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RHT Alkylation: Breakthrough Technology for Refinery Gasoline Economics

Discover how RHT's smart technologies are changing the economics of refinery gasoline through innovative RHT-ISO-OCTENE and RHT-ISO-OCTANE processes. Presented by Dr. Amarjit Bakshi at the International Conference on Chemical Engineering 2016.

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RHT Alkylation: Breakthrough Technology for Refinery Gasoline Economics

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  1. RHT- ALKYLATION RHT-ISO-OCTENE & ISO-OCTANE TECHNOLOGY CHANGE REFINERY GASOLINE ECONOMICS BY BREAKTHROUGH SMART TECHNOLOGIES Dr. Amarjit Bakshi President, Refining Hydrocarbon Technologies Texas, USA. www.rhtgulfcoast.com Presented at International Conference on Chemical Engineering Chemical Engineering 2016 Organizing Committee Member Sep 12-14, 2016 Phoenix, USA. Confidential 1 RHT

  2. Valuable C4 Components • Butadiene ~ > 99.7 % -- Used for Synthetic rubber, tires,Nylon, Latex, ABS resins and other plastics • Butene-1 ~ > 99.0 % -- Used as Co-monomer for PE and higher Alcohol production. • Isobutylene ~ 99.8 % -- Used for Butyl rubber production,lube oil,additives,antioxidants,specility resin . RHT Confidential

  3. Valuable C4 Components • Diisobutylene ~ 99.0 % • -- Used for surfactants, dispersents and rubber processing chemicals. • Mixed Butylenes • -- Used for producing Alkylate, Iso-Octane and Ethers • Polyisobutylene • -- Used for lube additives etc RHT Confidential

  4. Why RHT LLC Technology • Conventional Technology • LOW COST, HIGH YIELD PROCESS • For ETBE, No Dehydration Unit Required, Reducing Cost by a Factor • Costs of Dehydration is 30 to 50% of the MTBE Unit • No Proprietary Catalyst and Loading Required • Catalyst can be changed on the run/during operation • Can provide Selective Hydrogenation in the Reactor so as to Save the Expensive Catalyst in the Column Confidential RHT

  5. Mixed Butylene Production Steam Cracker FCC Units Other Thermal Crackers For MTBE and other special use from Dehydrogenation Confidential RHT Confidential 5

  6. Uses Of Butylenes Mixed Butylenes for Alkylationand ether Production Mixed Butylenes for MMA Pure Isobutylene for Rubber and Lubes Pure 1- Butene as Monomer Butene-2 for butanol and metathesis for Propylene production Isobutane goes to alkylation RHT Confidential Confidential 6

  7. RHT-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. 7 RHT Confidential

  8. RHT-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 8 Confidential RHT

  9. RHT-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 %. 9 Confidential RHT 6

  10. RHT-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. Confidential RHT

  11. RHT-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. Confidential 11 RHT

  12. Alkylation Chemistry • Reaction Chemistry is pretty complex but same as conventional Alkylation Process chemistry though better yield observed at low temperature (US Pat. 5095068) • Process Selective at low temperature hence less acid soluble oil produced (US Pat. 7,652,187 ) • Reference US Pat. 5284990 Confidential RHT

  13. Alkylation ChemistryMain 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 Confidential RHT RHT

  14. Figure1RHT-Alky: Block Flow Diagram Confidential RHT

  15. Figure 2RHT Novel C4 Vapor RecoverySystem Confidential RHT

  16. RHT-Alkylate Revamp • Additional reactor and pumps • Absorption system if compression bottleneck • Coalescers to handle acid separation • Existing de-isobutaner revamp • Easy to convert HF alkylation • Vertical equipment, plot area not major constraint • Easy to add additional capacity Confidential RHT

  17. Reactor Comparisons ConventionalRHT- 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 Confidential RHT

  18. Operating Variables • Hydrocarbon / Acid Mixing • Reactor temperature • Isobutane concentration in Reactor and Reactor effluent • Acid concentration • Olefin space velocity is olefin volume fed to Reactor per hour per volume of acid catalyst Confidential RHT

  19. Operating Variables • Hydrocarbon / Acid mixing is a major variable in the alkylation reaction so that 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 Confidential

