CN106925272A - Fe-Cu selective hydrogenation catalyst, preparation method and application thereof - Google Patents
Fe-Cu selective hydrogenation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN106925272A CN106925272A CN201511032409.2A CN201511032409A CN106925272A CN 106925272 A CN106925272 A CN 106925272A CN 201511032409 A CN201511032409 A CN 201511032409A CN 106925272 A CN106925272 A CN 106925272A
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- Prior art keywords
- catalyst
- carrier
- selective hydrogenation
- temperature
- hydrogenation catalysts
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 229910002549 Fe–Cu Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 6
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 26
- 230000009467 reduction Effects 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 150000001361 allenes Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 abstract 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- 238000001994 activation Methods 0.000 description 19
- 230000004913 activation Effects 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 239000010949 copper Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 150000001345 alkine derivatives Chemical class 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 229910021304 Co4Al13 Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 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
- 239000003643 water by type Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021007 Co2Al5 Inorganic materials 0.000 description 1
- 229910021214 Co2Al9 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910019108 CoAl3 Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a Fe-Cu selective hydrogenation catalyst, which contains 2-15% of Fe and 0.05-0.5% of CuO. The rest is oxygen element and carrier. The specific surface of the catalyst is 10-300 m2The pore volume is 0.2 to 0.65 ml/g. The catalyst of the present invention can be used in C2～3Selective hydrogenation of acetylene, propyne and propadiene (MAPD) in the cracked fraction. The catalyst has mild hydrogenation activity, excellent olefin selectivity, high olefin increment, good operation elasticity, low green oil generation amount and good long-period running performance. And the catalyst cost is far lower than that of the noble metal Pd catalyst.
Description
Technical field
The present invention relates to a kind of Fe-Cu selective hydrogenation catalysts, preparation method and applications, the catalyst can be used for ethene
Atmosphere trace acetylene and propine (MA), allene (PD) selective hydrogenation prepare ethene.
Background technology
Ethene, propylene are one of most important basic materials of petro chemical industry, as the monomer for synthesizing various polymer,
The overwhelming majority is obtained by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel) steam cracking.Obtained through this method
To the C2 cuts based on ethene in also containing 0.5%~2.5% (molar fraction) acetylene.The presence of acetylene can make ethene
Polymerization process complicate, deteriorate polymer performance.When polyethylene is produced with high-pressure process, due to the accumulation of acetylene, have quick-fried
Fried danger；In addition, when polyethylene is produced, the presence of acetylene can also reduce polymerization catalyst, increase disappearing for catalyst
Consumption.So the acetylene in ethene must be dropped to below certain value, could be used as the monomer of synthetic high polymer.
Precious metals pd series hydrocatalyst, the acetylene and C3 being selectively removed in C2 cuts is generally used to evaporate in industry at present
Propine (MA), allene (PD) in point.Patent US4404124 is prepared for active component palladium shell and is distributed by step impregnation method
Selective hydrogenation catalyst, the selection hydrogenation of carbon two, C3 fraction is can be applied to, with eliminating acetylene and propylene in ethene
Propine allene.With aluminum oxide as carrier, regulation co-catalyst silver is acted on US5587348 with palladium, adds alkali metal, chemical bonding
Fluorine be prepared for the C2 hydrogenation catalyst of function admirable.The catalyst has reduction green oil generation, improves ethylene selectivity, subtracts
The characteristics of few oxygenatedchemicals growing amount.US5519566 discloses a kind of method that wet reducing prepares silver and palladium catalyst, leads to
The addition organic or inorganic reducing agent in maceration extract is crossed, silver and palladium bi-component selective hydrogenation catalyst is prepared.
Due to using precious metals pd as active component, catalyst cost remains high, and noble metal catalyst due to
It is active high, gone into operation stability in device, there are some problems in operating flexibility and catalyst long-term operation aspect of performance.Research and development valency
The hydrogenation catalyst system of New Type of Carbon two that lattice are cheap, performance is remarkable, is always the target of field scientific research personnel effort.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst by selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium second component group
Into catalyst also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound in addition.Urge
Agent calcining, using or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably sintering temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With active, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. as active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and
The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
Described intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between described metal
Compound is prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stabilization reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provides a kind of new Fe series hydrocatalysts and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of Fe-Cu catalyst, add for alkynes in C-2-fraction and diene hydrocarbon-selective
Hydrogen.Using catalyst of the invention, contained a small amount of acetylene and propine (MA), allene (PD) in cracking atmosphere can be selected
Selecting property is hydrogenated with, and is converted into ethene, propylene.Ethene, propylene refining reaction are can be used for, will be contained in ethene, propylene feedstocks gas
Trace acetylene and propine (MA), allene (PD) are removed completely, for producing polymer grade raw material.
