GTC Technology
Naphtha Valorization to its Highest Value
Presented at IOCL Petrochemical Conclave by
Joseph C. Gentry – Director, Global Licensing
February 12, 2015
Petrochemicals Have Higher Value
•
•
•
Component
Refiners have opportunity to upgrade
naphtha into higher-value blendstock
or petrochemicals
By-product naphtha from cracking
processes have great potential for
upgradation
Molecule management is the key to
understanding the best method to
process the naphtha
CH3
Value Relative to Naphtha
(Average Estimates)
Naphtha
1.00
Unleaded Gasoline
1.15
Toluene
1.20
Mixed Xylenes
1.25
Ethylene
1.50
Benzene
1.50
Paraxylene
1.55
Propylene
1.55
Styrene
1.70
Isoprene
2.10
C5/C9 HCR
2.5-3.00
CH3
CH3
Benzene Toluene
Mixed Xylene
Propylene
Styrene
DCPD
Isoprene
Naphthalene
Conventional Refinery Naphtha Utilization
Typical disposition
Straight Run
(Paraffins)
Thermal or
Catalytic Cracked
(Olefins)
Cracking, Isomerization,
Reforming
Fuels or Gasoline
Page 3
Technology Options for Straight Run Gasoline
n-C4
Light Naphtha
C7 Paraffins
Heavy Naphtha
Isomalk-3
Isomalk-2
Isomalk-4
Semi-Regenerative
Reforming
i-C4
C5/C6 Isomerate and
Food Grade Hexane
C7 Isomerate
Reformate
Page 4
C5/C6 Isomerisation: Technology Choices
Three light gasoline isomerization processes

Zeolite catalysts
– High operating temperature
– Less favorable for formation of high-branched isomers

Chlorinated aluminum oxide catalysts
– Reasonable octane increase
– Regular organochloride additions required
– Spent caustic disposal also required
– Extreme measures for H20 and impurity removal

SI-2 Mixed metal oxide catalysts
– Advantages over chlorinated aluminum and zeolite,
with none of the disadvantages
Technology
Performance
Robust Operation
Environment
Zeolite
Chlorinated Alumunim
Isomalk-2SM
Page 5
Case study, World-Scale Grass-Root
Isomalk-2SM Unit.
Process scheme
Capacity, t/y
Full Recycle Scheme (DIP, DIH, DP)
1.0 MMTA
Isomerate yield, %
99
i-Pentane cut, RON
92.0-93.0
Light Isomerate, RON
91.5-92.5
Space velocity in the reactor block, hour-1
Start-up year
2.0 -2.5
November, 2010
First World-Scale isomerization unit to use non-chlorinated catalyst
and achieve 92.5 RON for final isomerate
Typical BFD for Processing
Light and Heavy Naphtha
Hydrocarbon Gas
IBP - 800С
(С7 < 2%)
25%
Fractionation
Column
Isomerization Unit
Aromatics: 0%
ISOMERATE
Yield: 97%
RON 90
24.2%
Blending
Section
RON 94.4
Feed
Hydrotreatment
Unit
IBP - 1800С
Benzene: 1.4%
Aromatics: 42.7%
100%
Yield: 86%
Hydrogen Gas
Reforming Unit
80 -
1800С
(С6 < 0.5%)
Benzene: 2%
Aromatics: 7%
REFORMATE
Yield: 88%
RON 100
60%
75%
Hydrocarbon Gas
Page 7
BFD for naphtha processing with C7
isomerization technology available
Hydrocarbon Gas
IBP - 700С
(С7 < 1%)
Fractionation
Column
23%
Isomerization Unit
Aromatics: 0%
ISOMERATE
Yield: 98%
RON 91
22.5%
Blending
Section
Hydrocarbon Gas
Feed
Hydrotreatment
Unit
IBP - 1800С
70 - 1050С
Isomerization Unit
70-105°C Fraction
100%
10%
Yield: 93%
Aromatics: 0%
ISOMERATE
RON 85
9.3%
RON 95-98
Benzene: 0.9%
Aromatics: 33.8%
Yield: 88%
Hydrocarbon Gas
Reforming Unit
105 -
1800С
(С6 < 0.3%)
Benzene: 1.2%
Aromatics: 60%
REFORMATE
Yield: 88%
RON 100
56.3%
67%
Hydrogen Gas
Page 8
Comparison of the 2 process configurations
From a recent case study made for a plant with light naphtha Isomerization unit (DIP,
Super DIH) and CCR Reforming unit for a 2 MMTA naphtha stream.
