CN1604955A - 加氢催化剂和加氢方法 - Google Patents
加氢催化剂和加氢方法 Download PDFInfo
- Publication number
- CN1604955A CN1604955A CNA028204689A CN02820468A CN1604955A CN 1604955 A CN1604955 A CN 1604955A CN A028204689 A CNA028204689 A CN A028204689A CN 02820468 A CN02820468 A CN 02820468A CN 1604955 A CN1604955 A CN 1604955A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- hydrogenation
- diene
- alkene
- unsaturated compound
- 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.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 150000001993 dienes Chemical class 0.000 claims abstract description 23
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 54
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 41
- 238000007598 dipping method Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 22
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- -1 acetylene compound Chemical class 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 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
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—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
- 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
- B01J23/8953—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 zinc, cadmium or mercury
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—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
- 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
- B01J23/8973—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 arsenic, antimony or bismuth
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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
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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
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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
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Abstract
一种负载型加氢催化剂,包括(1)Pd,或含有Pd及一种其他第8族金属的第8族金属,优选第8族金属选自Pt、Ir、Ru、Co或Ni,及(2)至少两种金属选自Ag、Zn或Bi,优选Ag和至少一种Zn或Bi。任选催化剂可含有K。催化剂负载于多孔载体例如氧化硅、氧化铝、氧化硅-氧化铝或碳上。优选载体的平均孔径为180,没有小于35的孔,总孔体积大于0.65cc/g,及BET表面积优选小于约100m2/g。催化剂用于氢化不饱和烃例如各种混合烯烃物流中的乙炔和二烯。