In order to achieve the above object, the present invention uses following technical scheme：With high-temperature inorganic oxide as carrier, to urge
Agent quality 100% is counted, and catalyst contains Fe 2~15%, and containing Cu 0.05~0.5%, preferred content is Fe 4~12%, Cu
0.08~0.3%；Catalyst specific surface is 10~300m2/ g preferably 30~170m2/ g, pore volume is 0.2~0.65ml/g, preferably
0.30~0.63ml/g；Wherein Fe is loaded with carrier, through 250 DEG C~600 DEG C roastings, with hydrogen by impregnation method
Atmosphere is reduced at a temperature of 200~400 DEG C and is obtained, and the Fe elements in catalyst are main with α-Fe2O3Form is present.
Fe elements can be with Fe, Fe in catalyst of the invention2O3、Fe3O4, the variform such as FeO exist, but wherein α-
Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for more than the 50% of Fe gross masses.
Carrier of the invention is high-temperature inorganic oxide, key problem in technology of the invention be containing Fe in catalyst, and
Roasting and reduction process are have passed through, to carrier and is had no special requirements, such as can be aluminum oxide, silica, zirconium oxide, magnesia
In one or more.But it is the most frequently used, it is also most preferably aluminum oxide or alumina series carrier, alumina series carrier refers to oxygen
Change the complex carrier of aluminium and other oxides, wherein aluminum oxide accounts for more than the 50% of complex carrier quality, such as can be aluminum oxide
With the compound of the oxide such as silica, zirconium oxide, magnesia, preferably alumina-zirconia composite carrier, wherein aluminum oxide
Content is more than 60%.Aluminum oxide can be θ, α, γ type or the mixture of its various crystal formation, preferably α-Al2O3Or containing α-
Al2O3Mixing crystal formation aluminum oxide.
Present invention also offers the preparation method of the catalyst：
Catalyst distinguishes impregnated carrier, is aged respectively, does by preparing the Fe predecessors aqueous solution, the Cu predecessor aqueous solution
It is dry, roasting or with after its mixed solution impregnated carrier be aged, dry, roasting, finally reduction obtain.
Preferred condition is in preparation method of the present invention：
30~60 DEG C of dipping temperature, 10~60min of load time, maceration extract pH value 1.5~5.0, Aging Temperature 30~60
DEG C, 30~120min of digestion time, 300 DEG C~400 DEG C of sintering temperature, 180~300min of roasting time.
Dried in the present invention and be preferably temperature programming drying, drying temperature program setting is：
Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：
Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
The method for preparing catalyst that the present invention recommends is comprised the following steps that：
(1) carrier is weighed after measurement carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity,
According to carrier water absorption rate and dipping method, dipping solution, and regulation maceration extract pH value 1.5~5.0 on request are prepared, and by solution
Be heated to 30~60 DEG C it is standby.
(3) using incipient impregnation or when spraying method, the carrier that will can be weighed is put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, it is totally turned over carrier, the maceration extract of 30~60 for preparing DEG C is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier that will be weighed is placed in container, is subsequently adding 30~60 DEG C of preparation of dipping
Solution, the visibly moved device of Quick shaking, liberated heat discharges rapidly in making adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier that will be weighed is placed in cyclonic evaporator, is vacuumized, and adds 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst for having impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution unnecessary after dipping is leached, is then dried using the method for temperature programming in an oven, dried
Temperature program(me)：
(6) dried catalyst is calcined in Muffle furnace or tube furnace and is activated, be calcined heating schedule：
Catalyst Cu components are loaded using above-mentioned same steps, 250~600 DEG C of sintering temperature, preferably 300~
400 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
Catalyst of the present invention is using preceding, it is necessary to be reduced with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature is most
It it is well 200~400 DEG C, the condition of recommendation is to use N2+H2Gaseous mixture is reduced for 260~330 DEG C under the conditions of pressure-fired, also
The former time is preferably 240~360min, the best 60~500h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
The active component of catalyst is mainly Fe in the present invention, can be non-precious metal catalyst, it might even be possible to without cobalt,
Nickel, molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms are present in FeO, pushed away in the present invention
Recommend and at least add Cu in the activity composition of iron content, be conducive to formation, the dispersion of activation of catalyst phase, and be conducive to activation
The stabilization of phase, improves catalyst choice and anticoking capability.
