US20060084830A1 - Selective hydrogenation process and catalyst - Google Patents
Selective hydrogenation process and catalyst Download PDFInfo
- Publication number
- US20060084830A1 US20060084830A1 US10/969,613 US96961304A US2006084830A1 US 20060084830 A1 US20060084830 A1 US 20060084830A1 US 96961304 A US96961304 A US 96961304A US 2006084830 A1 US2006084830 A1 US 2006084830A1
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- US
- United States
- Prior art keywords
- catalyst
- support
- catalyst according
- alumina
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 59
- 229910052596 spinel Inorganic materials 0.000 claims description 21
- 239000011029 spinel Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 92
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 59
- 238000000151 deposition Methods 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 229910052792 caesium Inorganic materials 0.000 abstract description 2
- 229910052730 francium Inorganic materials 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 229910052701 rubidium Inorganic materials 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 229910052712 strontium Inorganic materials 0.000 abstract description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 23
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 18
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
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- 150000001336 alkenes Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
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- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 6
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- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000895 extractive distillation Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- -1 ethylene, propylene, butadiene Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BOFLDKIFLIFLJA-UHFFFAOYSA-N 2-methylbut-1-en-3-yne Chemical compound CC(=C)C#C BOFLDKIFLIFLJA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- VBUBYMVULIMEHR-UHFFFAOYSA-N [H]C#CC([H])([H])[H].[H]C([H])=C=C([H])[H] Chemical compound [H]C#CC([H])([H])[H].[H]C([H])=C=C([H])[H] VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 150000005673 monoalkenes Chemical class 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
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- 238000004230 steam cracking Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- 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
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/892—Nickel and noble metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Definitions
- the present invention relates to the selective removal of acetylenic compounds from hydrocarbon streams using specific Ni-based catalysts and the process of making the catalysts.
- the process is particularly useful in cleaning up MAPD (methyl acetylene and propadiene) and acetylene in crude mixed olefin streams or phenylacetylene in crude styrene streams by selective hydrogenation in the presence of the Ni-based catalyst.
- MAPD methyl acetylene and propadiene
- Acetylenic impurities such as acetylene, methyl acetylene, vinyl acetylene, ethyl acetylene, and 2-methyl-1-buten-3-yne are found in various crude mixed C 2 -C 5 streams, for example in the manufacture of olefins such as ethylene, propylene, butadiene and isoprene.
- olefins such as ethylene, propylene, butadiene and isoprene.
- These acetylenic impurities need to be removed with a minimum loss of the useful olefinic materials, i.e., ethylene, propylene, butenes, butadiene, isoprene and the like.
- 1,3-butadiene is an important raw material used to produce various polymers such as butadiene-styrene copolymer.
- One of the processes for producing 1,3-butadiene is co-production of various olefins by steam cracking of petroleum fractions.
- the crude mixed C 4 stream from a steam cracker is selectively hydrogenated to partially remove C 4 acetylenic compounds.
- the selectively hydrogenated stream is sent to the 1,3-butadiene recovery unit where solvent extractive distillation techniques are used to separate 1,3-butadiene from the rest of components in the mixed stream.
- Solvent extractive distillation is expensive to operate and energy consumption is intensive.
- the preferred technique for the purification in commercial practice is the selective hydrogenation of acetylenic compounds over hydrogenation catalysts.
- Supported Pd, Ni, Cu and Co catalysts are known as useful for the hydrogenation of acetylenes (Handbook of Commercial Catalysts, pp. 105-138, Howard F. Rase, CRC Press, 2000).
- the most preferred catalysts in prior commercial applications of selective hydrogenation of acetylenes are palladium-based catalysts such as Pd, Pd/Pb, Pd/Ag or Pd/Au on a support such as alumina and the copper catalysts on a support such as alumina.
- Pd catalysts were the most preferred catalysts because of high activity and higher selectivity compared with other known metal catalysts.
- palladium-based catalysts are not selective enough to completely remove C 4 acetylenes without an unacceptable amount of 1,3-butadiene loss due to over-hydrogenation.
- Another inherent problem of palladium-based catalysts is the loss and migration of palladium due to the formation of soluble Pd complex compounds by the reaction of Pd atoms on the catalyst surface with vinyl acetylene, if the hydrogenation is carried out with a liquid phase.
