WO2008082866A1 - Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins - Google Patents
Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins Download PDFInfo
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- WO2008082866A1 WO2008082866A1 PCT/US2007/087065 US2007087065W WO2008082866A1 WO 2008082866 A1 WO2008082866 A1 WO 2008082866A1 US 2007087065 W US2007087065 W US 2007087065W WO 2008082866 A1 WO2008082866 A1 WO 2008082866A1
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- Prior art keywords
- catalyst
- fluidized bed
- stream
- mixed fluidized
- mixed
- Prior art date
Links
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 47
- 238000002156 mixing Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 102
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 230000003197 catalytic effect Effects 0.000 claims description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000001282 iso-butane Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 30
- 239000012071 phase Substances 0.000 description 25
- 238000000926 separation method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 olefin hydrocarbons Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
- C07C5/324—Catalytic processes with metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/321—Catalytic processes
- C07C5/324—Catalytic processes with metals
- C07C5/325—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/36—Rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- This invention relates to a catalytic dehydrogenation process and system with improved conversion and selectivity and lower operating and installation costs.
- alkanes paraffin hydrocarbons
- alkenes olefin hydrocarbons
- propylene can be used in the production of polymers and propylene glycol
- butylenes can be used in the production of high octane motor fuel
- isobutylenes can be used to produce methyl-t-butyl ether, a gasoline additive.
- the catalytic dehydrogenation of alkanes is an endothermic reaction. The reaction is very fast and reversible and conversion rates are limited by the thermodynamic equilibrium conditions. High temperatures and low pressures favorably displace the reaction toward the formation of alkenes.
- the interheaters are positioned between the reactors to ensure that at the entrance of each of the reactors, the temperature conditions necessary for the endothermic dehydrogenation reaction are met.
- a set of catalytic dehydrogenation reactors are operated in a cyclic non-steady-state mode with regeneration of a catalyst bed every 10 to 30 minutes, as described in US 6,392,113.
- the catalyst bed is heated during regeneration and this heat is used to carry out the dehydrogenation reaction.
- Reactors are large and multiple reactors in parallel are needed for large plant sizes. Frequent cycling of the system can lead to operational and maintenance problems and the non-continuous system is less thermally efficient than a continuous process.
- the formation of heavy byproducts can foul the reactors, with the result that the catalytic dehydrogenation system has to be shut-down periodically and cleaned.
- the heavy byproducts are separated from the unconverted alkane prior to recycle of the unconverted alkane using a front-end distillation column.
- Deactivated catalyst is withdrawn from the reactor and sent to a regenerator where coke is burned off the catalyst to regenerate it. Additional fuel is also burned in the regenerator to raise the temperature of the catalyst.
- the hot catalyst is then returned to the fluidized bed reactor, providing the heat necessary for the endothermic dehydrogenation of the alkane-rich stream.
- the fluidized bed is designed to be highly back-mixed in the fluidized phase. Because the reactor has a highly back-mixed solids phase, the alkanes are not exposed to high temperatures and the fluidized bed is maintained at an essentially isothermal condition. Eliminating exposure to high temperatures reduces selectivity losses due to thermal cracking reactions and the formation of heavy byproducts.
- FIG. 1 is a schematic view of a flow scheme of the present invention.
- FIG. 2 is a schematic drawing of a reactor of the present invention.
- a feed comprising one or more alkanes enters the process through a line 1.
- the feed is heated in a furnace 2 and is passed through a line 3 to a back-mixed fluidized bed reactor 4.
- the feed is heated in the furnace 2 to a reaction temperature.
- the reaction temperature is preferably in the range from 300° to 700 0 C and most preferably about 580° to 620 0 C.
- the feed in the present invention is not preheated to a temperature well- above the final reaction temperature.
- the lower feed temperatures utilized in the present invention advantageously reduce or eliminate undesired thermal cracking reactions. This increases the desired product yield. Using lower temperatures also reduces operating costs.
- the back-mixed fluidized bed reactor 4 contains a back-mixed fluidized bed of a suitable catalyst for dehydrogenation of alkanes.