The activity composition of the activation temperature of catalyst and catalyst, content and carrier related, activated mistake in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be too high；On the other hand, its activation degree is again
Determine the reducing condition of catalyst, provided in the present invention in the catalyst for using still with α-Fe2O3The Fe of form for it is main into
Point, undue reduction can influence the effect of catalyst, influence selectivity, easy coking on the contrary.
Recommend to add Cu in the activity composition of iron content in the present invention, be more beneficial for reducing activation temperature, be conducive to urging
Formation, the dispersion of agent activation phase, improve catalyst choice.
Catalyst of the present invention has the advantages that：
(1) catalyst cost of the present invention is far below precious metals pd catalyst, the harmless easy acquirement of raw materials, and prepares
Method is simple, technically easily realizes.
(2) catalyst hydrogenation activity of the present invention is gentle, and operating flexibility is good, is suitable to industrialized unit application.
(3) catalyst choice of the present invention is good, and alkene increment is higher than noble metal catalyst.
(4) catalyst " green oil " growing amount of the present invention is far below noble metal catalyst, is suitable to catalyst long period fortune
OK.
Brief description of the drawings
Fig. 1 is XRD spectra (deduction vector background) after the catalyst reduction of the embodiment of the present invention 3.
Fig. 2 is XRD spectra (deduction vector background) after the high-temperature roasting catalyst reduction of comparative example 2.
Fig. 3 is XRD spectra (deduction vector background) after the catalyst high temperature reduction of comparative example 5.
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature
The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity
Symbol description in Fig. 1：
▲ it is α-Fe2O3, ◆ it is Cu, ■ is Fe3O4。
Symbol description in Fig. 2：
▲ it is α-Fe2O3, ● it is CuFeO3, ■ is Fe3O4。
Symbol description in Fig. 3：
★ is Fe for α-Fe, ■3O4, ◆ it is Cu.
α-Fe in Fig. 12O3Relative amount 11.20%.
Fe and second component combine to form CuFe in Fig. 22O4, help component to be sintered with active component, destroy active component
Distribution and structure.
α-Fe are free of in Fig. 32O3Phase, Fe mainly with simple substance α-Fe forms occur, relative amount 8.92%, third component with
Simple substance Cu forms occur.
Specific implementation method is as follows：
Analysis test method：
Specific surface：GB/T-5816
Pore volume：GB/T-5816
Different crystal forms Fe oxide contents：XRD
Active component content in catalyst：Atomic absorption method
Conversion ratio and selectivity are calculated by formula below in embodiment：
Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content
Ethylene selectivity (%)=100 × △ ethene/△ acetylene
Embodiment 1
The trifolium-shaped alpha-alumina supports 100ml of 4.5 × 4.5mm of Φ is weighed, is placed in 1000ml beakers.Take nitric acid
Iron, heating for dissolving in 60ml deionized waters, adjust pH value 2.5, maceration extract temperature 50 C, incipient impregnation in carrier surface,
Rapid shake carrier impregnation 6min, stands 30min to adsorption equilibrium, beaker mouthful is fully sealed with preservative film, in 60 DEG C of water-baths
Ageing 30min, then in an oven according to program：Drying catalyst,
Catalyst is moved into evaporating dish, activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： Weigh copper nitrate,
Impregnated according to above-mentioned preparation process.Physical index and catalyst components content are shown in Table 1.
Evaluation method：
Catalyst performance evaluation is carried out on 10ml micro-reactors, catalyst is crushed in mortar, takes 10~20 mesh sieves point
3ml, is diluted to 5ml and is loaded with 20 mesh beades.
Catalyst is first reduced with the nitrogen of 40% hydrogen+60%, 300 DEG C of reduction temperature, pressure 0.5MPa, recovery time
4h。
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 1.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated
Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized+And Cl-Ion, is subsequently adding matter
Amount concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-Al and answer
Carrier is closed, aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.
Complex carrier 100ml is weighed, is placed in 1000ml large beakers.Iron chloride and copper chloride are taken, heating for dissolving is in 100ml
In deionized water, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min, will be many
Remaining maceration extract is filtered, and catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Drying catalyst, evaporating dish is moved into by catalyst, and programmed temperature method is used in Muffle furnace
Carry out activation of catalyst, activation procedure：
Physical index and catalyst components content are shown in Table 1.