- Silver and gold have been used to minimize the loss of palladium and reduce catalytic polymerization of acetylenic compounds.
- the copper-based catalysts are very selective so that the recovery of 1,3-butadiene from the mixed stream is very high compared with palladium-base catalysts.
- the activity of copper catalysts is very low compared with palladium-based catalysts, and a large volume of catalyst and large reactor are required. Also because the deposition of heavy carbonaceous materials on the catalyst occurs quickly, frequent regeneration of catalysts necessitates multiple reactors.
- Ni catalysts in any form are very active catalysts for selective hydrogenation of acetylenes and dienes.
- Ni and Ni—Cu alloy catalysts are effective for methyl acetylene hydrogenation.
- the catalytic activity rapidly increases with addition of copper to nickel up to 25 wt. % in alloy catalyst.
- the selectivity to propylene and extent of polymerization increase with the increase of copper in the alloy.
- Nickel-based catalysts have been used in commercial processes for the selective hydrogenation of acetylenic impurities in mixed steams of olefins and diolefins.
- the present catalyst is a supported catalyst for selective hydrogenation of acetylenes comprising Ni deposited with a promoting amount of Pd on an aluminum oxide support, which contains mixed oxides of MAI 2 O 4 with spinel structures, where M is any divalent cation, preferably comprising 3-15 wt. % Ni promoted with 0.005-0.2 Pd on a support.
- the catalysts are prepared by depositing nickel promoted with palladium on a support, containing one or more optional elements from copper, silver, Group IA (Li, Na, K, Rb, Cs, Fr) and Group IIA (Be, Mg, Ca, Sr, Ba, Ra) and B (Zn, Cd) of the periodic table of elements and characterized as: Range of component Preferably Component wt. % wt. % Ni 3-15 4-11 Cu 0-1 0.01-0.6 Pd 0.005-0.2 0.01-0.1 Ag 0-10 0-5 Group IA 0-2.5 0-1.5 Group IIA & B 0-25 0.1-5 Where the weight % of the active components are based on the total weight of active components and support.
- a promoting amount of Pd means an amount less than 10% of the Ni present.
- the catalysts are useful for hydrogenation reactions such as selective hydrogenation to remove acetylenic impurities in various mixed streams of C 2 -C 12 olefins, diolefins and styrene, and hydrogenation of benzene to cyclohexane. Passing a mixture of a hydrocarbon feed stream and hydrogen gas through a catalytic reaction zone or a series of two catalytic reaction zones which carries out hydrogenation reactions such as the selective hydrogenation of acetylenic compounds.
- a catalytic reaction zone may contain one catalyst or several different catalysts. If the selective hydrogenation is carried out in a series of two catalytic reaction zones, optionally the catalyst in the second reaction zone may contain Cu as a promoter and modifier.
- the poisoning effects of organic mercaptans and organo-mercuric compounds for the nickel catalysts promoted with Cu in the second catalytic reaction zone are neutralized in the first catalytic reaction zone.
- a portion of the catalyst in the first catalytic reaction zone is sacrificed as a guard bed for the poisonous impurities.
- the improvement made for the hydrogenation process in this invention is higher selectivity or higher recovery of the useful materials such as mono-olefins, diolefins, or both, than those processes based on conventional nickel catalysts or conventional palladium-based catalysts.
- the C 4 acetylenic impurities in a mixed crude butadiene stream can be completely removed by selective hydrogenation with higher recovery of 1,3-butadiene in the present process, than prior art nickel catalysts. Therefore, this invention allows elimination of one of two extractive distillation columns, resulting in simpler and cheaper separation of 1,3-butadiene from the mixed stream.
- the catalyst is particularly useful for removing MAPD or acetylene in crude mixed C 2 -C 3 olefin streams and phenyl acetylene in crude styrene stream by selective hydrogenation.
- MAPD Methyl acetylene/propadiene
- the improvement is made by depositing Ni promoted with palladium and preferably copper on a support.
- the catalyst may contain one or more optional elements from Group I and Group II, such as Ag, Ca, Mg, etc.
- silver is deposited on a support in any of following methods; prior-deposition or post-deposition to deposition of nickel, co-deposition with nickel, combinations of two or all of these.
- the optional components, other than Ag are deposited on alumina prior to deposition of active metal components Ni, Cu, Pd and Ag. Deposition of Ni on a support can be carried out by performing either a single or multiple impregnations in any method.