Description
发明领域
本发明涉及高度不饱和化合物的多组分加氢催化剂,所述的催化剂包括具有特定特征载体上的Pd和一组选择的改进剂,及不饱和烃的加氢方法,更特别涉及高度不饱和烃例如乙炔的选择加氢。更特别的,本发明涉及C2~C4混合烯烃物流中乙炔化合物的选择加氢。
背景技术
负载Pd和Ni催化剂已经用于各种加氢工艺中有相当长的时间。这样的工艺包括各种混合烯烃物流中的乙炔化合物和二烯的选择加氢,及汽油和苯的加氢。
DE 2,412,191公开了通过使用微粒分散的催化剂或负载催化剂选择氢化乙炔化合物,精制1,3-丁二烯和异戊二烯物流。优选的催化金属是贵金属例如Pd或非贵金属例如Co、Fe或Mo。声称的改进是利用贵或非贵催化剂,使用环戊二烯烃提高1,3-丁二烯的选择性。
文献中公认的是负载Pd催化剂对于乙烯基乙炔的选择加氢不稳定,因为乙烯基乙炔与Pd形成了络合物。Pd络合物可溶于烃物流中。已经发现在Pd催化剂中加入银导致稳定由于Pd金属流失的催化剂失活,并改进希望的烯烃产品的选择性。见,M.L.Derrien et al.Studies inSurface Science and Catalyst,Vol 27,page 613(1986),和Elsvier and K.James Sasski,Petrochemical and Gas Processing,113 PTQ Autumn,1997。
US 4,533,779公开了负载于载体例如氧化铝(1~100m2/g)Pd-Au催化剂,用于乙炔化合物的加氢。在实施例中使用的氧化铝的表面积为70m2/g,总孔体积为0.6cc/g,及平均孔径为200。在两个连续的步骤中沉积Pd和Au。使用在非极性有机溶剂中将有机钯化合物(乙酰丙酮化物)吸附到氧化铝上的技术将Pd化合物浸渍到氧化铝上。催化剂中Pd和Au的含量分别为0.03~1wt%和0.003~0.3wt%。
US 4,762,956公开了一种新颖的烯烃原料中氢化二烯和乙炔杂质的催化剂和方法。催化剂是负载于基本上为结晶α-氧化铝上的Pd催化剂,所述的氧化铝的平均孔径为200~2000,至少80%的孔的孔径为100~3000。活性Pd金属表面积小于50m2/g,平均Pd粒度至少为25。通过雾化将氯化钯水溶液溶液喷雾到氧化铝上及随后在80℃下干燥,进行Pd的浸渍。
US 5,866,735公开了使用负载于载体例如氧化铝上的Pd催化剂的加氢方法,但利用碱金属碘化物例如碘化钾进行改性以减少在选择性氢化混合烃物流中的二烯烃和/或乙炔化合物的过程中重产物的形成。
US 5,877,363公开了利用负载的Pt、Fe等催化剂,选择氢化富含C4混合烯烃中的乙炔杂质并将1,2-丁二烯异构化为1,3-丁二烯。
EP 0567198公开了一种用于炔烃和二烯加氢的Pd-Cu-K/Al2O3催化剂。优选的催化剂组成为0.2%Pd、0.3%Cu及0.41%K。优选的氧化铝载体是γ-Al2O3,表面积为100~250m2/g,及孔体积为0.4~0.7cm2/g。
US 4,644,088和US 4,658,080公开了去除乙炔的方法。催化剂是多组分催化剂,至少含有Fe和Ni,其他的选自元素周期表B、IB、IIB、IVB、VIB和VIIB族的元素及碱土金属和碱金属。催化剂制备如下:混合ZnFe2O4、BaCO3和NiCO3干粉,随后用NaOH水溶液捏合干混物,并成型为适当大小的小球,进行干燥。刚刚制备的催化剂包括金属氧化物、盐和氢氧化物。活化使用的催化剂主要由金属和金属氧化物组成。氧化铝不是该催化剂的一部分。通过使进料与催化剂在气相250℃~900℃下接触除去乙炔。
根据V.Rlves et al.,将Zn加入到混合烯烃物流中乙炔加氢Ni-Al Cr氧化物催化剂中可阻止催化剂表面的结焦形成,对于Zn/Ni原子比为4时可实现乙烯的最大转化率(Applied Clay Science 13(1998)363-379)。
A.Sarkany发表了一篇文章,关于1,3-丁二烯加氢的负载于α-氧化铝上的蛋壳型Pd和Pd-Ag催化剂(Applied Catalysis:General175(1998)245~253)。在催化剂表面积上沉积的低活性的重烃引起了催化剂失活及过渡加氢为烃烷烃产物。