Evaluating catalyst is carried out using the same procedure of embodiment 1, is reduced with 30% hydrogen, 260 DEG C of reduction temperature, pressure
Power 0.5MPa, recovery time 4h.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 1.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Take ferric nitrate to be dissolved in 40ml deionized waters, adjust pH
Value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly, bears
Carry process control to be completed in 6min, then in an oven according to program：
Drying catalyst, evaporating dish is moved into by catalyst, and activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence： Obtain a leaching
Catalyst.
Using first step same procedure, copper nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, be calcined,
Obtain final catalyst.Drying program：Calcination procedure：It is catalyzed after reduction
Agent XRD analysis are as shown in Figure 1.Physical index and catalyst components content are shown in Table 1.
Evaluated using the same procedure of embodiment 1, catalyst is reduced with 20% hydrogen, 280 DEG C of reduction temperature, pressed
Power 0.5MPa, recovery time 4h.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 1.
Embodiment 4
Ball-aluminium oxide-the titanium dioxide carrier of the Φ 2.0mm of 50ml is weighed, is placed in rotary evaporator.Take ferric nitrate molten
Solution is in 15ml deionized waters, and regulation pH value 3.5 is standby.Rotary evaporator vacuum pumping pump is opened, to vacuum 0.1mmHg, so
The maceration extract for preparing is slowly added to from charge door afterwards, 5min is added, rotation is evaporated to catalyst table under 60 DEG C of heating water baths
Face mobile moisture is wholly absent, and completes load, and the catalyst that will have been loaded removes rotary evaporator, in an oven according to program： Drying, in Muffle furnace according to： Roasting.Obtain a leaching catalyst.
Copper nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Dry journey
Sequence：Calcination procedure：
Physical index and catalyst components content are shown in Table 1.
Evaluated using the same procedure of embodiment 1, catalyst is reduced with 15% hydrogen, 300 DEG C of reduction temperature, pressed
Power 0.5MPa, recovery time 4h.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 1.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature
400℃。
Obtain physical index and catalyst components content is shown in Table 1.
Catalyst is reduced with 25% hydrogen, 320 DEG C of temperature, pressure 0.5MPa, soak time 4h.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Reaction result is as shown in table 1.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are well mixed according to a certain percentage, Ran Hou
Extruded moulding on banded extruder, 120 DEG C of dryings, 550 DEG C of roasting 3h, obtain Zr-Si-Al composite oxide carriers in Muffle furnace.
The Zr-Si-Al carriers of preparation are weighed, catalyst is prepared using the same procedure of embodiment 4.
Obtain physical index and catalyst components content is shown in Table 1.
Catalyst carries out high-temperature activation in tube furnace, and activation phenomenon is the nitrogen of 45% hydrogen+55%, 360 DEG C of temperature, pressure
Power 0.5MPa, soak time 4h.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane is Balance Air), constitute as follows：
Reaction result is as shown in table 1.
Embodiment 7
The aluminum oxide for taking Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C
Change.Obtain physical index and catalyst components content is shown in Table 1.
Catalyst is reduced, 280 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 20% hydrogen
Between 4h.Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
Reaction result is as shown in table 1.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 4.5m2/ g, pore volume is 0.32ml/g.Using equi-volume impregnating,
By silver nitrate solution incipient impregnation on carrier, ageing-dry-roasting obtains a leaching catalyst, then by palladium bichloride
Dissolving, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute PAH-01 hydrogenation catalysts).Urge
Agent Pd contents are that 0.050%, Ag contents are 0.20%.Physical index and catalyst components content are shown in Table 1.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h at 100 DEG C-1。
Evaluate unstripped gas composition：
Reaction result is as shown in table 1.
Comparative example 2
Carrier is made with Φ 4.0mm aluminum oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃。
Catalyst is reduced with 25% hydrogen, 300 DEG C of temperature, pressure 0.5MPa, time 4h.Reduction rear catalyst
XRD diffraction spectrograms are as shown in Figure 2.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Reaction result is as shown in table 1.
Comparative example 3
The alumina support of Φ 4.0mm is weighed, low iron content catalyst is prepared using the same procedure of embodiment 1.Obtain thing
Property index and catalyst components content are shown in Table 1.
Catalyst is reduced with 35% hydrogen, 300 DEG C of temperature, pressure 0.5MPa, soak time 4h.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Reaction result is as shown in table 1.