  20. Operating Variables • Temperature, another variable which is very important for alkylation. RHT configuration provides the best results due to essentially isothermal conditions (25-30 F) in the reactor. Higher reaction temperature favors polymerization reactions, which reduces the acid concentration, increases acid consumption, corrosion and reduces Product Quality/Octane. RHT has the system working at isothermal conditions • providing optimal reaction conditions. Confidential RHT

  21. Operating Variables • Isobutane concentration is kept at the optimum condition I/O ratio ranges from 6 to 15 to provide good product quality and selectivity. Optimum ratio is used so as to optimize de-isobutanizer utilities. Lower I/O ratio enhances the olefin polymerization, which is not good for quality and increases acid consumption. Isobutane in Reactor effluent is 53% to 75% by Vol. Confidential RHT

  22. Operating Variables • Acid concentration is very important for alkylation reaction. At lower acid concentration, ASO increases and product quality goes down. Normal acid concentrations are kept in the range of 89% to 95%. With concentration below 86%, activity is decreased, enhancing polymerization. Confidential RHT

  23. 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 in the Reactor is optimized in relation to olefin, providing optimum results in the range of 40% to 60%. RHT Confidential

  24. CASE STUDY Sulfuric Acid Alkylation : Conventional/CDAlky VS RHT- ALKYLATION • Basis of design and assumptions • 100,000 Bbls/d FCC unit • C4 Stream of 20100 Bbls/d based on operation and catalyst. • 63 % Lv of olefins in C4 stream • Mature technology as regards to Sulfuric acid alkylation RHT Confidential

  25. CASE STUDY TABLE 1 Sulfuric Acid Alkylation : Conventional/CDAlky VS RHT- ALKYLATION Stream FCC C4s BPSD 20100 LV% of Olefins 63.0 Composition LV % C3’s 0.1 ibutane 28.6 ibutene 16.2 1-butene 15.5 2-butene 31.3 1,3 butadiene 0.1 nbutane 8.2 Total 100.0 RHT Confidential

  26. CASE STUDY Sulfuric Acid Alkylation : Conventional Propane 99.5 LV% C4’s 0.5 LV% 238 bbl/d C3’s Product 20100 Bbl/d Table 1 n-Butane Product to NGPSA spec FCC C4’s STREAM TO ALKY Conventional LV% LV% LV% Isobutane 2.5 n-butane 96.5 C5’s 1.0 10848 Bbl/d ISOBUTANE FEED bbl/d 3401 % LV Alkylate Product Bbl/d 23504 Road Octane 94.1 RVP, psia 5.0 CON Propane 2.0 Isobutane 80.0 Butane 18.0 Make Up Acid Water 3.2 % Sulfuric Acid 90.0% ASO 6.8 % Spent Acid, lb/h 24558 Lb/h 22171 Sulfuric acid 99.0 % Water 1.0% Confidential RHT

  27. CASE STUDY Sulfuric Acid Alkylation : Summary • Alky Product ConventionalRHT • Bbl/d 23504 23762 • (R+M)/2 94.1 95.2 • RVP, psia 5.0 5.0 • Capital Cost(1) USD/bbl • 4145 2419 • 1) Gulf coast basis 2 Q 2016 Confidential RHT

  28. CASE STUDY Sulfuric Acid Alkylation : Economic Summary Conventional RHT Acid Cost MM $/y(1) 10.7 5.1 Utilities Cost MM $/y 14.8 10.9 Octane Value MM$/y(2) Base +18.4 Total dollar advantage/y(3) Base +27.9 Acid: lbs/gallon alkylate: 0.55 0.25 (1) Sulfuric Acid at 125 USD/Mt (2) Octane advantage at 1.0 USD/Octane barrel (3) Operating cost savings excluding Acid regeneration. (4) Capex advantage not taken into account for revamps. RHT Confidential

  29. RHT-Alkylate TechnologyAdvantages • 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 Confidential RHT

  30. Why RHT Alkylation Technology • We have the answers. • Simple design to meet your requirements with unique eductor mixing device • Simple Acid/Hydrocarbon separation system • No special internals to be provided by single source • Unique absorption system instead of compression • Lower Capex and Opex, Higher octane and lower acid consumption Confidential RHT