H.Uygur et al.发表了一篇文章(J.Chem.Eng.Japan,Vol.31,No 2,178(1998)),关于混合C3物流中甲基乙炔和丙二烯(MAPD)的液相选择加氢。他们发现随加氢温度的增加在0.3%Pd催化剂上MAPD的转化率下降。S.D.Jackson et al.(App.Catalysis A:General134(1996)91~99)在研究苯基乙炔和苯乙烯在碳负载的Pd催化剂上的液相加氢时发现随吸附温度增加苯基乙炔的吸附增加。N.R.M.Sassenet al(Faraday Discuss,Chem.,Soc.,89(1998),331~320)发现当温度从-20℃提高到0℃时,在Pd(111)面上吸附的次乙基物种增加。我们发现对于在负载的Pd-Ag催化剂上混合粗丁二烯物流的C3和C4炔键化合物的选择加氢,也存在上述的情况。这种表面上看来奇怪的行为是选择加氢非常低的活化能(<0.5kcal/mole)、在较低的温度下进料物流中较高的氢溶解度、及在气相、液相和固相的三相反应体系中Pd催化剂表面上炔键化合物吸附的温度依赖性共同结合的效果。即,液相中氢的浓度比表观活化能对炔键化合物选择加氢速度更具影响力。
发明内容
本发明涉及负载催化剂,包括(1)Pd,或含有Pd及一种其他第8族金属的第8族金属,优选第8族金属选自Pt、Ir、Ru、Co或Ni,及(2)至少两种选自Ag、Zn或Bi的金属,优选Ag和至少一种Zn或Bi。任选催化剂可含有K。催化剂中K的含量通常小于0.5wt%。
通过使含有少量炔键化合物的烃物流与本发明的各种布置和构造的催化剂接触使不饱和化合物加氢的方法也是本发明的一部分。
优选的载体是高度多孔的,平均孔径大于约180,没有孔小于35,总孔体积大于约0.65cc/g,及BET表面积优选小于约100m2/g。
发明的详细描述
本发明包括一种改进的催化剂,和使用该催化剂的加氢方法。特别是加氢方法涉及多个不饱和化合物例如炔键化合物和二烯加氢为等量的单和双不饱和产物或饱和产物,这取决于工艺的目的,和芳香化合物如苯加氢为环状化合物。所述的加氢可以在气相、液相及气相和液相混合相存在的条件下进行。加氢可以在溶剂存在或没有溶剂存在的情况下,以任何的固定床反应器、滴流床反应器、催化蒸馏反应器或其任意组合而进行。优选的溶剂例子是四氢呋喃、苯、甲苯等。
本发明特别用于通过选择加氢为单或双不饱和或饱和有机化合物而去除C2~C12有机化合物中的炔键化合物和二烯。这样原料流的例子是裂化C2、C3、C4、C5馏分物流或C2~C6混合物流及汽油沸程的燃料。
本发明公开的改进催化剂是负载于高度多孔的载体例如氧化铝、氧化硅、氧化铝-氧化硅、碳等上的多组分催化剂,载体的总孔体积至少为0.65cm3/g,平均孔径大于180。氧化铝是优选的载体,其BET表面积为10~100m2/g,优选为20~70m2/g。氧化铝的物理形状是球形、粒状、颗粒或挤出物,大小为1/32~1/4英寸。成型氧化铝载体的表观堆积密度(ABD)小于0.7g/cm3,但不大于约0.8g/cm3。氧化铝是一种过渡氧化铝,取决于焙烧温度和一水合原料氧化铝的结晶结构具有混合α、κ、θ、δ、ρ、η、γ和χ的结晶形式。大部分由γ或χ结晶形式组成的氧化铝是不优选的载体。为制备优选的氧化铝,球形的氧化铝原料例如氧化铝凝胶或一水合氧化铝在约650℃~1250℃温度下焙烧。最后的焙烧温度由氧化铝载体的物理性质决定以得到用于特定加氢工艺的最佳性能的催化剂。
本发明中公开的优选氧化铝可通过大量的本领域普通的技术人员熟知的制备氧化铝技术而进行制备。本发明公开的一种优选氧化铝可通过所谓的油滴流凝胶化技术进行制备。现有技术的例子公开于US2,620,314、US 4,273,735和US 4,179,408。球形的氧化铝由通过将铝金属溶解在盐酸水溶液中制备的羟基氯化铝而制备。以液滴形式生成的球形氧化铝凝胶物料通过在碱性液体油相中进行凝胶,随后老化、洗涤、干燥,和取决于氧化铝希望性质在不同温度下焙烧为过渡态氧化铝。另外,优选的球形氧化铝也可通过油滴凝胶化技术使用分散的勃姆石或假勃姆石氧化铝溶胶制备。氧化铝溶胶可这样制备,分散由水解铝醇盐得到的适当的勃姆石、假勃姆石或勃姆石和假勃姆石氧化铝的混合物,然后结晶或用铝盐例如硫酸铝或硝酸铝溶液与铝酸钠溶液反应,然后再结晶。各种勃姆石氧化铝或分散的勃姆石氧化铝溶胶可在市场中得到。Condea是其中之一的供应商。为制备优选的其物理性质公开于本发明的球形氧化铝,Dispersal HP14/2、Dispal 11N7-80、Dispal 23N4-20、Disperal HP 14、Deperal 40、Pural 200、Pural 100、PuralNG或这些的混合物可以作为原料。其他的用于制备本发明公开的优选氧化铝载体,因为有太大的表面积,太窄的孔径分布及太小的孔体积。这些原料可得到如US 4,493,906和4,440,956中公开的氧化铝。各种挤出物或片状形式的优选的氧化铝也可通过挤出优选的如上所述的勃姆石或假勃姆石氧化铝,并在约650℃~约1250℃的高温下进行焙烧得到。任选,由金属或陶瓷材料制造的用于蒸馏塔的不同构造的填充材料用作载体。