Configuration
Conventional
With
Isomalk-4SM
Benefit
Value to
Refinery Per
Annum
Overall gasoline yield,
wt.%
88.7%
90.8%
2.1%
16.8 MM USD *
Octane Number, RON
94.0
95.5
1.5
15.0 MM USD *
Benzene in the
gasoline pool, vol.%
1.5%
0.6%
0.9% less
Varies
Aromatics in the
gasoline pool, vol.%
37.0%
33.5%
3.5% less
Varies
* - based on $400/ton differential for liquid yield over gas; and $5/ton-octane number
Total benefit is over 30 MM USD/yr with the C7 paraffins routed to Isomalk-4SM
Page 9
Aromatics Removal from Steam Cracker Feed
Tailoring the feed
may be useful
Steam Cracker
Dearomatization
(GT-DeAromsm)
C2=, C3=, BD, Bz, H2
BTX+
Page 10
Cracked Gasoline Management –
FCC Desulfurization
Conventional Three-Stage Process
LCN
C5-iC6-
(optional)
FCC
Naphtha
MCN
70-150oC
HCN
150oC-EP
Caustic
Extraction
ULS
Gasoline
Mild HDS
ULS
Gasoline
Medium HDS
ULS
Gasoline
C6-C9 Olefins
Sulfur
Saturation
(unavoidable)
Desulfurization
(needed)
Severe HDS
ULS
Gasoline
FCC Gasoline Desulfurization
Alternate Option to Extract Sulfur from the Olefins
(optional)
FCC
Naphtha
ULS
Gasoline
Caustic
Extraction
LCN
C5-iC6-
Mild HDS
ULS
Gasoline
Raffinate: Paraffins + Olefins
Extract: Sulfur + Aromatics
MCN
70-150oC
Medium HDS
HDS
Aromatics
Sulfur
H2
Solvent
HCN
150oC-EP
H2S
GT-BTX PluS®
Severe HDS
ULS
Gasoline
GT-BTX PluS® - Enabling Technology
• Technically advanced extraction process enables
— Desulfurized gasoline to < 15 ppm sulfur with zero octane loss
— Reduced benzene in cracked gasoline to < 0.5% benzene
— FCC olefins preserved for conversion to aromatics or propylene
Patented process – available through GTC Technology
Typical Refinery Configuration with
GT-BTX PluS® - Products to Gasoline
Crude Oil
Crude Distillation
Wide Naphtha
Range
Hydrotreating
Isomerization
Naphtha
Reforming
Gasoline
Gasoline
Kerosene
Desulfurization
Gasoil
FCCU
FCC
Naphtha
Fuel
Olefinic
Raffinate
to Gasoline
GT-BTX PluS®
Gasoline
• Zero Δ in octane value
• Low benzene
• Low sulfur
Refinery Configuration with GT-BTX PluS®
to facilitate increased Propylene
Crude Oil
Crude Distillation
Wide Naphtha
Range
Hydrotreating
Isomerization
Naphtha
Reforming
Kerosene
Desulfurization
Gasoline
Gasoline
Fuel
Additional
Propylene
Aromatization
Olefinic Raffinate
Gasoil
FCCU
FCC
Naphtha
GT-BTX PluS®
Extends Range of FCC Naphtha Recycle
Aromatics
Economical Ethylene Capacity
for Recovering By-products
Economical to Produce
, Secondary Deriv.
Naphthalene, Secondary Deriv.
