylene yields
Low coking tendency = long run lengths
Opportunity for petrochemical producers to transition to biorenewable
feeds without modifying process
Reduced carbon footprint for olefin plants
ConclusionsEPC, San Atonio, TX, 22/03/2010
36
37
Thank you for your attention!
GCGC: Optimization Offline analysisEPC, San Atonio, TX, 22/03/2010
38
Detector FID, 300°C Tof-MS, 35-400 amu
Injection 0.2 μl, split flow 150 ml/min, 250°C
First columnRtx-1 PONAa
50 m L × 0.25 mm I.D. × 0.5 μm df
Second columnBPX-50b
2 m L × 0.15 mm I.D. × 0.15 μm df
Oven temperature 50°C 250°C at 3°C/min
Modulation Period 4 s
Carrier gasHe, constant flow
2.1 ml/minHe, constant flow
1.6 ml/min
a dimethyl polysiloxane (Restek); b 50% phenyl polysilphenylene-siloxane (SGE)
Other GC’sEPC, San Atonio, TX, 22/03/2010
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PGA DHAInjection Gas injection, 55°C Gas injection, 250°C
Carrier gas He He
Pre-column Hayesep N (2 m L × 1/8” I.D.) -
ColumnCarbosphere
(1.8 m L × 1/8” I.D.)Rtx-1 PONAa
(50 m L × 0.2 mm I.D. × 0.55 μm df)
Oven temperature 55°C -40°C 40°C (5°C/min) 90°C (3°C/min) 250°C (5°C/min)
Detector TCD, 160°C FID, 250°C
a dimethyl polysiloxane (Restek)
Other GC’sEPC, San Atonio, TX, 22/03/2010
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RGAChannel 1 Channel 2 Channel 3
Injection Gas injection, 80°C Gas injection, 80°C Gas injection, 80°CCarrier gas He He N2
Pre-columnRtx-1a
(15 m L × 0.53 mm I.D. × 3 μm df)
Hayesep Q(0.25 m L × 1/8” I.D.)
Hayesep T(1 m L × 1/8” I.D.)
ColumnRt-Alumina BONDb
(25 m L × 0.53 mm I.D. × 15 μm df)
Hayesep N (1 m L× 1/8” I.D.),
Molsieve 5A (1 m L × 1/8” I.D.)
Carbosphere(2 m L × 1/8” I.D.)
Oven temperature 50 120°C at 5°C/min 80°C 80°C
Detector FID, 200°C TCD, 160°C TCD, 160°C
a dimethyl polysiloxane (Restek); b Al2O3/KCl (Restek)