催化剂中的K含量通常小于0.5wt%。催化剂中金属的含量Pd优选为0.005~1wt%,更优选为0.01~0.3wt%,Ni优选为0.0~15wt%,更优选为0~10wt%,Ag优选为0.002~20wt%,更优选为0.005~5wt%,Zn优选为0~5wt%,更优选为0.002~1wt%,和Bi优选为0~5wt%,更优选为0.01~3wt%。
为在载体上沉积需要的元素,可以使用各种技术例如使用旋转蒸发仪的溶液浸渍法、初始孔浸渍法、使用雾化器的喷涂浸渍法、气相沉积技术、共沉淀技术等。本发明中优选的技术是喷涂浸渍法和初始孔浸渍法。特别是,喷涂浸渍是本发明中最优选的。
取决于具体加氢反应的目的,所述的目的决定催化剂中需要何种元素及需要多少,可以进行一步浸渍或两步浸渍。如果需要Pd、Ag和Zn是需要的元素,那么制备Pd、Ag和Zn化合物的水或有机溶液。在旋转浸渍器中将溶液喷雾到滚动的载体上例如氧化铝,随后用热气体例如空气或氮气在60℃~300℃的温度下进行干燥。干燥的浸渍产品通常在约250℃~600℃下空气中进行焙烧。如果为得到更好的催化剂使用性能需要进行两步浸渍,取决于催化剂具体的使用目的,用Zn化合物、Ag和Zn化合物或Pd、Ag和Zn化合物的水溶液通过初始孔浸渍技术在适当的载体上进行第一步浸渍。浸渍的产品在60℃~300℃的温度下干燥,随后在250℃~600℃下温度下进行焙烧。用Pd和Ag或Pd、Ag和Zn化合物的混合溶液利用喷涂浸渍技术,在用雾化器雾化并随后在如上所述适当温度下进行干燥和焙烧得到的第一浸渍产品上进行第二步浸渍。对于大多数的选择加氢反应例如在烯烃和二烯不同混合物料中去除炔键化合物,Pd从载体几何外表面穿透进入载体内表面在决定催化剂的选择性和稳定性中起非常重要的作用。小于0.08mm,优选小于约0.06mm的Pd穿透是极其希望的。本发明的目的可以通过使用压缩气体雾化器在形成悬浮在气相中的微细液体雾的浸渍溶液而实现。而且,对于给定量载体液体浸渍溶液的体积是重要的。希望的溶液体积小于约载体孔体积的85vol%,优选小于65vol%。
当Bi是其中之一催化剂需要的组分时,可以一步或两步进行催化剂的制备。对于一步浸渍,通过喷涂技术在旋转浸渍器中滚动载体的内部上或初始孔浸渍技术,随后进行如上所述的干燥和焙烧,在载体上进行Pd、Zn、Ag和Bi化合物混合溶液的浸渍。如果需要进行两步浸渍,在第一步骤中,Bi化合物溶液或Bi和Zn化合物混合溶液用于初始孔浸渍金技术中或者喷涂技术中,随后在如上所述适当的温度下进行干燥和焙烧。另外一种可选择的将Bi或Bi和Zn加入氧化铝载体中的技术是将Bi化合物或Bi和Zn化合物混合溶液浸渍到未焙烧的氧化铝上,随后在650℃~1300℃温度下干燥和焙烧浸渍产品。通过喷涂浸渍技术或初始孔浸渍技术及随后在如上所述的条件下进行干燥和焙烧,在第一浸渍步骤中得到的产品上进行Pd、Ag和Zn化合物或Pd、Ag、Zn和Bi化合物第二浸渍。
对于制备含有Zn或Zn和Bi的多组分催化剂,可以利用制备氧化铝载体的油滴流凝胶技术将Zn或Zn和Bi引入。氧化铝载体可以这样制备,将含有溶解Zn化合物或Zn和Bi化合物的氧化铝溶胶滴入碱性油相中形成凝胶,随后老化、洗涤、干燥和在650℃~1250℃的温度下焙烧。任选,氧化铝载体可以这样制备,将Zn或Bi化合物溶液,或Zn和Bi化合物混合溶液浸渍到氧化铝粉末上,所述的氧化铝粉末具有如上所述的优选载体的物理特征。制备这样的氧化铝粉末的适当的原料是如上所述的勃姆石粉末和假勃姆石粉末。原料在350℃~约750℃温度下进行焙烧,之后进行浸渍。浸渍的产品在约250℃~600℃温度下进行焙烧,然后成型为需要尺寸的挤出物或粒子。最后,成型的物料在空气中约650℃~1300℃的高温下进行焙烧。含有Pd和Ag化合物或Pd、Ag和Zn化合物混合溶液利用如上所述的任意一种浸渍技术随后进行干燥和焙烧而浸渍到如此制备的氧化铝载体上。
利用一种或多种催化剂进行不饱和有机化合物的加氢。对于选择加氢,可以使用一种、两种或多种以提高需要产品的产率。例如,使裂化丁二烯物流的物流中的乙烯基乙炔、乙基乙炔和甲基乙炔完全或接近完全转化,两种或多种组成和金属负载量不同的催化剂可用于得到高质量的产品同时具有经济上最檄文希望的结果。催化剂可以装填于单一的反应器或两种反应器中。在单一反应器操作(固定床或催化蒸馏反应器操作)中较高活性的催化剂装填于较小活性催化剂前面,这样进料物料首先通过较高活性催化剂区域。氢进料物流可以在进入催化反应区域之前单一点处或沿反应器两个或多个位置处加入进料烃物流中以得到最希望的结果,因为两种不同活性催化剂在特定的炔键化合物浓度、温度、压力及烃流速给定的条件下,在进料中具有不同的最佳的氢与炔键化合物的比例。如果使用两个反应器,较高活性的催化剂装填于第一反应器中。