  31. C4 Other uses • C4 refinery economics enhancement • Isobutylene Dimerization • Smart Configuration RHT Confidential

  32. NEW DEVELOPMENTS IN RHT-ISOOCTENESM RHT-ISOOCTANESM TECHNOLOGY Confidential RHT

  33. WHY RHT-Iso-octeneSM • Novel configuration provides low cost simple catalyst system , improves conversion and catalyst life. • With a new Selectivator, the RHT process provides higher yield and selectivity than other processes, Isobutylene conversion of 97 to 99 % to Iso-octene product. Confidential RHT

  34. WHY RHT-Iso-octeneSM • Lower codimers produced by reducing the per pass conversion in First Reactor. • Reduces loss of normal olefins for Alkylation. • Conventional catalyst and configuration lends to catalyst change while on line, hence conversions are higher on an average compared to any technology available in the market. Confidential RHT

  35. Figure 1 RHT Iso-Octene Process Water wash Column Mixer Reactor Debutanizer C4 Raffinate LP H2 CW Water Wash C4 Feed (1) Iso-Octene Product Confidential RHT (1) 1 to 3% propylene in feed

  36. Figure 2 RHT Iso-Octene Process Water wash Column Mixer Debutanizer 1 st Reactor Finishing Reactor Iso-octene Column C4 Raffinate Selectivator Recycle LP H2 Water Wash C4 Feed (1) Iso-Octene Product Water to Treatment Confidential RHT (1) 1 to 3% propylene in feed

  37. Figure 3 RHT Iso-Octene Process Debutanizer Water wash Column Mixer Reactor Iso-octene column C4 Raffinate IPA LP H2 Water Wash (multiple) C4 Feed (1) Iso-Octene Product Confidential RHT (1) 1 to 3% propylene in feed

  38. Figure 4 RHT Iso-Octene Process Revamp of Conventional MTBE Unit Mixer NEW MeOH Column Existing Water Wash Column Existing MeOH Extractor Existing Deleted Finishing Reactor Existing Debutanizer Existing 1 st Reactor Existing MeOH C4 Raffinate IPA Recycle to Reactor LP H2 CW Water Wash CW C4 Feed (1) Iso-Octene Product Water to Treatment Confidential MTBE Product (1) 1 to 3% Propylene in the feed RHT 42

  39. Figure 6RHT Iso-octene to Iso-octane Hydro Mixer 1 st Reactor K.O.Drum Finishing Reactor Iso-octane Stripper Iso-octene Vent 7 H2 CW 1 6 2 Cooler 4 3 Hydrogen Iso-octane Product Confidential RHT

  40. WHY RHT-Iso-octeneSM • Distillation performed at optimum conditions. • Easy to revamp the existing MTBE units. • Low cost revamp most of the equipment can be used from MTBE unit. Confidential RHT

  41. WHY RHT-Iso-octaneSM • The hydrogenation/olefin Saturation is done at lower pressure , which reduces the capital cost and utilities. • Conventional but high activity dual catalysts use for olefin saturation. • Essentially over 99 % olefin hydrogenation to Paraffins is achieved. Confidential RHT

  42. RHT Portfolio • Please see website www.rhtgulfcoast.com and LINKEDIN for other details and presentations attached to profile. • RHT LLC provides essentially all hydrogenation technologies ( selective hydrogenation, HDS of Naphtha and Diesel, isomerization, Benzene Saturation with Smart Configuration and enhanced economics and other renewable fuels and in the petrochemical area. • Information provided under NDA please contact us and look up the Patents/IP. • RHT provides multi Client studies, consultation to Fund Managers through third party and EHS and FEED, Basic Engineering & EPC services to major Clients. Confidential RHT

  43. Thank You Refining Hydrocarbon Technologies LLC 20130 Chateau Bend Drive Katy ( Houston Suburb), Texas 77450 USA Dr. Amarjit Bakshi Phone 281-398-8408/281-235-7780 E-mail:abakshi@rhtgulfcoast.com www.rhtgulfcoast.com RHT Confidential

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