Rht Sulfuric Acid Alkylation Rht Presentation Revision 1


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LOw temperature Low cost Sulfuric acid alkylation 50% Capex and Opex savings

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Rht Sulfuric Acid Alkylation Rht Presentation Revision 1

  1. 1. NEW DEVELOPMENTS IN SULFURIC ACID ALKYLATION RHT-Alkylation SM TECHNOLOGY RHT <ul><ul><li>D r. Amarjit Bakshi: </li></ul></ul><ul><ul><li>Refining Hydrocarbon Technologies LLC </li></ul></ul><ul><ul><li>Katy ( Houston Suburb), Texas 77450 , USA </li></ul></ul>
  2. 2. RHT-Alkylate Process <ul><ul><li>Why RHT-Alkylate </li></ul></ul><ul><ul><li>Paradigm Shifts </li></ul></ul><ul><ul><li>No Major Complex Internals in the </li></ul></ul><ul><ul><li>Reactor </li></ul></ul><ul><ul><li>No Maintenance and Mechanical Problems </li></ul></ul><ul><ul><li>Isothermal Low Temperature Operation </li></ul></ul><ul><ul><li>Provides mixing with a simple Eductor providing good interfacial area. </li></ul></ul>RHT
  3. 3. RHT-Alkylate Process <ul><ul><li>Auto refrigeration vapor can be absorbed and Compressor can be deleted. A major </li></ul></ul><ul><ul><li>Paradigm shift and low cost option for grass root and revamps including HF units. Low maintenance option. </li></ul></ul><ul><ul><li>Hydrocarbon /Acid separation by low cost coalescers with optimized design. </li></ul></ul><ul><ul><li>No waste production. </li></ul></ul><ul><ul><li>Standard Process industry equipment </li></ul></ul><ul><ul><li>Standard Reactor internals, no proprietary internals. </li></ul></ul>RHT
  4. 4. RHT-Alkylate Process <ul><ul><li>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. </li></ul></ul><ul><ul><li>Lower Capex by 33 to 45 %, due to economy of scale and other improvement. </li></ul></ul><ul><ul><li>Depending upon the option used for vapor recovery from auto refrigeration( Absorption or Compression) lower Opex by 35 to 45 %. </li></ul></ul>RHT
  5. 5. RHT-Alkylate Process <ul><ul><li>Better Octane </li></ul></ul><ul><ul><li>Lower Acid Consumption </li></ul></ul><ul><ul><li>Easier to revamp the unit with Reactor and novel mixing Concept. </li></ul></ul><ul><ul><li>Vapor absorption rather than expense of compressor replacement or revamp. </li></ul></ul><ul><ul><li>No complex seals or proprietary internals which either require regular replacement or maintenance. </li></ul></ul>RHT
  6. 6. RHT-Alkylate Process <ul><ul><li>Reactor can be sized to any size no scale up issues. Multiple eductor systems to provide good mixing. </li></ul></ul><ul><ul><li>RHT-Alkylate process uses standard equipment used in Refining or Petrochemical industry. </li></ul></ul><ul><ul><li>Flexible operation. No internals so no undue risk of any mishap due to internals, maintenance or replacement of internals. </li></ul></ul><ul><ul><li>Propylene can be fed at the motive fluid pump discharge with inline mixer, higher OSV and acid concentration, provides better efficiency. </li></ul></ul>RHT
  7. 7. Alkylation Chemistry <ul><li>Reaction Chemistry is pretty complex but same as conventional Alkylation Process chemistry though better yield observed at low temperature (US Pat. 5095068) </li></ul><ul><li>Selective at low temperature hence less acid soluble oil produced </li></ul>RHT
  8. 8. Alkylation Chemistry Main Reactions <ul><li>Olefins + Isobutane 2,2,4 TMP </li></ul><ul><li>2,3,4 TMP 2,3,3 TMP </li></ul><ul><li>Other reaction products are made; </li></ul><ul><li>2,4 and 2,3 Dimethylpentane ( DMP) , Dimethylhexanes, Isopentane and other C 9 to C 12 compounds in the alkylate. </li></ul>H2SO4 RHT
  9. 9. Alkylation Chemistry Secondary Reactions <ul><li>Polymerization reaction </li></ul><ul><li>Cracking Reactions </li></ul><ul><li>Disproportionation reaction </li></ul><ul><li>Hydrogen Transfer reaction </li></ul><ul><li>Esterification reaction </li></ul>RHT