在存在或不存在溶剂的情况下,催化蒸馏加氢是优选的用于选择氢化不同混合物流中炔键化合物的模式以得到最佳的选择性及长的使用寿命。在催化蒸馏加氢中,聚合物前体和较重的聚合物连续用液相洗去,并作为一部分塔底产物被除去,保持催化剂表面比固定床操作更清洁。通常,需要产品的选择性比固定床操作的选择性要好,因为与固定床情况相比,通过适当操作蒸馏塔可在催化蒸馏区域中保持较高浓度的炔键化合物。如果使用溶剂,催化蒸馏塔可以两种方法进行操作。蒸馏塔可以溶剂全部内部回流的方式进行操作,或溶剂可加入到催化蒸馏区域上方塔的顶部,并根据溶剂的熔点作为一部分塔底产物被除去。从塔底产物流中除去的溶剂循环回催化蒸馏塔催化区域上方的位置。
实施例
对比实施例1
工业用负载于氧化铝(从UCI得到的G681)上的蛋壳型Pd-Ag催化剂用于去除粗裂化丁二烯物流中的炔键化合物。36g商业可获得催化剂(0.2%Pd-0.1Ag%/氧化铝)与100ml直径为3mm的玻璃球混合装填于垂直安装的向上流动的不锈钢反应器中(1英寸直径×20英寸长)。催化剂的ABD为0.97g/cc。具有平均孔径的催化剂为2.5mm直径×6mm长的挤出物。催化剂在230F下通过1mm/min(在环境温度下进行测量)的丁二烯和15cc/min的氢气(He中有10vol%的H2)在200psig下活化2小时。将反应器冷却到预定的温度,然后将反应器压力设定为预定的加氢压力。在停止向反应器送入氢气和丁二烯后,在烃物料和氢同时缓慢地引入时并监测反应器的温度。由于加氢反应的放热性,如果不小心,温度可能会突然升高,因此催化剂床起始段的温度比催化剂床末尾段的温度低。
混合C4物流中的炔键化杂质包括570ppm丙烯、6550ppm乙烯基乙炔、1497ppm乙基乙炔、55.47%的1,3-丁二烯、0.22%的1,2-丁二烯和15.41%的1-丁烯等,通过在活化的G681催化剂上进行选择加氢而被除去。
本发明相对现有技术的改进是较高的生产率、较高的产品流质量、较高的希望产品的产率及节约氢。
实施例1
球形γ-氧化铝(2mm直径)用于制备本发明公开的适当载体。球形的γ-氧化铝其本身不是合适的载体,因为有太高的表面积和活性。该氧化铝的物理性质列于表1中。氧化铝在1150℃下空气中焙烧3小时。
表1
ABC,g/cc | 0.53 |
单点BET,m2/g | 157.5 |
多点BET,m2/g | 170.2 |
中孔孔表面,m2/g | 170.2 |
大孔孔表面,m2/g | 0 |
累计吸附表面积,m2/g | 172.6 |
累计脱附表面积,m2/g | 230.4 |
在P/P0=0.9801下半径小于493孔的总孔体积(cc/g) | 0.912 |
20~300孔的累计吸附孔体积 | 0.852 |
17.5~300半径孔的累计总脱附孔体积 | 0.930 |
平均孔径, | 214.4 |
通过将3.79g Zn(NO3)2·6H2O、0.52g AgNO3和13g 10%Pd的硝酸盐溶解于100g去离子水的10%的HNO3溶液中制备混合溶液。使用压缩雾化器和旋转浸渍器将混合溶液喷涂到300g焙烧的氧化铝上,在约200℃下热空气中加热1小时。干燥的产品在350℃下焙烧2小时。基于使用的化学品量该催化剂计算的组成为0.20wt%Pd/0.11wt%Ag/0.28wt%Zn。
36g该催化剂(Pd/Ag/Zn/Al2O3)和100ml 3mm直径的玻璃球混合装填于如对比实施例1相同的反应器中。以如下的方式活化催化剂。催化剂用流速200cc/min的N2在15psig下进行吹扫,缓慢加热到235°F,100cc/min的H2流切入N2流中并保持1小时。在停止N2后,将氢气流增加到300cc/min,然后将温度提高到550°F保持2小时。在氢气流中将反应器冷却到希望的加氢反应温度。反应器用氮气(150cc/min)吹扫,并设定到预定的加氢压力。原料烃和氢进料气体缓慢切入氮物流中同时监测反应器的温度,并缓慢停止氮气流。烃进料与对比实施例1相同。对比实施例1和实施例1的结果列于表2中。
从表2列出的结果清楚可见,负载于氧化铝上的三组分(Pd/Ag/Zn)催化剂比常规的催化剂具有优异的使用性能。实施例1中的产品质量优于对比实施例1中的产品质量。实施例1进料中的乙烯基乙炔杂质被完全除去。但1,3-丁二烯的回收率提高超过4wt%。一般地说,与较低活性催化剂相比,在相等或更高转化率下具有更高的需要产品的产率是非常罕见的。
实施例2
用于制备实施例1的氧化铝载体的球形γ-氧化铝在1100℃下空气中焙烧3小时。