Isoprene, DCPD, Pips
Styrene Extraction, C9 Resins
Butadiene, Benzene, Toluene, Xylenes
Ethylene, Propylene, Primary Derivations
200
400
600
800
Ethylene rate, KTA
(Liquids feed)
1000
1200
1400
C4 Utilization
Butadiene product
MTBE product
Butadiene
Extraction Unit
MTBE Unit
Raffinate 1
Crude
Mixed
C4
Selective
Hydrogenation
Unit
Skeletal
Isomerization
Unit
Isobutene product
MTBE Backcracking Unit
Raffinate 2
Butene-1 product
C4/C4O
Extraction
Unit
Butene-1
Recovery
Unit
Butene-2
Butane
Oxidative
Dehydro
Unit
N-Butene
Isomerization
Unit
Crude butadiene
Propylene product
TransMetathesis
Unit
Ethylene
Dimerization
Unit
Page 17
Pygas C5 Utilization – GTC GT-C5/Isoprene
Lights
Mono Olefins/ Paraffins
High Purity Isoprene
Raw C5
Lights
Removal
Section
Dimerization
Section
Extraction
Section
Finishing
Section
C5 Splitter
Section
C6 Stream
PIPS and
DCPD
Finishing
Section
PIPS
60 – 75 %DCPD
85 %DCPD
Pygas C6-C8 Utilization: GT-BTX®
Extractive Distillation depends on a selective solvent to alter the boiling points
of aromatics & non-aromatics to facilitate their separation by distillation.
Solvent selectivity is critical
Solvent
α n-C7/Benzene
Techtiv-100tm
2.44
Sulfolane
2.00
N-methyl Pyrolidone
1.95
N-formyl Morpholine
1.89
Glycol blends
1.35
None
0.57
Proprietary solvent of
GT-BTX® Technology
Pygas C6-C8 Utilization
Benzene, Toluene, Xylene need to be extracted from C6 – C8 cut of pygas
in order to meet petrochemical quality
C5s
H2
Raw Pygas
1st
Stage
H2
C6-c8
Raffinate
H2s
C6-c8 Cut
2nd
Stage
Aromatics
Extraction Unit
Clariant catalysts available for
both stages of Pygas HDT
DeC7
DeC5
Benzene
Toluene
Mixed Xylene
C9+
World-Class Extraction Technology
for BTX Purification
Hydrocarbon
Feed
Aromatics to
downstream
fractionation
Raffinate
Lean solvent
Extractive
Distillation Column
(EDC)
Solvent Recovery
Column (SRC)
Aromatics rich solvent
Page 21
Pygas C8 Utilization – GT-Styrene
Heart cut distillation followed by ED
Light Cut
C5
C6
C7
Pygas
C8
C8 Cut
C9
C10
Heavy Cut
GT-Styrene
99.8+ wt.%
Styrene
Pygas C8 Utilization – GT-Styrene
•
Recovery of styrene from the raw pyrolysis gasoline derived from the steam
cracking of naphtha, gas oils, and natural gas liquids (NGL)
C8 aromatics
99.9+ wt%
styrene product
Finishing
treatment
H2
Pygas C8 cut
PA
Hydrogenation
Lean solvent
Feed
Pretreatment
Extractive
Distillation
Heavies
Solvent
Recovery
Styrene
Finishing
Economics of Styrene Recovery
Basis - 25,000 mt/yr Styrene (2014 pricing)
Parameters
Capital cost
GT-Styrene®
$28 MM
Feedstock cost, $/ton
$600
Processing cost, $/ton
$200
Total production cost, $/ton
$800
Sales price, $/ton
Net margin
Pre-tax ROI
$1250
$11.25 MM
40%
Page 24
Pygas C9+ Utilization –
Naphthalene, Solvent, & Resin
Lights
Removal
Column
Purification System
Water
C9 to HCR Feed
PGO Feed
Finishing Section
Naphthalene
Fractionator
Naphthalene
Solvent
Solvent Flasher
PFO or Fuel
Conclusions
• The nature of raw materials leads to proper processing scheme
• Non-chlorinated isomerization catalysts are the optimum to boost
gasoline octane for C4 – C7 fractions of straight run gasoline
• Refinery/petrochemical integration, in addition to propylene
recovery, captures aromatics and preserves olefins from FCC
gasoline
• Steam cracker by-products are important to recover from large
plants using naphtha feedstock
• Technology is available to upgrade products from C4 – C12
boiling range
Page 26