1

NEW DEVELOPMENTSNEW DEVELOPMENTS

ININ

SULFURIC ACIDSULFURIC ACID

ALKYLATIONALKYLATION

RHT-AlkylationRHT-AlkylationSMSM TECHNOLOGY TECHNOLOGY

NEW DEVELOPMENTSNEW DEVELOPMENTS

ININ

SULFURIC ACIDSULFURIC ACID

ALKYLATIONALKYLATION

RHT-AlkylationRHT-AlkylationSMSM TECHNOLOGY TECHNOLOGY

RHT

D r. Amarjit Bakshi:

Refining Hydrocarbon Technologies LLCKaty ( Houston Suburb), Texas 77450 , USA

2

RHT-Alkylate ProcessRHT-Alkylate Process

Why RHT-Alkylate

Paradigm Shifts 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.

RHT

3

RHT-AlkylateRHT-Alkylate ProcessProcess

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

4

RHT-AlkylateRHT-Alkylate ProcessProcess 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 %.

RHT

5

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

6

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.

RHT

7

Alkylation ChemistryAlkylation Chemistry• Reaction Chemistry is pretty

complex but same as conventional Alkylation Process chemistry though better yield observed at low temperature (US Pat. 5095068)

• Selective at low temperature hence less acid soluble oil produced

RHT

8

Alkylation ChemistryAlkylation ChemistryMain ReactionsMain Reactions

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

2,3,3 TMP

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

Dimethylhexanes, Isopentane and other C9 to C12 compounds in the alkylate.

H2SO4

RHT

9

Alkylation ChemistryAlkylation Chemistry Secondary ReactionsSecondary Reactions

• Polymerization reaction•Cracking Reactions•Disproportionation reaction•Hydrogen Transfer reaction•Esterification reaction

RHT

15

OPERATING VARIABLES• Hydrocarbon/ Acid mixing.

• Temperature.

• Isobutane concentration in reactor and in reactor effluent .

• Acid Concentration.

• Olefin Space Velocity,is olefin Volume fed to reactor per hour per volume of Acid Catalyst

RHT

16

OPERATING VARIABLES• Hydrocarbon/ Acid mixing is major

variable in the alkylation reaction so that all the acid interfacial area is available to olefin and isobutane to react. The eductor device provides this function very efficiently.The OSV is kept in 0.2 to 0.4 1/hr range.

RHT

17

OPERATING VARIABLES• Temperature is another variable which is

very important and present RHT configuration, provides the best results due to essentially isothermal conditions (25 -27 F) in the reactor. Higher reaction temperature favors polymerization reactions, which reduces the acid concentration, increases acid consumption, corrosion and reduces the Product Quality/Octane.

RHT

18

OPERATING VARIABLES• Isobutane concentration is kept at the

optimum condition I/O ratio of 6 to 15 to provide good product quality and selectivity and still not increasing de-isobutanizer loads. Lower I/O ratio enhances the olefin polymerization, which is not good for quality and increases the acid consumption. Isobutane in Reactor effluent 53 to 75 % by Vol.

RHT

19

OPERATING VARIABLES• Acid concentration is very important

for alkylation reaction. At lower acid concentration ASO make increases, product quality goes down. Normal acid concentrations are kept in the range of 89 to 95 %. Concentration below 86 % Acid concentration, activity is decreased, enhancing polymerization, this condition is known as close to acid run away as acid concentration is difficult to control.

RHT

20

OPERATING VARIABLES• Olefin Space Velocity is a Measure of

Olefin Volume compared to Acid volume in the reactor. Higher Space velocity enhances the acid consumption and lower product quality. The Volume of acid is optimized in relation to olefin to provide optimum results.

RHT

21

OPERATING VARIABLES• Acid hydrocarbon separation is very

important issue. RHT uses Coalescer, so as to remove traces of acid from hydrocarbon. RHT has patented the higher temperature separation/acid settling from the hydrocarbon, which favors the acid settling from the hydrocarbon. Vertical or horizontal coalescers can be used.

RHT

22

OPERATING VARIABLES

RHT process reduces all the equipment which is used for neutralization and wash and produces Caustic waste stream. This provides major savings to Capex and also Opex for deleting the requirements for treating the waste stream.

24

OPERATING VARIABLES

RHT

The conventional processes use the settling together with neutralization (wet system), which dilutes the acid , produces caustic waste and corrosion problems. Conventional process have reduced acid carry over from settlers by using coalescers. RHT has enhanced that concept to the ultimate with patented temperature for coalescer operation.