- a preferred catalyst is a supported catalyst for selective hydrogenation of acetylenes selected from the group consisting of 3-15 wt. % Ni, 0.005-0.2 Pd, 0.0-1 wt. % copper, 0.0-10 wt. % Ag, 0-1.5 of at least one member of Group IA and 0.0-25 wt. % of at least one member of Group IIA and IIB deposited on a support, more preferably selected from the group consisting of 4-11 wt. % Ni, 0.01-0.1 Pd, 0.01-0.6 wt. % copper, 0.0-5 wt. % Ag, 0.0-1.5 of at least one member of Group IA and 0.1-5 wt. % of at least one member of Group IIA and IIB deposited on a support.
- the preferred support will have BET surface area from about 10 to 100 m 2/g, preferably from about 12 to 75 m 2/g.
- supports are alumina, silica, beta-silicon carbide, carbon, mixed metal oxides, ceramics, various structured materials for column packing, etc.
- the preferred alumina is prepared by calcining at a temperature from about 1000 to 1250° C.
- the diameter of a preferred shaped support is from 0.2 mm to 3 mm, preferably from 0.4 to 2.5 mm, most preferably from 0.7 mm to 1.5 mm.
- the preferred alumina is alpha, theta, delta-alumina or a mixture of these, which have BET surface area, preferably from 10 to about 75 m 2/g. Additional optional elements are any elements from Group 1 and 11 in the Periodic Table.
- a preferred support is aluminum oxide, which contains mixed oxides of MAI 2 O 4 with spinel structures, where M is any divalent cation, such as Mg, Ca, Zn, Ni, Co, Cu, Mn, etc. Also, up to 30% of aluminum in mixed oxides can be replaced with Ga or In.
- the content of spinel in aluminum oxide support can be any amount, but preferably from 0.1% to 50%, most preferably from 0.2% to 20%.
- catalyst containing optional elements are prepared with alumina support
- one or more elements from Group II is deposited on preferably gamma or eta-alumina and then calcined at from about 900 to 1250° C. to prepare a spinel containing alumina support.
- the selective hydrogenation can be carried out in any physical device in the presence of one or two catalysts, which have different compositions within this invention or are a combination of catalysts in this invention and other Ni-based catalysts or palladium-based catalysts.
- Examples of such devices are fixed bed reactors, catalytic distillation reactors, boiling point reactors, extractive distillation reactors, divided wall distillation reactors, moving bed reactors, stirred tank reactors, and trickle bed reactors.
- a combination of two or three of these physical devices can be used for multi-step selective hydrogenation.
- the crude feed stream may be partially hydrogenated to remove acetylenic compounds in a catalytic distillation column reactor or extractive distillation column reactor as first reaction zone.
- the reaction product stream from the first reaction zone may be further hydrogenated to remove remaining acetylenic compounds in a fixed bed reactor as a second reaction zone.
- the catalyst deactivates slowly while in service.
- Partially deactivated catalyst is treated by washing with a solvent from about 170 to 600° F., preferably from 200 to 400° F. in the presence or absence of hydrogen to recover the catalyst activity.
- suitable solvent for the catalyst washing are ethers, hydrocarbons, organic carbonates and ketones such as diethyl ether, tetrahydrofuran, furfural, gamma-butyrolactone, dimethyl carbonate, ethylene carbonate, alkyl nitriles, amides, methylpyrrolidinone, formylmorpholine, benzene, toluene, cyclohexane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, etc.
- a solvent is fed to the reactor together with a hydrocarbon feed stream and hydrogen.
- a solvent is occasionally co-fed to the reactor with hydrocarbon feed.
- the solvent is recovered from the reactor effluent stream for the recycle.
- Still another option is, after interrupting the hydrocarbon feed, washing the catalyst with a solvent at temperature from about 100 to 450° F. and under a pressure from ambient to about 350 psig preferentially in the presence of a small amount of or in the absence of hydrogen depending on the washing temperature and the nature of the chosen solvent.
- the washed catalyst may be subjected to a post-washing thermal treatment at a temperature from about 170 to about 800° F. in a flow of hydrogen gas under a pressure from ambient to about 350 psig.
- a solvent is introduced into the column either at a position above the catalyst bed or a position in the middle of the catalytic reaction zone with no reflux or minimum reflux of the overhead product stream.