通过将4.31g Bi(NO3)3·6H2O溶解于用六滴浓硝酸溶液酸化的285ml去离子水中制备硝酸铋溶液,用该溶液在300g上述焙烧的氧化铝上进行初始孔浸渍。浸渍的产品在旋转浸渍器中冷滚动10分钟,在约200℃下热空气中干燥1小时。干燥的产品在450℃下空气中焙烧2小时。通过将3.79g Zn(NO3)2·H2O、0.52g AgNO3和13.3g 10%硝酸钯溶解于100ml去离子水的10%的HNO3溶液中制备混合溶液。使用压缩雾化器和旋转浸渍器将该混合溶液喷涂到上述焙烧的产品上,在约200℃下热空气中干燥1小时。干燥的产品在350℃下焙烧2小时。基于使用的化学品量该催化剂计算的组成为0.20wt%Pd/0.11wt%Ag/0.27wt%Zn/1.42wt%Bi。
36g该催化剂(Pd/Ag/Zn/Bi/Al2O3)和100ml 3mm直径的玻璃球混合装填于如对比实施例1相同的反应器中。以如实施例1的方式活化催化剂。如对比实施例1相同的烃原料和氢物流缓慢切入氮物流中同时监测反应器的温度,并缓慢停止氮气流。结果列于表2中。
表2
对比实施例1 | 实施例1 | 实施例2 | ||
温度(°F)* | 120 | 110 | 120 | 120 |
压力(psig) | 108 | 125 | 108 | 108 |
WHSV HC进料 | 4 | 3 | 4 | 6.1 |
H2速度,HC scft/lb | 1.34 | 1.56 | 1.34 | 1.31 |
产物组成(ppm)** | ||||
VA | 85 | 36 | 0 | 0 |
EZ | 278 | 159 | 91 | 0 |
MA | 38 | 18 | 6 | 1 |
丙二烯 | 105 | 80 | 81 | 110 |
1,2-BD | 1322 | 1170 | 1212 | 1230 |
1,3-BD回收率 | 91.9 | 89.6 | 94.3 | 92.5 |
*催化剂床末尾段的温度
结果清楚地显示负载于本发明公开氧化铝上的四组分(Pd/Ag/Zn/Bi)催化剂的性能优于现有技术的催化剂性能。原料中所有的C4炔键杂质被完全去除,甚至在在进料速度为50%以上的情况下。但1,3-丁二烯的回收率仍然优于现有技术的回收率。
Claims (20)
1、一种不饱和化合物选择加氢的催化剂,包括负载催化剂,包括(1)Pd,或含有Pd及一种其他第8族金属的第8族金属,及(2)至少两种选自Ag、Zn或Bi的金属。
2、如权利要求1的催化剂,包括Pd和一种其他的第8族金属。
3、如权利要求2的催化剂,其中所述的第8族金属选自Pt、Ir、Ru、Co或Ni。
4、如权利要求1的催化剂,包括Ag和至少一种Zn或Bi。
5、如权利要求1的催化剂,其中所述的催化剂负载在载体上,所述的载体是高度多孔的,平均孔径大于约180,没有小于35的孔,总孔体积大于约0.65cc/g,及BET表面积优选小于约100m2/g。
6、如权利要求1的催化剂,包括K。
7、如权利要求1的催化剂,其中Pd含量为0.005~1wt%,Ni为0.0~15wt%,Ag为0.002~20wt%,Zn为0~5wt%,和Bi为0~5wt%。
8、如权利要求1的催化剂,其中Pd含量为0.01~0.3wt%,Ni为0~10wt%,Ag为0.005~5wt%,Zn为0.002~1wt%,和Bi为0.01~3wt%。
9、如权利要求6的催化剂,其中K的含量小于0.5wt%。
10、如权利要求5的催化剂,其中所述的载体是氧化铝,其BET表面积为10~100m2/g。
11、如权利要求10的催化剂,其中所述的载体的BET表面积为20~70m2/g。
12、如权利要求5的催化剂,其中所述的氧化铝载体是成型过渡氧化铝,表观堆积密度为0.7~0.8g/cm3,是α、κ、θ、δ、ρ、η、γ和χ的混合结晶形式。
13、一种选择氢化不饱和化合物的方法,包括在如权利要求1的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
14、一种选择氢化不饱和化合物的方法,包括在如权利要求2的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
15、一种选择氢化不饱和化合物的方法,包括在如权利要求3的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
16、一种选择氢化不饱和化合物的方法,包括在如权利要求5的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