25

28RHT

29RHT

30RHT

31

RHT-ARHT-Alkylate Revamplkylate Revamp Additional reactor and Pumps Absorption system if Compression bottleneck. Coalescers to handle the acid separation. Existing De-isobutanizer revamp Easy to convert HF alkylation Vertical equipment , plot area not major constraint. Easy to add on additional capacity.

RHT

32

General Considerations• Inerts, components which do not

contribute in the reaction, take up the Reactor space, reduce the space velocity and Capex.

• Water in acid, lowers acid concentration produces low octane alkylate.

• Polymerization reaction form conjunct polymers (ASO) and dilute the acid concentration and acid consumption.

• Contaminants like diolefins, sulfur compounds and oxygenates consume more acid.

RHT

33

Alkylate yields Etc

• Alkylate Yield C3= C4

= C5=

• Volume V/V O 1.67-1.78 1.70-1.76 1.67-1.83 • Mass M/M O 2.28- 2.39 2.05-2.09 1.85-2.07• Molar m/m O 0.91-1.1 0.96-1.04 1.02-1.22• RON C 89-92 94.5- 97.5 92.5-93.5 • MON C 88.5-90.5 92-95 91.4-92.4• Isobutane V/V O 1.02-1.22 1.17-1.2 1.32-1.55• Acid cons lb/g Alk 0.55/0.65 0.19/0.26 0.28/0.38

• O=Olefin,RHT

34

Safety consideration• Spent acid could form mist and SO2 if

released under pressure.

• Monitor no acid goes to fractionation

• Spent Acid regeneration off-site

• Non volatile liquid

• Highly corrosive, causes burns on skin

• Adequate monitoring for acid so it is completely taken out before fractionation.

RHT

35

Safety ConsiderationCaution and measures to Be taken• Monitor spent acid strength

during transfer to storage and transportation.

• To complete Hazop studies• No volatile hydrocarbon or low

strength acid to be sent to storage.

• Prevent acid run away by extensive education and training.

RHT

36

Causes of Acid Runaway• Poor mixing• Low acid in the reactor• Low acid recycle rates• High content oxygenates• Low Acid strength• High Reactor temperature• Excessive contaminants• Loss of acid strength• Alkylate turns light reddish in color.

RHT

37

Safety Measures• Monitor Alkylate color

• Reactor gets cold without Feed reduction

• Control Acid Strength

• Watch for Acid carry over for multiple reasons

• Check acid reactivity before sending to storage for non-reactivity of acid

• Stop feed

• Cold circulation of Isobutane RHT

38

Reactor ComparisonsReactor Comparisons Conventional RHT-

Alkylate Standard sizes Economy of

Scale No moving parts Simple

Eductors complicated seals/ as Mixing device, internals no scale up issues

Frequent Normal process

Maintenance equipment , safe

internal piping.

RHT

39

Auto Refrigeration vaporAuto Refrigeration vapor

Compression is normally used. Option to use low cost absorptions system patented by RHT- Alkylate.

Easier to revamp with this option.

Simple design and operating system , no moving parts, lower capex and Opex.

RHT

40

RHT-Alkylate Technology RHT-Alkylate Technology AdvantagesAdvantages

Novel reactor and Mixing device No Complex internals in the Reactor No Maintenance and mechanical

Problems Isothermal Low temperature operation Unique Configuration allows good

mixing and interfacial area. Auto refrigeration vapor can be

absorbed which is low cost option, and unique for revamps.

Acid/ Hydrocarbon separation by standard coalescers.

Standard Process industry equipment

RHT

41

RHT-Alkylate Technology RHT-Alkylate Technology AdvantagesAdvantages

Lower capex by 33 to 45 % due to economy of scale and absorption and Acid/ Hydrocarbon coalescers.

Lower Opex by >35 % and with absorption system more cold energy is available.

Better Octane Product Lower acid consumption isothermal Low temperature operation Easier revamps.

RHT

42

We have the answers Simple Design to meet your requirements. Thought of C3/C4 /C5 injection system. Simple Acid/Hydrocarbon separation

system. No special internals to be provided by

single source. Unique absorption system instead of

compressor. Lower capex and opex Higher octane and lower acid consumption

WHY RHT WHY RHT TechnologyTechnology

RHT