Cat Tech Global Catalyst Forum June 2011 Dubrovnik

Enhance Refinery EconomicsEnhance Refinery Economics

Through C4 Chemistry & Through C4 Chemistry & AdvancesAdvancesDr. Amarjit BakshiDr. Amarjit Bakshi

PresidentPresidentRefining Hydrocarbon TechnologiesRefining Hydrocarbon Technologies

Texas, USA.Texas, USA. www.rhtgulfcoast.comwww.rhtgulfcoast.com

Presented atPresented atCAT-TECHCAT-TECH

Global Catalyst Technology ForumGlobal Catalyst Technology Forum13 & 14 June, 201113 & 14 June, 2011

Rixos Libertas, Dubrovnik, CroatiaRixos Libertas, Dubrovnik, Croatia1 RHT

http://www.rhtgulfcoast.com/

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

2RHTConfidential

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

3RHT

2424 ConfidentialConfidential 44

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

RHT


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.

RHT


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


Alkylation ChemistryAlkylation ChemistryMain ReactionsMain Reactions

• Olefins + Isobutane Olefins + Isobutane 2,2,4 TMP 2,2,4 TMP 2,3,4 TMP2,3,4 TMP

2,3,3 TMP 2,3,3 TMP

Other reaction products are made;Other reaction products are made;2,4 and 2,3 Dimethylpentane ( DMP) , 2,4 and 2,3 Dimethylpentane ( DMP) ,

Dimethylhexanes, Isopentane and other Dimethylhexanes, Isopentane and other CC99 to C to C1212 compounds in the alkylate. compounds in the alkylate.

H2SO4

RHTRHTRHT


Figure 1RHT-Alky: BLOCK FLOW DIAGRAM

Isobutane Make-up

Mix Olefin Feed

C3 purge

Condensed C4's C3 Removal

Compressor*

Olefin/HC Reactor Feed Iso-butaneC4's

Reactor effluent crude n-butaneReactor Feed alkylate

Acid Return

Acid Return

Acid Make up Alkylate ProductSpent Acid Acid

Recycle *or to absorber

ReactorSystem

C4 System

HC/Separation FinishingCoalescer

AlkylateSeparation

Depropanizer

FigureFigure 11RHT-Alky: Block Flow DiagramRHT-Alky: Block Flow Diagram

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Figure 2RHT Novel C4 Vapor Recovery System

VentDemister

PadDemister Pad

Note 1

Acidto reactor

Heavy Liquid

Recycle to Reactor

Note 1: Alternate option to use Isobutane from de-isobutanizer column overhead.

Reactor

Figure 2Figure 2RHT Novel C4 Vapor RHT Novel C4 Vapor RecoveryRecovery

SystemSystem

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RHT-Alkylate RevampRHT-Alkylate Revamp• Additional reactor and pumpsAdditional reactor and pumps

• Absorption system if compression Absorption system if compression bottleneckbottleneck

• Coalescers to handle acid separationCoalescers to handle acid separation

• Existing de-isobutaner revampExisting de-isobutaner revamp

• Easy to convert HF alkylation Easy to convert HF alkylation

• Vertical equipment, plot area not Vertical equipment, plot area not major constraintmajor constraint

• Easy to add additional capacityEasy to add additional capacity

RHT


Reactor Comparisons

Conventional RHT- Alkylate

• Standard sizes Economy of scale

• Impeller parts Simple eductors complicated seals/ as mixing device, internals no scale up issues

• Frequent process Normal refinery maintenance equipment/low and corrosion maintenance

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Operating VariablesOperating Variables

1.1. Hydrocarbon / Acid MixingHydrocarbon / Acid Mixing

2.2. Reactor temperatureReactor temperature

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


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.



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.



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

optimize de-isobutanizer utilities. Lower I/O optimize de-isobutanizer utilities. Lower I/O

ratio enhances the olefin polymerization, ratio enhances the olefin polymerization,

which is not good for quality and increases which is not good for quality and increases

acid consumption. Isobutane in Reactor acid consumption. Isobutane in Reactor

effluent is 53% to 75% by Vol.effluent is 53% to 75% by Vol.



4.4. Acid concentration is very important for Acid concentration is very important for

alkylation reaction. At lower acid alkylation reaction. At lower acid

concentration, ASO increases and product concentration, ASO increases and product

quality goes down. Normal acid quality goes down. Normal acid

concentrations are kept in the range of 89% concentrations are kept in the range of 89%

to 95%. With concentration below 86%, to 95%. With concentration below 86%,

activity is decreased, enhancing activity is decreased, enhancing

polymerization. polymerization.



5.5. Olefin Space Velocity is a measure of Olefin Space Velocity is a measure of

Olefin Volume compared to Acid Volume Olefin Volume compared to Acid Volume

in the Reactor. Higher Space Velocity in the Reactor. Higher Space Velocity

enhances the acid consumption and enhances the acid consumption and

lower product quality. The Volume of acid lower product quality. The Volume of acid

in the Reactor is optimized in relation to in the Reactor is optimized in relation to

olefin, providing optimum results in the olefin, providing optimum results in the

range of 40% to 60%. range of 40% to 60%.



• Lower Capex by 33% to 45% due to mixing device, economy of scale, absorption and Acid / Hydrocarbon coalescers

• Lower Opex by >35% with absorption system application

• Better Octane Alkylate

• Lower acid consumption

• Isothermal low temperature operation

• Easier revamps

RHT-Alkylate TechnologyRHT-Alkylate TechnologyAdvantagesAdvantages

RHT


• We have the answers.We have the answers.

• Simple design to meet your requirements Simple design to meet your requirements with unique eductor mixing devicewith unique eductor mixing device

• Simple Acid/Hydrocarbon separation systemSimple Acid/Hydrocarbon separation system

• No special internals to be provided by single No special internals to be provided by single sourcesource

• Unique absorption system instead of Unique absorption system instead of compressioncompression

• Lower Capex and Opex, Higher octane and Lower Capex and Opex, Higher octane and lower acid consumptionlower acid consumption

Why RHT Alkylation Technology

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CC44 Other uses Other uses

• CC44 refinery economics refinery economics

enhancement enhancement

• Isobutylene Dimerization Isobutylene Dimerization

• Smart ConfigurationSmart Configuration

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NEW DEVELOPMENTS

IN

RHT-ISOOCTENESM

RHT-ISOOCTANESM

TECHNOLOGY

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WHY RHTWHY RHT-Iso-octene-Iso-octeneSMSM

• 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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• 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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Water wash Column Mixer Debutanizer

WaterWash

C4 Feed

(1)


LP

H2

C4 Raffinate

Iso-Octene Product

SelectivatorRecycle

Water to Treatment

1 st Reactor Finishing Reactor Iso-octene Column

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Water wash Column Mixer

WaterWash

C4 Feed

(1)


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

34

Iso-octane Product

Finishing Reactor Iso-octane Stripper

6

7

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• 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.

RHT


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.

RHT

http://www.rhtgulfcoast.com/

3535 ConfidentialConfidential 3535RHT

Thank You Refining Hydrocarbon Technologies LLC

20130 Chateau Bend DriveKaty ( Houston Suburb),

Texas 77450USA

Dr. Amarjit BakshiPhone 281-398-8408/281-235-7780E-mail:[email protected]

www.rhtgulfcoast.com

Cat Tech Global Catalyst Forum June 2011 Dubrovnik

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