- the fluidized bed reactor 4 is designed to be highly back-mixed in the fluidized phase; i.e., solids within the back-mixed fluidized bed reactor 4 behave as if they are in a continuously stirred tank reactor (CSTR). It is also preferred that the back-mixed fluidized bed reactor 4 comprises a fast fluidized bed of catalyst.
- Suitable catalysts are well known to those skilled in the art and typically comprise a support material chosen from the group comprising: alumina, silica, aluminosilicates, aluminophosphates, natural and synthetic zeolites, clays and metal oxides on which is dispersed a metal from the group comprising iron, nickel, chromium, molybdenum, tungsten, palladium, platinum, rhenium and cobalt.
- the catalyst preferably has a particle size in the range 10 to 500 micrometers and more preferably in the range 20 to 200 micrometers.
- Use of a fast back-mixed fluidized bed minimizes carbonaceous deposits within the back- mixed fluidized bed reactor 4 and makes the process of the present invention more resistant to coking or fouling than prior art fixed or moving bed processes.
- the back-mixed fluidized bed reactor 4 is maintained at a low process pressure, to favor the equilibrium of the alkane dehydrogenation reaction.
- the low process pressure is preferably in the range from an absolute pressure of 50 kPa to an absolute pressure of 500 kPa and is most preferably about 125 to 250 kPa.
- a dehydrogenation reactor product is withdrawn from the back-mixed fluidized bed reactor 4 through a line 5 and is cooled by heat exchange in a heat exchange system 6.
- the heat exchange system 6 may comprise one or more heat exchangers for recovery of heat from the dehydrogenation reactor product for various uses in the process.
- a cooled dehydrogenation reactor product is withdrawn from the heat exchange system 6 through a line 7 and is sent to a separation section 8.
- the cooled dehydrogenation reactor product is separated into a hydrogen-rich product, an alkane- rich product and an alkene-rich product.
- the hydrogen-rich product leaves the separation section 8 in a line 9 and is available for sale as hydrogen or for use as a process fuel.
- the alkane-rich product leaves the separation section 8 in a line 10 and can be recycled to the feed and returned to the line 1, or else can be used as fuel.
- the alkene-rich product leaves the separation section 8 in a line 11 and is suitable for sale or further processing.
- An air stream is drawn via a suction line 70 into an air compressor or blower 71, where it is compressed to form a compressed air stream.
- the compressed air stream is preferably at a pressure in the range 100 to 3,000 kPa and most preferably in the range 200 to 500 kPa.
- the compressed air stream is sent via a line 72 to a precombustor 73, where it meets a fuel stream entering via a line 74 and undergoes a combustion reaction to form a preheated air stream.
- the energy released from the combustion reaction raises the temperature of the preheated air stream to a preheat temperature.
- the preheated air stream is sent via a line 75 to a regenerator 76.
- the regenerator 76 comprises one or more reactors suitable for regenerating the catalyst.
- the regenerator 76 may comprise a bubbling bed reactor or a fast fluidized bed reactor.
- the regenerator 76 comprises a single fast fluidized bed reactor.
- a first supplementary fuel stream may also be fed to the regenerator 76 via a line 77.
- the preheated air stream reacts with any coke that is deposited on deactivated catalyst contained in the reactor or reactors of the regenerator 76, forming a hot flue gas, which leaves the regenerator 76 and can be vented to atmosphere via a line 78.
- the hot flue gas leaving the regenerator 76 may be expanded in a turbine (not shown for clarity) to form a low-pressure flue gas.
- the low-pressure flue gas is withdrawn from the turbine in a line and is sent to a waste heat boiler for recovery of heat before being vented to the atmosphere via a line.
- the hot flue gas leaving the regenerator 76 may be combined with a second supplementary fuel stream and fed to a waste heat boiler (not shown for clarity) for recovery of heat before being vented to atmosphere via a line.
- a stream of deactivated catalyst is withdrawn continuously from the back-mixed fluidized bed reactor 4 via a line 38, and is sent to the regenerator 76.
- a stream of regenerated catalyst is withdrawn continuously from the regenerator 76 via a line 36, and is sent to the back-mixed fluidized bed reactor 4.
