Enhance Refinery Enhance Refinery Economics Economics Through C4 Chemistry & Through C4 Chemistry & Advances Advances Dr. Amarjit Bakshi Dr. Amarjit Bakshi President President Refining Hydrocarbon Technologies Refining Hydrocarbon Technologies Texas, USA. Texas, USA. www.rhtgulfcoast.com www.rhtgulfcoast.com Presented at Presented at CAT-TECH CAT-TECH Global Catalyst Technology Forum Global Catalyst Technology Forum 13 & 14 June, 2011 13 & 14 June, 2011 Rixos Libertas, Dubrovnik, Croatia Rixos Libertas, Dubrovnik, Croatia RHT
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Cat Tech Global Catalyst Forum June 2011 Dubrovnik
New technologies for alkylation with same reaction chemistry but smart configuration and equipment with essentially low risk as reaction chemistry as been used for 50 years
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Mixed Butylene ProductionMixed Butylene Production
• Steam CrackerSteam Cracker
• FCC UnitsFCC Units
• Other Thermal CrackersOther Thermal Crackers
• For MTBE and other special use For MTBE and other special use from Dehydrogenation from Dehydrogenation
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Uses Of ButylenesUses Of Butylenes • Mixed Butylenes for AlkylationMixed Butylenes for Alkylation and ether and ether ProductionProduction• Mixed Butylenes for MMAMixed Butylenes for MMA• Pure Isobutylene for Rubber and LubesPure Isobutylene for Rubber and Lubes• Pure 1- Butene as Monomer Pure 1- Butene as Monomer • Butene-2 for butanol and metathesis for Butene-2 for butanol and metathesis for Propylene productionPropylene production• Isobutane goes to alkylationIsobutane goes to alkylation
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RHT-Alkylate ProcessRHT-Alkylate Process Why RHT-Alkylate• Paradigm Shift• No Major Complex Internals in
the Reactor• No Maintenance and Mechanical
Problems• Isothermal Low Temperature
Operation• Provides mixing with a simple
Eductor providing good interfacial area.
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RHT-Alkylate ProcessRHT-Alkylate Process
• Auto refrigeration vapor can be absorbed and Compressor can be deleted. A major
Paradigm shift and low cost option for grass root and revamps including HF units. Low maintenance option.
• Hydrocarbon /Acid separation by low cost coalescers with optimized design.
• No waste production.• Standard Process industry
equipment• Standard Reactor internals, no
proprietary internals
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RHT-Alkylate ProcessRHT-Alkylate Process • Absorption is a low Capex option,
improves system reliability. Liquid from absorber is sent to reactor which saves utilities. Compression can still be used in the existing units if so desired.
• Lower Capex by 33 to 45 %, due to economy of scale and other improvement.
• Depending upon the option used for vapor recovery from auto refrigeration( Absorption or Compression) lower Opex by 35 to 45 %.
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RHT-Alkylate ProcessRHT-Alkylate Process
• Better Octane • Lower Acid Consumption• Easier to revamp the unit with
Reactor and novel mixing Concept.
• Vapor absorption rather than expense of compressor replacement or revamp.
• No complex seals or proprietary internals which either require regular replacement or maintenance.
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RHT-Alkylate ProcessRHT-Alkylate Process• Reactor can be sized to any size no
scale up issues. Multiple eductor systems to provide good mixing.
• RHT-Alkylate process uses standard equipment used in Refining or Petrochemical industry.
• Flexible operation. No internals so no undue risk of any mishap due to internals, maintenance or replacement of internals.
• Propylene can be fed at the motive fluid pump discharge with inline mixer, higher OSV and acid concentration, provides better efficiency.
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Alkylation ChemistryAlkylation Chemistry• Reaction Chemistry is pretty Reaction Chemistry is pretty
complex but same as conventional complex but same as conventional Alkylation Process chemistry though Alkylation Process chemistry though better yield observed at low better yield observed at low temperature (US Pat. 5095068)temperature (US Pat. 5095068)
• Process Selective at low Process Selective at low temperature hence less acid temperature hence less acid soluble oil produced (US Pat. soluble oil produced (US Pat. 7,652,187 )7,652,187 )
• Reference US Pat. Reference US Pat. 52849905284990RHT
3.3. Isobutane concentration in Isobutane concentration in Reactor and Reactor effluentReactor and Reactor effluent
4.4. Acid concentrationAcid concentration
5.5. Olefin space velocity is olefin Olefin space velocity is olefin volume fed to Reactor per hour volume fed to Reactor per hour per volume of acid catalystper volume of acid catalyst
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1.1. Hydrocarbon / Acid mixing is a major Hydrocarbon / Acid mixing is a major variable in the alkylation reaction so variable in the alkylation reaction so that the acid interfacial area is available that the acid interfacial area is available to olefin and isobutane to react. The to olefin and isobutane to react. The eductor device provides this function eductor device provides this function very efficiently. The OSV is kept in 0.2 very efficiently. The OSV is kept in 0.2 to 0.4 1/hr range.to 0.4 1/hr range.