- the solvent is recovered from the bottom stream or by sidedraw from the lower section of the column for recycle.
- the catalyst washing with solvent can be either continuous or occasional.
- the evaluation of the catalyst performance is carried out by comparing recovery of a desired product for a given feedstock at a given conversion of acetylenic compounds or at the conversion required to meet specific product qualifications. For example, when acetylenic compounds in a crude mixed C 3 olefin feed stream are selectively hydrogenated, propylene is the desired product to be recovered from the product stream.
- the following mathematical formula defines the recovery of propylene.
- MAPD can be converted to propylene by selective hydrogenation, the recovery of propylene can be larger than 100 mole %.
- a commercial eggshell type Pd catalyst supported on alpha-alumina (2.5 mm spheres) was used to remove MAPD in a mixed C 3 stream by selective hydrogenation.
- 40 grams of the catalyst were loaded in a vertically mounted up-flow stainless steel fixed bed reactor (1 inch diameter ⁇ 20 inches long). Two thermocouples at each end of the catalyst zone are installed to control the reactor temperature.
- the catalyst was activated at 220° F. by passing hydrogen at 350 cc per minutes for 2 hours.
- the selective hydrogenation of MAPD impurities in a C 3 feed stream was carried out at a fixed flow rate of 4.5 ml/min and hydrogen flow rate of from 20 to 110 sccm/min under 380 psig total reactor pressure.
- the feed comprised of 2.01 wt.
- Another commercial eggshell type catalyst (0.3 wt. %) supported on alpha-alumina (3 ⁇ 3 mm pellets) was used to remove MAPD in the same feed used in the Control Example 1 by selective hydrogenation. 40 grams of the catalyst were loaded in the same reactor used in the Control Example 1. The catalyst was activated in an identical manner to the Control Example 1. The selective hydrogenation of MAPD impurities in the same feed used in the Control Example 1 was carried out at a constant flow rate of 4.5 ml/min and hydrogen flow rate of from 60 to 111 sccm/min under 380 psig total reactor pressure. The temperatures of the hydrogenation were about 135° F. at the end of the catalyst bed and 68-70° F. at the beginning of the catalyst bed. The test result is listed in Table 1. The performance of the catalyst was inferior to the palladium catalyst in the Control Example 1. The average MAPD content in the product at the highest MAPD conversion was 57 wt.ppm MAPD with 34.7 mole % of the average selectivity of MAPD to propylene.
- a Ni catalyst supported on a transition alumina was prepared.
- a gamma alumina trilope extrudate (1.3 mm diameter) was calcined at about 1000° C. for 3 hours in air.
- a solution of nickel nitrate was prepared by dissolving 183.6 g Ni(NO 3 ) 2 .6H 2 O in 300 g water.
- 300 grams of the calcined alumina support were placed in a rotary impregnator and then the nickel nitrate solution was poured on tumbling alumina extrudate support in the rotary impregnator. After 15 minutes cold roll, the contents in the rotary impregnator were dried at about 200° C. by blowing hot air into the rotary dryer.
- the dried product was calcined at 380° C. for 2 hours. Based on the amount of nickel nitrate used to prepare this catalyst, the finished catalyst would have 11 wt. % Ni on alumina support. Measurement of the physical properties of the finished catalyst indicated 133 m 2 /g BET surface area, a total nitrogen adsorption pore volume of 0.669 cc/g and an average pore diameter of 18.6 nm.
- This example demonstrates the preparation technique of a nickel-based catalyst promoted with copper and palladium supported on a nickel spinel containing alumina support. A double impregnation technique was used.
- the gamma-alumina (1.3 mm diameter trilope extrudate) support used in the Control Example 3 was calcined at 1100° C. in air for 3 hours.
- the calcined alumina had 96.6 m 2/g BET surface area, a total nitrogen adsorption pore volume of 0.622 cc/g and an average pore diameter of 27.7 nm.
- this calcined alumina was not used to prepare the nickel catalyst.
- the spinel containing calcined alumina had 26 m 2/g BET, a total nitrogen pore volume of 0.167 cc/g and an average pore diameter of 25.2 nm. This material was used to prepare a nickel-based catalyst as follows.