- a first product defined as [(catalyst mass flow rate x catalyst specific heat capacity) x(temperature of the hot regenerated catalyst-temperature of the back-mixed fluidized bed of catalyst)] is substantially equal to a second product defined as [moles of the alkane stream converted x molar heat of reaction for dehydrogenation of the alkane stream].
- the back-mixed fluidized bed reactor 4 for the dehydrogenation of alkanes is illustrated in schematic form.
- the back-mixed fluidized bed reactor 4 comprises a disengaging zone 62 and a lower reaction zone consisting of a dense phase zone 44 and a transition phase zone 46.
- a vapor phase feed comprising one or more alkanes enters via the line 3 to a feed inlet 14.
- the vapor phase feed passes through a feed distributor 34 and enters the dense phase zone 44.
- the feed distributor 34 comprises a sieve plate which permits the vapor phase feed to pass through while retaining a catalyst above the sieve plate.
- the catalyst in the dense phase zone 44 and the transition phase zone 46 comprises a suitable catalyst for dehydrogenation of paraffinic hydrocarbons.
- Suitable catalysts are well known to those skilled in the art and typically comprise a support material chosen from the group comprising: alumina, silica, aluminosilicates, aluminophosphates, natural and synthetic zeolites, clays and metal oxides on which is dispersed a metal from the group comprising iron, nickel, chromium, molybdenum, tungsten, palladium, platinum, rhenium and cobalt.
- the dense phase zone 44 is operated in a regime of fluidization characterized by extensive back-mixing of the fluidized (solids) phase, such that the temperature of the catalyst is substantially uniform at all points in the dense phase zone 44.
- the dehydrogenation reactor product stream comprises alkenes, unconverted alkanes and hydrogen.
- a carbonaceous deposit is produced on the catalyst, reducing the activity of the catalyst.
- the dehydrogenation reactor product stream and a catalyst mixture comprising active catalyst and some deactivated catalyst are conveyed into the transition phase zone 46 in an intermediate portion of the lower reaction zone.
- the cross-sectional area of the flow path through the back-mixed fluidized bed reactor 4 is reduced from the cross-sectional area of the dense phase zone 44 by a reducing means 25, or cone section, to the cross-sectional area of the riser section 26.
- the superficial velocity through the transition phase zone 46 varies between about 1 and 3 meters per second (about 3 to about 10 feet per second).
- the riser section 26 has a smaller diameter and a smaller cross- sectional area than the dense phase zone 44 which increases the superficial velocity through the riser section 26 relative to that through the dense phase zone 44.
- the cross-sectional area of the overall back-mixed fluidized bed reactor 4 can be decreased by about a factor of 2 or 3 times compared to the cross-sectional area of a bubbling bed reactor.
- the back- mixed fluidized bed lower reaction zone provides more precise control of the feedstock and catalyst rates without the need for external catalyst addition or removal.
- the back- mixed fluidized bed reaction system of the present invention provides significantly decreased catalyst inventories over a traditional bubbling bed reactor.
- the dehydrogenation reactor product stream and catalyst mixture continue to be conveyed through the riser section 26.
- the riser section 26 discharges the dehydrogenation reactor product stream and catalyst mixture through a separation zone comprising distributor arms 24, or discharge opening, and a separation vessel 22.
- the discharge opening 24 tangentially discharges the dehydrogenation reactor product stream and catalyst mixture to create a centripetal acceleration of the catalyst mixture and a vapor portion of the dehydrogenation reactor product stream within the separation vessel 22 that provides an initial stage cyclonic separation.
- the catalyst mixture falls to the bottom of the disengaging zone 62 which defines a particle outlet for discharging fluidized catalyst particles and the vapor portion of the dehydrogenation reactor product stream passes upwardly through a gas recovery outlet 23 for withdrawing gaseous fluids from the separation vessel 22.
- the vapor portion of the dehydrogenation reactor product comprising entrained catalyst, continues upwards to a dilute phase separator typically in the form of a series of one to three conventional cyclone separation stages shown in the drawing as 20 and 21.