Operating VariablesOperating Variables
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2.2. Temperature, another variable which is Temperature, another variable which is very important for alkylation. RHT very important for alkylation. RHT configuration provides the best results due configuration provides the best results due to essentially isothermal conditions (25-27 to essentially isothermal conditions (25-27 F) in the reactor. Higher reaction F) in the reactor. Higher reaction temperature favors polymerization temperature favors polymerization reactions, which reduces the acid reactions, which reduces the acid concentration, increases acid concentration, increases acid consumption, corrosion and reduces consumption, corrosion and reduces Product Quality/Octane.Product Quality/Octane.
Operating VariablesOperating Variables
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3.3. Isobutane concentration is kept at the Isobutane concentration is kept at the
optimum condition I/O ratio ranges from 6 optimum condition I/O ratio ranges from 6
to 15 to provide good product quality and to 15 to provide good product quality and
selectivity. Optimum ratio is used so as to selectivity. Optimum ratio is used so as to
• Novel configuration provides Novel configuration provides low cost simple catalyst low cost simple catalyst system , improves conversion system , improves conversion and catalyst life.and catalyst life.
• With a new Selectivator, the With a new Selectivator, the RHT process provides higher RHT process provides higher yield and selectivity than other yield and selectivity than other processes, Isobutylene processes, Isobutylene conversion of 97 to 99 % to conversion of 97 to 99 % to
Iso-octene product. Iso-octene product.
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WHY RHTWHY RHT-Iso-octene-Iso-octeneSMSM
• Lower codimers produced by Lower codimers produced by reducing the per pass conversion in reducing the per pass conversion in First Reactor.First Reactor.
• Reduces loss of normal olefins for Reduces loss of normal olefins for Alkylation. Alkylation.
• Conventional catalyst and Conventional catalyst and configuration lends to catalyst configuration lends to catalyst change while on line, hence change while on line, hence conversions are higher on an conversions are higher on an average compared to any technology average compared to any technology available in the market.available in the market.
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Figure 1RHT Iso-Octene Process
Water wash Column Mixer Reactor Debutanizer
WaterWash
C4 Feed
(1)
(1) 1 to 3% propylene in feed
LP
H2
CW
C4 Raffinate
Iso-Octene Product
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Figure 2RHT Iso-Octene Process
Water wash Column Mixer Debutanizer
WaterWash
C4 Feed
(1)
(1) 1 to 3% propylene in feed
LP
H2
C4 Raffinate
Iso-Octene Product
SelectivatorRecycle
Water to Treatment
1 st Reactor Finishing Reactor Iso-octene Column
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Figure 3RHT Iso-Octene Process
Water wash Column Mixer
WaterWash
C4 Feed
(1)
(1) 1 to 3% propylene in feed
LP
H2
C4 Raffinate
Iso-Octene Product
IPA
Reactor
(multiple)
Debutanizer Iso-octene column
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Figure 4
RHT Iso-Octene ProcessRevamp of Conventional MTBE Unit
Water Wash ColumnExisting
MixerNEW
1 st ReactorExisting
Finishing Reactor Existing
DebutanizerExisting
MeOH Extractor Existing Deleted
MeOH ColumnExisting
MeOH
WaterWash
C4 Feed(1)
(1) 1 to 3% Propylene in the feed
Water to Treatment
LPH2
CW
CW
IPARecycle to
Reactor
C4 Raffinate
Iso-OcteneProduct
MTBE Product
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Figure 6Figure 6RHT Iso-octene to Iso-octane HydroRHT Iso-octene to Iso-octane Hydro
Iso-octene
H2 CW
Vent
Mixer 1 st Reactor K.O.Drum
1
2
Hydrogen
Cooler
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Iso-octane Product
Finishing Reactor Iso-octane Stripper
6
7
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WHY RHTWHY RHT-Iso-octene-Iso-octeneSMSM
• Distillation performed at Distillation performed at optimum conditions.optimum conditions.
• Easy to revamp the existing Easy to revamp the existing MTBE units.MTBE units.
• Low cost revamp most of the Low cost revamp most of the equipment can be used from equipment can be used from MTBE unit.MTBE unit.
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WHY RHTWHY RHT-Iso-octane-Iso-octaneSMSM
• The hydrogenation/olefin Saturation The hydrogenation/olefin Saturation is done at lower pressure , which is done at lower pressure , which reduces the capital cost and utilities.reduces the capital cost and utilities.
• Conventional but high activity dual Conventional but high activity dual catalysts use for olefin saturation.catalysts use for olefin saturation.
• Essentially over 99 % olefin Essentially over 99 % olefin hydrogenation to Paraffins is hydrogenation to Paraffins is achieved.achieved.
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RHT PortfolioRHT Portfolio• Please see website Please see website www.rhtgulfcoast.comwww.rhtgulfcoast.com
and linkedin for other details and and linkedin for other details and presentations attached to profile. presentations attached to profile.
• RHT LLC provides essentially all RHT LLC provides essentially all hydrogenation technologies ( selective hydrogenation technologies ( selective hydrogenation, HDS of Naphtha and Diesel, hydrogenation, HDS of Naphtha and Diesel, isomerization, Benzene Saturation with Smart isomerization, Benzene Saturation with Smart Configuration and enhanced economics.Configuration and enhanced economics.
• Information provided under NDA please Information provided under NDA please contact us and look up the Patents/IP.contact us and look up the Patents/IP.