Comparative example 4
The same catalyst of Example 1, directly drives after being activated at 450 DEG C, is reduced without hydrogen.
Obtain physical index and catalyst components content is shown in Table 1.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Reaction result is as shown in table 1.
Comparative example 5
The same catalyst of Example 1, in 350 DEG C of activation.Obtain physical index and catalyst components content is shown in Table 1.
Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 500 DEG C of temperature, pressure
0.5MPa, soak time 4h.The XRD diffraction spectrograms for reducing rear catalyst are as shown in Figure 3.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane is Balance Air), constitute as follows：
Reaction result is as shown in table 1.
The embodiment of table 1 and comparative example carrier, catalyst physical property and catalyst reaction performance
Note：Acetylene and ethene gather and generation n-butene, further gather and generate " green oil ", are generally given birth to n-butene in analysis
Catalyst green oil is levied into scale " growing amount.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of Fe-Cu selective hydrogenation catalysts, are non-precious metal catalysts, and carrier is high-temperature inorganic oxide, its feature
It is that active component at least contains Fe, Cu, in terms of catalyst quality 100%, catalyst contains Fe 2~15%, containing Cu 0.05~
0.5%, preferred content is Fe 4~12%, Cu 0.08~0.3%；Catalyst specific surface is 10~300m2/ g, preferably 30~
170m2/ g, pore volume is 0.2~0.65ml/g, and preferably 0.30~0.63ml/g, wherein Fe are loaded with carrier by impregnation method
On, through 250 DEG C~600 DEG C roastings, reduced at a temperature of 200~400 DEG C with the atmosphere of hydrogen and be obtained；In catalyst, Fe master
Will be with α-Fe2O3Form is present.
2. Fe-Cu selective hydrogenation catalysts according to claim 1, it is characterised in that α-Fe2O3The Fe of form will account for the total matter of Fe
More than the 50% of amount.
3. Fe-Cu selective hydrogenation catalysts according to claim 1, it is characterised in that carrier is that aluminum oxide or alumina series are carried
Body, alumina series carrier refers to the complex carrier of aluminum oxide and other oxides, and wherein aluminum oxide accounts for complex carrier quality
More than 50%, more particularly described alumina series carrier refers to aluminum oxide and silica, zirconium oxide, the compound of magnesia, most
It is well alumina-zirconia composite carrier, wherein alumina content is more than 60%；Aluminum oxide can be for θ, α, γ type or it is more
Plant the mixture of crystal formation, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal formation aluminum oxide.
4. Fe-Cu selective hydrogenation catalysts according to claim 1, it is characterised in that the impregnation method is isometric leaching
Stain, excessive dipping, surface are sprayed, vacuum impregnation or multiple dipping.
5. the preparation method of any Fe-Cu selective hydrogenation catalysts of a kind of claim 1-4, it is characterised in that catalyst
Preparation process includes：The aqueous solution of predecessor containing Fe, the maceration extract of the Cu predecessor aqueous solution are prepared, impregnated carrier, difference are old respectively
Change, dry, being calcined or with ageing, dry, roasting, finally reduction acquisition after its mixed solution impregnated carrier.
6. the preparation method of Fe-Cu selective hydrogenation catalysts according to claim 5, it is characterised in that dipping temperature 30~60
DEG C, 10~60min of load time, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time,
250 DEG C~600 DEG C of sintering temperature, preferably 300~400 DEG C, 180~300min of roasting time.
7. the preparation method of Fe-Cu selective hydrogenation catalysts according to claim 5, it is characterised in that it is temperature programming to dry
Dry, drying temperature program setting is：
8. the preparation method of Fe-Cu selective hydrogenation catalysts according to claim 5, it is characterised in that be roasted to temperature programming
It is calcined, sintering temperature program setting is：
9. the preparation method of Fe-Cu selective hydrogenation catalysts according to claim 5, it is characterised in that catalyst reduction refers to
Catalyst uses preceding, the catalyst N after roasting2+H2Gaseous mixture gas is reduced, H2Content is preferably 10~50%, reduction
200~400 DEG C of temperature, 240~360min of recovery time, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；It is excellent
It is to be reduced at 260~330 DEG C to select condition, 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
10. the purposes of Fe-Cu selective hydrogenation catalysts described in a kind of claim 1, it is characterised in that Fe-Cu selects hydrogenation catalyst
Agent is used for contained acetylene and propine, the selective hydrogenation and removing of allene in ethene atmosphere.
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