- the cyclone separation stage 20 represents a primary cyclone separation wherein a primary cyclone vapor stream is passed to the secondary cyclone separation stage 21 and the secondary vapors from the secondary cyclone separation stage 21 are conveyed via a conduit 17 to a plenum chamber 16.
- a net dehydrogenation reactor product stream comprising less than about 100 ppm-wt catalyst is withdrawn via the line 5 from a reactor outlet 12.
- the net dehydrogenation reactor product stream withdrawn from the fast-fluidized bed lower reaction zone comprises less than about 70 ppm-wt catalyst.
- Catalyst separated in the primary cyclone separation stage 20 drops through a dip leg 59 into the bottom of the disengaging zone 62.
- Catalyst separated from the dehydrogenation reactor product stream in the secondary cyclone separation stage falls through a dip leg 60 into the bottom of the disengaging zone 62.
- the dip legs 59 and 60 are fitted with flapper valves (not shown) at their base to prevent the back flow of vapors through the cyclone separation stages 20 and 21.
- Catalyst accumulated in the bottom of the disengaging zone 62 is allowed to achieve an upper catalyst level and any excess catalyst is passed through at least one external catalyst recirculation standpipe 28 through a recirculation slide valve 32, and returned to the dense phase zone 44.
- at least two external catalyst recirculation standpipes are employed to return catalyst from the disengaging zone 62 to the dense phase zone 44.
- a heat transfer zone 30 is disposed in the external catalyst recirculation standpipe 28 at a point above the recirculation slide valve 32.
- the use of the heat transfer zone 30 allows the addition of heat to the circulating catalyst to meet the needs of the endothermic reactions taking place in the lower reaction zone.
- the activity of the catalyst in the lower reaction zone gradually is reduced by the buildup of coke on the catalyst.
- a portion of the catalyst mixture is withdrawn as a spent catalyst stream from the upper disengaging zone 62 and passed through a spent catalyst standpipe 42.
- the spent catalyst stream is stripped with a stripping medium such as steam introduced in a line 37 to produce a stripped catalyst stream 56.
- the spent catalyst standpipe 42 will typically include a stripping section that contains grids or baffles to improve contact between the spent catalyst stream 56 and the stripping medium.
- the stripped catalyst stream 56 is conveyed through a line 38 and a spent catalyst slide valve 39.
- the stripped catalyst stream 56 is passed to a catalyst regeneration zone (not shown).
- the spent catalyst stream 56 is at least partially regenerated either by oxidation or reduction to produce a regenerated catalyst stream 52.
- Such regeneration schemes are well known to those skilled in the art of fluidized bed reaction systems.
- the regenerated catalyst stream 52 is returned to the lower reaction zone via a regenerated catalyst standpipe comprising a line 40, a regenerated catalyst slide valve 41, and a line 36 to a point above the dense phase zone 44.
- the regenerated catalyst return is shown at a point above the dense phase zone 44.
- the return of the regenerated catalyst stream 52 to the lower reaction zone may be provided at any point in the riser section 26 or any portion of the back-mixed fluidized catalyst bed.
- the dense phase zone 44 is operated to maintain a bed height of between about 2 meters (7 feet) and about 6 meters (20 feet) above the feed distributor 34 and below the intermediate portion of the lower reaction zone in the dense phase zone 44. More preferably, the bed height of the dense phase zone 44 comprises between about 2.4 meters (8 feet) and about 4 meters (13 feet).
- a mixture of hydrogen and propane is fed to a single-stage back- mixed reactor with inlet temperature of 632°C and outlet pressure of 170 kPa (10 psig).
- the process achieves a conversion of 40% of the propane with 96% molar selectivity to propylene.
