CN108246296A - Fe-Co selective hydrogenation catalyst, preparation method and application thereof - Google Patents
Fe-Co selective hydrogenation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN108246296A CN108246296A CN201611249103.7A CN201611249103A CN108246296A CN 108246296 A CN108246296 A CN 108246296A CN 201611249103 A CN201611249103 A CN 201611249103A CN 108246296 A CN108246296 A CN 108246296A
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- Prior art keywords
- catalyst
- carrier
- temperature
- preparation
- selective hydrogenation
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 171
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910017061 Fe Co Inorganic materials 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 31
- 230000009467 reduction Effects 0.000 claims description 24
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 18
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 238000002803 maceration Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- -1 magnesia compound Chemical class 0.000 claims description 10
- 150000001361 allenes Chemical class 0.000 claims description 8
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 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
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- 238000001994 activation Methods 0.000 description 21
- 230000004913 activation Effects 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 150000001345 alkine derivatives Chemical class 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
- 229910052709 silver Inorganic materials 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 229910021304 Co4Al13 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 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
- 239000003643 water by type Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001704 evaporation Methods 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
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229910002518 CoFe2O4 Inorganic materials 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000004939 coking Methods 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
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018580 Al—Zr Inorganic materials 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
- 229910003321 CoFe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 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
- 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
- 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 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
- 239000008246 gaseous mixture Substances 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
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 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
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 150000002927 oxygen compounds Chemical class 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
- 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
- 230000006641 stabilisation Effects 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- B01J23/75—Cobalt
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
-
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Abstract
The invention relates to a Fe-Co selective hydrogenation catalyst, a preparation method and application thereof, wherein the catalyst contains 2-15% of Fe, 0.5-4.0% of Co, preferably 3-12% of Fe and 1.0-2.5% of Co; the specific surface of the catalyst is 10-300 m2A concentration of 30 to 170m2The pore volume is 0.2-0.65 ml/g, preferably 0.30-0.63 ml/g, wherein the catalyst is prepared by loading active components on a carrier in an impregnation mode, roasting and reducing in hydrogen atmosphere, and Fe is α -Fe mainly2O3Co exists mainly in the form of CoO. The catalyst has mild hydrogenation activity, excellent olefin selectivity, high olefin increment, good operation elasticity, low green oil generation amount, good long-period running performance and far lower catalyst cost than a noble metal Pd catalyst. The catalyst of the present invention resists S, NOx、COxThe capacity is greatly improved.
Description
Technical field
The present invention relates to a kind of Fe-Co selective hydrogenation catalysts, which cracks institute in fraction especially suitable for carbon two
It is prepared in ethylene, propene technique containing acetylene and propine (MA), allene (PD) selective hydrogenation.
Background technology
Ethylene, propylene are one of most important basic materials of petro chemical industry, as the monomer for synthesizing various polymer,
The overwhelming majority is made by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel) steam cracking.It is obtained through this method
To the C2 fractions based on ethylene in also contain 0.5%~2.5% (molar fraction) acetylene.The presence of acetylene can make ethylene
Polymerization process complicate, deteriorate polymer performance.When producing polyethylene with high-pressure process, due to the accumulation of acetylene, have quick-fried
Fried danger；In addition, when producing polyethylene, the presence of acetylene can also reduce polymerization catalyst, increase disappearing for catalyst
Consumption.So the acetylene in ethylene must be dropped to certain value hereinafter, could be as the monomer of synthetic high polymer.
Generally use precious metals pd series hydrocatalyst in industry, the acetylene and C3 being selectively removed in C2 fractions evaporate at present
Propine (MA), allene (PD) in point.Patent US4404124 is prepared for active component palladium shell by step impregnation method and is distributed
Selective hydrogenation catalyst, carbon two is can be applied to, the selection of C3 fraction adds hydrogen, to eliminate in acetylene and propylene in ethylene
Propine allene.US5587348 adjusts co-catalyst silver and is acted on palladium, add in alkali metal, chemical bonding using aluminium oxide as carrier
Fluorine be prepared for the C2 hydrogenation catalyst of function admirable.The catalyst, which has, reduces green oil generation, improves ethylene selectivity, subtracts
The characteristics of few oxygenatedchemicals production quantity.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, prepares silver and palladium bi-component selective hydrogenation catalyst.