17、一种选择氢化不饱和化合物的方法,包括在如权利要求7的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
18、一种选择氢化不饱和化合物的方法,包括在如权利要求8的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
19、一种选择氢化不饱和化合物的方法,包括在如权利要求11的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
20、一种选择氢化不饱和化合物的方法,包括在如权利要求12的催化剂存在下,至少部分液相的包括含有乙炔、二烯和烯烃的不饱和化合物的进料与氢接触以选择氢化乙炔、二烯或烯烃。
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- 2002-09-18 CN CNB028204689A patent/CN1281720C/zh not_active Expired - Fee Related
- 2002-09-25 TW TW091122032A patent/TW583168B/zh not_active IP Right Cessation
- 2002-09-25 AR ARP020103612A patent/AR036628A1/es active IP Right Grant
- 2002-10-20 SA SA02230391A patent/SA02230391B1/ar unknown
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2004
- 2004-08-05 US US10/912,252 patent/US7288686B2/en not_active Expired - Fee Related
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CN102164669A (zh) * | 2008-09-25 | 2011-08-24 | 南方化学触媒株式会社 | 1,3-丁二烯中的炔类化合物的选择氢化用催化剂及其制造方法、和其使用方法 |
CN102019180A (zh) * | 2009-09-21 | 2011-04-20 | 环球油品公司 | 在mlab制造中二烯的选择性氢化 |
CN102020524A (zh) * | 2009-09-21 | 2011-04-20 | 环球油品公司 | Mlab生产中二烯烃的选择性氢化 |
CN102125839A (zh) * | 2011-01-21 | 2011-07-20 | 北京三聚环保新材料股份有限公司 | 一种炔烃加氢催化剂及其制备方法 |
CN102125839B (zh) * | 2011-01-21 | 2014-06-04 | 北京三聚环保新材料股份有限公司 | 一种炔烃加氢催化剂及其制备方法 |
CN104588006A (zh) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | 一种用于炔烃选择加氢的含钯的合金单原子催化剂 |
CN106890637A (zh) * | 2015-12-17 | 2017-06-27 | 正大能源材料(大连)有限公司 | 一种乙炔选择加氢催化剂的制备方法 |
CN106890637B (zh) * | 2015-12-17 | 2020-03-31 | 正大能源材料(大连)有限公司 | 一种乙炔选择加氢催化剂的制备方法 |
Also Published As
Publication number | Publication date |
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TW583168B (en) | 2004-04-11 |
US20050203320A1 (en) | 2005-09-15 |
WO2003033136A2 (en) | 2003-04-24 |
AU2002341704A1 (en) | 2003-04-28 |
SA02230391B1 (ar) | 2009-01-31 |
US20050010070A1 (en) | 2005-01-13 |
AR036628A1 (es) | 2004-09-22 |
US7288686B2 (en) | 2007-10-30 |
CN1281720C (zh) | 2006-10-25 |
WO2003033136A3 (en) | 2003-11-27 |
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