  10. 10. Alkylation Chemistry Secondary Reactions <ul><li>Polymerization reaction </li></ul><ul><li>Second olefin addition to C 8 or C 12 </li></ul><ul><li>results in polymerization and bigger molecules.These reactions are kept to minimum and some of these compounds tend to go with Acid soluble oil(conjunct polymer). </li></ul><ul><li>C 8 H 18 +C 4 H 8 +H 2 C 12 H 28 </li></ul>RHT
  11. 11. Alkylation Chemistry Secondary Reactions Cracking Reactions Larger isoalkyl compounds crack to form smaller compounds and olefins, which than can get into earlier mentioned reactions. i-C 12 H 26 i- C 5 H 12 +i-C 7 H 14 or i-C 12 H 26 i-C 6 H 14 + i-C 6 H 12
  12. 12. Alkylation Chemistry Secondary Reactions H2SO4 <ul><li>Disproportionation reaction </li></ul><ul><li>Two molecules of alkylate forming a lower and a higher molecular weight isoparaffin compound. This normally happens when isoparaffin comes in contact with Acid in the absence of olefin. </li></ul><ul><li>2 C 8 H 18 C 7 H 16 + C 9 H 20 </li></ul>RHT
  13. 13. Alkylation Chemistry Secondary Reactions H2SO4 <ul><li>Hydrogen Transfer reaction </li></ul><ul><li>Alkylating isobutylenes and amylenes, hydrogen transfer reaction takes place. This provides higher yield and isobutane consumption together with isopentane production. </li></ul><ul><li>2 i-C 4 H 10 +C 5 H 10 C 8 H 18 + C 5 H 1 2 </li></ul>RHT
  14. 14. Alkylation Chemistry Secondary Reactions H2SO4 <ul><li>Esterification reaction </li></ul><ul><li>Sulfuric acid reacts with olefins to form small amount of di-butyl sulfate, which is unstable at elevated temperatures. This could effect the product quality and also have corrosion problems. </li></ul>RHT
  15. 15. OPERATING VARIABLES <ul><li>Hydrocarbon/ Acid mixing. </li></ul><ul><li>Temperature. </li></ul><ul><li>Isobutane concentration in reactor and in reactor effluent . </li></ul><ul><li>Acid Concentration. </li></ul><ul><li>Olefin Space Velocity,is olefin Volume fed to reactor per hour per volume of Acid Catalyst </li></ul>RHT
  16. 16. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  17. 17. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  18. 18. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  19. 19. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  20. 20. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  21. 21. OPERATING VARIABLES <ul><li>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. </li></ul>RHT
  22. 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.
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  24. 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.
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  30. 31. RHT-A lkylate Revamp <ul><li>Additional reactor and Pumps </li></ul><ul><li>Absorption system if Compression </li></ul><ul><li>bottleneck. </li></ul><ul><li>Coalescers to handle the acid </li></ul><ul><li>separation. </li></ul><ul><li>Existing De-isobutanizer revamp </li></ul><ul><li>Easy to convert HF alkylation </li></ul><ul><li>Vertical equipment , plot area not major constraint. </li></ul><ul><li>Easy to add on additional capacity. </li></ul>RHT
  31. 32. General Considerations <ul><li>Inerts, components which do not contribute in the reaction, take up the Reactor space, reduce the space velocity and Capex. </li></ul><ul><li>Water in acid, lowers acid concentration produces low octane alkylate. </li></ul><ul><li>Polymerization reaction form conjunct polymers (ASO) and dilute the acid concentration and acid consumption. </li></ul><ul><li>Contaminants like diolefins, sulfur compounds and oxygenates consume more acid. </li></ul>RHT
  32. 33. Alkylate yields Etc <ul><li>Alkylate Yield C 3 = C 4 = C 5 = </li></ul><ul><li>Volume V/V O 1.67-1.78 1.70-1.76 1.67-1.83 </li></ul><ul><li>Mass M/M O 2.28- 2.39 2.05-2.09 1.85-2.07 </li></ul><ul><li>Molar m/m O 0.91-1.1 0.96-1.04 1.02-1.22 </li></ul><ul><li>RON C 89-92 94.5- 97.5 92.5-93.5 </li></ul><ul><li>MON C 88.5-90.5 92-95 91.4-92.4 </li></ul><ul><li>Isobutane V/V O 1.02-1.22 1.17-1.2 1.32-1.55 </li></ul><ul><li>Acid cons lb/g Alk 0.55/0.65 0.19/0.26 0.28/0.38 </li></ul><ul><li>O=Olefin, </li></ul>RHT