Due to the use of precious metals pd as active component, catalyst cost remains high, and noble metal catalyst due to
It is active high, it goes into operation stability in device, there are some problems for operating flexibility and catalyst long-term operation aspect of performance.Research and development valency
The two hydrogenation catalyst system of New Type of Carbon that lattice are cheap, performance is remarkable is always the target that field scientific research personnel makes great efforts.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst is by being selected from the first component of cobalt, gold, silver and selecting second of component group of nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium
Into in addition catalyst further includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.It urges
Fluorite structure is formed after agent calcining, use or regeneration.Catalyst oxide total content 0.01~50%, preferably calcination temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With activity, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. for 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 kinds, additionally include 1~10% auxiliary agent.The inventive technique is mainly used for second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, have good deep hydrogenation ability.The technology be mainly used for rich in CO and
The complete plus hydrogen of ethylene, propylene, butylene etc., is not suitable for alkynes, the selection of alkadienes adds hydrogen in the various industrial tail gas of hydrogen.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
The 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 the metal
Object is closed to be 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 stablizing 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 conclusion the selective hydrogenation of low-carbon alkynes and alkadienes, at present mainly using noble metal catalyst, 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 provide a kind of novel Fe series hydrocatalysts and preparation method thereof.
Invention content
The object of the present invention is to provide a kind of Fe-Co selective hydrogenation catalysts and preparation method thereof and purposes, are mainly used for
Selective hydrogenation, particularly for alkynes in C-2-fraction and alkadienes selective hydrogenation.Catalyst using the present invention, can be with
Contained a small amount of acetylene and propine (MA), allene (PD) in atmosphere will be cracked and carry out selective hydrogenation, be converted into ethylene, propylene.
Ethylene, propylene refining reaction are can be used for, by contained trace acetylene in ethylene, propylene feedstocks gas and propine (MA), allene
(PD) removal completely, for producing polymer grade raw material.
In order to achieve the above object, the present invention provides a kind of Fe-Co selective hydrogenation catalysts, is non-precious metal catalyst,
Carrier is high-temperature inorganic oxide, which is characterized in that active component at least contains Fe, Co, in terms of catalyst quality 100%,
Catalyst contains Fe 2~15%, and containing Co 0.5~4.0%, preferred content is Fe 3~12%, Co 1.0~2.5%；Catalyst
Specific surface is 10~300m2/ g, preferably 30~170m2/ g, Kong Rongwei 0.2~0.65ml/g, preferably 0.30~0.63ml/g,
Middle Fe is to be loaded with by impregnation method on carrier, fired, and hydrogen atmosphere reduction is made, in catalyst, Fe mainly with α-
Fe2O3In the presence of Co mainly exists in the form of CoO.
Fe elements can be with Fe, Fe in the catalyst of the present invention2O3、Fe3O4, the variforms 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.
The carrier of the present invention is one in high-temperature inorganic oxide, such as aluminium oxide, silica, zirconium oxide, magnesia
Kind is several.It is preferred that aluminium oxide or alumina series carrier, alumina series carrier refers to answering for aluminium oxide and other oxides
Carrier is closed, wherein aluminium oxide accounts for more than the 50% of carrier quality, such as can be aluminium oxide and silica, zirconium oxide, magnesia
The compound of oxide, preferably alumina-zirconia composite carrier, wherein alumina content is more than 60%.Aluminium oxide can
Think the mixture of θ, α, γ type or its a variety of crystal form, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal form aluminium oxide.
For the specific surface and Kong Rong of the catalyst of the present invention, can it is different with condition using field according to catalyst and
Difference, the present invention are not limited especially.
The present invention also provides the preparation methods of the catalyst：
Catalyst is by preparing the maceration extract of Fe predecessors aqueous solution, Co predecessor aqueous solutions, impregnated carrier, respectively respectively
It is aged, is dry, roasting or with its mixed solution impregnated carrier, afterwards reduction acquisition after ageing, drying, roasting.