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- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP07869106A EP2097163A4 (en) | 2006-12-28 | 2007-12-11 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
KR1020097013586A KR101489768B1 (en) | 2006-12-28 | 2007-12-11 | A catalytic dehydrogenation process and system for dehydrogenating an alkane stream |
CN2007800483344A CN101568379B (en) | 2006-12-28 | 2007-12-11 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
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US88234906P | 2006-12-28 | 2006-12-28 | |
US60/882,349 | 2006-12-28 |
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WO2008082866A1 true WO2008082866A1 (en) | 2008-07-10 |
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PCT/US2007/087065 WO2008082866A1 (en) | 2006-12-28 | 2007-12-11 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
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EP (1) | EP2097163A4 (en) |
KR (1) | KR101489768B1 (en) |
CN (1) | CN101568379B (en) |
MY (1) | MY145854A (en) |
WO (1) | WO2008082866A1 (en) |
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US8624074B2 (en) * | 2010-03-22 | 2014-01-07 | Uop Llc | Reactor flowscheme for dehydrogenation of propane to propylene |
CN103121892A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin by alkane |
CN103449948B (en) * | 2012-06-01 | 2015-02-25 | 中国石油天然气集团公司 | Method for preparing olefin through dehydrogenating alkane |
US20160068454A1 (en) * | 2013-04-08 | 2016-03-10 | Saudi Basic Industries Corporation | Reactor and process for paraffin dehydrogenation to olefins |
CN104072325A (en) * | 2014-07-10 | 2014-10-01 | 南京沃来德能源科技有限公司 | Method for improving performance of dehydrogenation reaction of light alkane |
US11186784B2 (en) * | 2018-10-15 | 2021-11-30 | Uop Llc | Dehydrogenation process having improved run time |
KR102610122B1 (en) * | 2021-10-15 | 2023-12-06 | 서울대학교산학협력단 | Composite Catalyst Physically Mixed with Nickel Oxide and Method for Manufacturing the Same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4613715A (en) * | 1985-07-12 | 1986-09-23 | Phillips Petroleum Company | Oxygen addition to a steam-active dehydrogenation reactor |
US5389342A (en) * | 1991-12-30 | 1995-02-14 | Pillips Petroleum Company | Apparatus for dehydrogenation process control |
WO2005077867A2 (en) * | 2004-02-09 | 2005-08-25 | The Dow Chemical Company | Process for the preparation of dehydrogenated hydrocarbon compounds |
Family Cites Families (4)
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US2820072A (en) * | 1955-04-25 | 1958-01-14 | Exxon Research Engineering Co | Catalytic dehydrogenation in transfer line reactor |
FI98529C (en) * | 1994-03-31 | 1997-07-10 | Neste Oy | Method and apparatus for the preparation of light olefins |
US20040092391A1 (en) * | 2002-11-08 | 2004-05-13 | Andrzej Rokicki | Fluid bed catalyst for dehydrogenation of hydrocarbons |
DE102004007358B4 (en) * | 2004-02-16 | 2017-10-12 | Chiron As | Congeners, chlorinated, brominated and / or iodinated fluorinated aromatic compounds containing two benzene rings in their basic structure, process for their preparation and their use |
-
2007
- 2007-12-11 MY MYPI20092488A patent/MY145854A/en unknown
- 2007-12-11 CN CN2007800483344A patent/CN101568379B/en active Active
- 2007-12-11 KR KR1020097013586A patent/KR101489768B1/en active IP Right Grant
- 2007-12-11 WO PCT/US2007/087065 patent/WO2008082866A1/en active Application Filing
- 2007-12-11 EP EP07869106A patent/EP2097163A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4613715A (en) * | 1985-07-12 | 1986-09-23 | Phillips Petroleum Company | Oxygen addition to a steam-active dehydrogenation reactor |
US5389342A (en) * | 1991-12-30 | 1995-02-14 | Pillips Petroleum Company | Apparatus for dehydrogenation process control |
WO2005077867A2 (en) * | 2004-02-09 | 2005-08-25 | The Dow Chemical Company | Process for the preparation of dehydrogenated hydrocarbon compounds |
Non-Patent Citations (1)
Title |
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See also references of EP2097163A4 * |
Also Published As
Publication number | Publication date |
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CN101568379A (en) | 2009-10-28 |
CN101568379B (en) | 2013-02-13 |
EP2097163A4 (en) | 2012-05-23 |
KR101489768B1 (en) | 2015-02-04 |
MY145854A (en) | 2012-04-30 |
KR20090103905A (en) | 2009-10-01 |
EP2097163A1 (en) | 2009-09-09 |
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