- a mixed solution of nickel nitrate and copper nitrate was prepared by dissolving 106 g Ni(NO 3 ) 2 .6H 2 O and 4.5 g Cu(NO 3 ) 2 .2.5H 2 O in 300 g water.
- 300 grams of the calcined nickel spinel containing alumina support were placed in a rotary impregnator and then the mixed solution was poured on tumbling extrudate support in the rotary impregnator. After 15 minutes cold roll, the content in a rotary impregnator was dried at about 200° C. by blowing hot air into the rotary impregnator. The dried product was calcined at 350° C. for 2 hours.
- Another mixed solution of nickel nitrate, copper nitrate and palladium nitrate was prepared by dissolving 60 g Ni(NO 3 ) 2 .6H 2 O, 2.54 g Cu(NO 3 ) 2 .2.5H 2 O and 0.74 g Pd(NO 3 ) 2 .xH 2 O (42.8% Pd) in 300 grams of water.
- a second impregnation was performed with this mixed solution on the first impregnation product in similar manner to the first impregnation.
- the impregnation product was calcined at 380° C. for 2 hours. Based on the amounts of materials used in two impregnations to prepare this catalyst, the finished catalyst would have 9.98 wt. % Ni, 0.57 wt. % Cu and 0.094 wt % Pd.
- This example demonstrates the preparation technique of a nickel-based catalyst promoted with copper and palladium supported on a nickel spinel containing alumina support. Double impregnation technique was used.
- nickel spinel containing alumina support 1 wt. % nickel was deposited on the gamma-alumina used in the Control Example 3 and then was calcined at 1125° C. for 3 hours in air.
- the physical properties of the spinel containing calcined alumina were 24.4 m 2 /g BET, a total nitrogen adsorption pore volume of 0.145 cc/g and an average pore diameter of 23.7 nm. This material was used to prepare a nickel-based catalyst.
- a mixed solution of nickel nitrate and copper nitrate was prepared by dissolving 127.2 g Ni(NO 3 ) 2 .6H 2 O and 5.41 g Cu(NO 3 ) 2 .2.5H 2 O in 300 grams of water.
- 300 grams of the calcined nickel spinel containing alumina support were placed in a rotary impregnator and then the mixed solution was poured on tumbling alumina extrudate support in the rotary impregnator. After 15 minutes cold roll, the content in the rotary impregnator was dried at about 200° C. by blowing hot air into the rotary impregnator. The dried product was calcined at 350° C. for 2 hours.
- Another mixed solution of nickel nitrate, copper nitrate and palladium nitrate was prepared by dissolving 38.8 g Ni(NO 3 ) 2 .6H 2 O, 1.63 g Cu(NO 3 ) 2 .2.5H 2 O and 0.44 g Pd(NO 3 ) 2 .xH 2 O (42.8% Pd) in 300 g water.
- a second impregnation was performed with this mixed solution on the first impregnation product in similar manner to the first impregnation.
- the impregnation product was calcined at 380° C. for 2 hours. Based on the amounts of materials used in two impregnations to prepare this catalyst, the finished catalyst would have 9.99 wt. % Ni, 0.57 wt. % Cu and 0.056 wt % Pd.
- This example demonstrates the preparation technique of a nickel-based catalyst promoted with copper and palladium supported on a nickel spinel containing alumina support. A single impregnation was performed.
- nickel spinel containing alumina support 1 wt. % nickel was deposited on the gamma-alumina used in the Control Example 3 and then was calcined at 1150° C. for 3 hours in air.
- the spinel containing calcined alumina had 16.8 m 2 /g BET, a total nitrogen adsorption pore volume of 0.09 cc/g and an average pore diameter of 21.1 nm.
- XRD indicates about 95% alpha-alumina, about 5% delta and trace theta. This material was used to prepare a nickel catalyst as follows.
- a mixed solution of nickel nitrate, copper nitrate and palladium nitrate was prepared by dissolving 166 g Ni(NO 3 ) 2 .6H 2 O, 7.04 g Cu(NO 3 ) 2 .2.5H 2 O and 0.74 g Pd(NO 3 ) 2 .xH 2 O (42.8% Pd) in 305 g water.
- 300 grams of the calcined nickel spinel containing alumina support were placed in a rotary impregnator, and then the mixed solution was poured on tumbling alumina extrudate support in a rotary impregnator. After 15 minutes cold roll, the content in the rotary impregnator was dried at about 200° C.