  33. 34. Safety consideration <ul><li>Spent acid could form mist and SO2 if released under pressure. </li></ul><ul><li>Monitor no acid goes to fractionation </li></ul><ul><li>Spent Acid regeneration off-site </li></ul><ul><li>Non volatile liquid </li></ul><ul><li>Highly corrosive, causes burns on skin </li></ul><ul><li>Adequate monitoring for acid so it is completely taken out before fractionation. </li></ul>RHT
  34. 35. Safety Consideration <ul><li>Caution and measures to Be taken </li></ul><ul><li>Monitor spent acid strength during transfer to storage and transportation. </li></ul><ul><li>To complete Hazop studies </li></ul><ul><li>No volatile hydrocarbon or low strength acid to be sent to storage. </li></ul><ul><li>Prevent acid run away by extensive education and training. </li></ul>RHT
  35. 36. Causes of Acid Runaway <ul><li>Poor mixing </li></ul><ul><li>Low acid in the reactor </li></ul><ul><li>Low acid recycle rates </li></ul><ul><li>High content oxygenates </li></ul><ul><li>Low Acid strength </li></ul><ul><li>High Reactor temperature </li></ul><ul><li>Excessive contaminants </li></ul><ul><li>Loss of acid strength </li></ul><ul><li>Alkylate turns light reddish in color. </li></ul>RHT
  36. 37. Safety Measures <ul><li>Monitor Alkylate color </li></ul><ul><li>Reactor gets cold without Feed reduction </li></ul><ul><li>Control Acid Strength </li></ul><ul><li>Watch for Acid carry over for multiple reasons </li></ul><ul><li>Check acid reactivity before sending to storage for non-reactivity of acid </li></ul><ul><li>Stop feed </li></ul><ul><li>Cold circulation of Isobutane </li></ul>RHT
  37. 38. Reactor Comparisons <ul><ul><li>Conventional RHT- Alkylate </li></ul></ul><ul><ul><li>Standard sizes Economy of Scale </li></ul></ul><ul><ul><li>No moving parts Simple Eductors complicated seals/ as Mixing device, internals no scale up issues </li></ul></ul><ul><ul><li>Frequent Normal process </li></ul></ul><ul><ul><li>Maintenance equipment , safe </li></ul></ul><ul><ul><li>internal piping. </li></ul></ul>RHT
  38. 39. Auto Refrigeration vapor <ul><ul><li>Compression is normally used. Option to use low cost absorptions system patented by RHT- Alkylate. </li></ul></ul><ul><ul><li>Easier to revamp with this option. </li></ul></ul><ul><ul><li>Simple design and operating system , no moving parts, lower capex and Opex. </li></ul></ul>RHT
  39. 40. RHT-Alkylate Technology Advantages <ul><li>Novel reactor and Mixing device </li></ul><ul><li>No Complex internals in the Reactor </li></ul><ul><li>No Maintenance and mechanical Problems </li></ul><ul><li>Isothermal Low temperature operation </li></ul><ul><li>Unique Configuration allows good mixing and interfacial area. </li></ul><ul><li>Auto refrigeration vapor can be absorbed which is low cost option, and unique for revamps. </li></ul><ul><li>Acid/ Hydrocarbon separation by standard coalescers. </li></ul><ul><li>Standard Process industry equipment </li></ul>RHT
  40. 41. RHT-Alkylate Technology Advantages <ul><li>Lower capex by 33 to 45 % due to economy of scale and absorption and Acid/ Hydrocarbon coalescers. </li></ul><ul><li>Lower Opex by >35 % and with absorption system more cold energy is available. </li></ul><ul><li>Better Octane Product </li></ul><ul><li>Lower acid consumption </li></ul><ul><li>isothermal Low temperature operation </li></ul><ul><li>Easier revamps. </li></ul>RHT
  41. 42. <ul><li>We have the answers </li></ul><ul><li>Simple Design to meet your requirements. </li></ul><ul><li>Thought of C3/C4 /C5 injection system. </li></ul><ul><li>Simple Acid/Hydrocarbon separation system. </li></ul><ul><li>No special internals to be provided by single source. </li></ul><ul><li>Unique absorption system instead of compressor. </li></ul><ul><li>Lower capex and opex </li></ul><ul><li>Higher octane and lower acid consumption </li></ul>WHY RHT Technology RHT