- the finished catalyst would have 9.98 wt. % Ni, 0.57 wt. % Cu and 0.094 wt % Pd.
- the finished catalyst had 9.4 m 2/g BET, a total nitrogen adsorption pore volume of 0.035 cc/g and an average pore diameter of 14.8 nm.
- the analysis of the catalyst indicates the following composition; 10.4 wt. % Ni, 0.55 wt. % Cu and 0.074 wt. % Pd.
- This example demonstrates the preparation technique of a nickel-based catalyst promoted with copper and palladium supported on magnesium-spinel alumina.
- a magnesium nitrate solution was prepared by dissolving 6 grams of Mg(NO3)2.6H20 in 320 grams water. 300 grams of gamma-alumina were impregnated with this magnesium nitrate solution. After drying the impregnated alumina at about 200° C. for 2 hours, the dried product was calcined at 1100° C. for 3 hours and then at 1150° C.
- the support had 60.4 m 2 /g BET surface area, a total nitrogen pore volume of 0.548 cc/g and an average pore diameter of 37.3 nm.
- a mixed solution of nickel nitrate and copper nitrate was prepared by dissolving 9681 grams of Ni(NO3)2.6H20 and 4.11 grams of Cu(NO3)2.2.5H20 in 300 grams of water. 274 grams of the magnesium-spinel/alumina were placed in a rotary impregnator and then the mixed solution was poured on the support. After 10 minutes cold rolling, the content in the impregnator was dried at about 200° C. by blowing hot air into the rotary impregnator. The dried product was calcined at 350° C. for two hours.
- Another mixed solution of nickel nitrate, copper nitrate and palladium nitrate was prepared by dissolving 54.8 grams of Ni(NO 3 ) 2 .6H 2 O, 2.32 grams of Cu(NO 3 ) 2 .2.5H 2 O and 0.66 grams of Pd(NO 3 ) 2 .xH 2 O (42.8 wt % Pd) in 300 grams of water. Second impregnation of the first impregnation product with the second mixed solution was performed in similar manner. The dried impregnation product was calcined at 380° C. for 2 hours.
- the active metal compositions on the support are 9.96 wt % Ni, 0.57 wt % Cu and 0.09 wt % Pd.
- the finished catalyst had 59.3 M/g BET surface area, a total nitrogen pore volume of 0.457 cc/g and an average pore diameter of 31.8 nm.
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US10/969,613 US20060084830A1 (en) | 2004-10-20 | 2004-10-20 | Selective hydrogenation process and catalyst |
MX2007003207A MX2007003207A (es) | 2004-10-20 | 2005-07-19 | Proceso y catalizador de hidrogenacion selectiva. |
RU2007114902/04A RU2355670C2 (ru) | 2004-10-20 | 2005-07-19 | Способ селективного гидрирования и катализатор |
KR1020077008829A KR20070074568A (ko) | 2004-10-20 | 2005-07-19 | 선택적 수소화 방법 및 촉매 |
PCT/US2005/025606 WO2006044005A2 (en) | 2004-10-20 | 2005-07-19 | Selective hydrogenation process and catalyst |
CNA2005800317059A CN101432247A (zh) | 2004-10-20 | 2005-07-19 | 选择加氢工艺和催化剂 |
JP2007537874A JP2008516765A (ja) | 2004-10-20 | 2005-07-19 | 選択的水素化方法及び触媒 |
TW094126451A TW200613060A (en) | 2004-10-20 | 2005-08-03 | Selective hydrogenation process and catalyst |
US12/539,229 US7838710B2 (en) | 2004-10-20 | 2009-08-11 | Selective hydrogenation process and catalyst |
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CN101432247A (zh) | 2009-05-13 |
WO2006044005A2 (en) | 2006-04-27 |
US20090299114A1 (en) | 2009-12-03 |
US7838710B2 (en) | 2010-11-23 |
MX2007003207A (es) | 2007-05-16 |
RU2007114902A (ru) | 2008-10-27 |
JP2008516765A (ja) | 2008-05-22 |
KR20070074568A (ko) | 2007-07-12 |
TW200613060A (en) | 2006-05-01 |
RU2355670C2 (ru) | 2009-05-20 |
WO2006044005A3 (en) | 2009-04-16 |
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