Method for preparing catalyst of the present invention is：
30~60 DEG C, 10~60min of dip time of dipping temperature, maceration extract pH value 1.5~5.0, Aging Temperature 20~60
DEG C, 30~120min of digestion time, 300 DEG C~600 DEG C of calcination temperature, preferably 400~500 DEG C, roasting time 240~
300min。
Dry in the present invention is preferably temperature programming drying, and drying temperature program setting is：
Roasting is activation process in the present invention, and preferably temperature-programmed calcination, calcination temperature program setting is：
Incipient impregnation may be used in heretofore described catalyst, excessive dipping, surface spray, 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 as follows：
(1) carrier is weighed after measuring 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 is prepared, and adjust maceration extract pH value 1.5~5.0 as required, and by solution
Be heated to 30~60 DEG C it is spare.
(3) using incipient impregnation or when spraying method, the carrier weighed can be put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, carrier is totally turned over, prepared 30~60 DEG C of maceration extract is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier weighed can be placed in container, then add in 30~60 DEG C of preparation
Dipping solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in adsorption process, and makes active component uniform load to load
On body, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier weighed can be placed in cyclonic evaporator, vacuumized, add in 30~60
DEG C maceration extract impregnate 5~10min, heating water bath to carrier surface moisture is completely dried.
(4) catalyst impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution extra after dipping is filtered out, is then dried in an oven using the method for temperature programming, it is dry
Temperature program(me)：
(6) dried catalyst in Muffle furnace or tube furnace is roasted and is activated, roast temperature program：
Catalyst Co components are loaded using above-mentioned same steps, 300~600 DEG C of calcination temperature, preferably 400~
500℃。
In catalyst preparation process can also first supported cobalt component load Fe components again.
Two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
It can also contain other active components in addition to containing Fe, Co in catalyst composition in the present invention.
Catalyst of the present invention is before use, need to be restored with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature is most
It is 200~350 DEG C well, the condition of recommendation is to use N2+H2Gaseous mixture is restored for 250~335 DEG C under the conditions of micro-positive pressure, also
The former time is preferably 240~360min, the best 60~500h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms exist in FeO, mainly with α-
Fe2O3Form exist, preferably containing a certain amount of Fe3O4.Recommend at least to add in iron-containing activity composition in the present invention
Co exists to correspond in the form of oxidation state, is conducive to formation, the dispersion of catalyst activity phase, and is conducive to the stabilization of active phase,
Improve catalyst activity, selectivity and anticoking capability.
Fe, Co and its different oxide relative amounts, pass through XRD diffraction peak areas integration method meters in catalyst of the present invention
It calculates.
The activation temperature of catalyst and activity composition, content and carrier related, the activated mistake of catalyst in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be excessively high；On the other hand, activation degree is again
It determines the reducing condition of catalyst, is provided in the catalyst used still with α-Fe in the present invention2O3The Fe of form for mainly into
Point, excessively reduction can influence the effect of catalyst instead, reduce activity, selectivity, easy coking.
Recommend to add Co in iron-containing activity composition in the present invention, advantageously reduce activation temperature, be conducive to be catalyzed
Formation, the dispersion of agent activation phase, improve catalyst choice.Meanwhile add in the conversion that Co is conducive to improve propine, allene
Rate.
Catalyst of the present invention has the advantages that：
(1) active component of catalyst is mainly Fe in the present invention, is non-precious metal catalyst, catalyst cost is far below
Precious metals pd catalyst.The harmless easy acquirement of raw materials, and preparation method is simple, technically easily realizes.
(2) catalyst hydrogenation activity of the present invention is mild, and operating flexibility is good, suitable for 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 " production quantity of the present invention is far below noble metal catalyst, is transported suitable for catalyst long period
Row.
(5) catalyst of the present invention anti-S, NOx、COxAbility greatly improves.
Description of the drawings
Attached drawing 1 is XRD spectra after 3 catalyst reduction of embodiment.
Attached drawing 2 is XRD spectra after 2 catalyst reduction of comparative example.
Attached drawing 3 is XRD spectra after 5 catalyst reduction of comparative example.
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 scanning ranges, 25 DEG C of temperature
1 wavelength of Co K α, abscissa is 2 θ of the angle of diffraction in figure, and ordinate is diffracted intensity
Different crystal forms Fe oxide contents are obtained using XRD diffraction peak areas integration method in catalyst, and benchmark is metal oxygen
Compound total amount.
Symbol description in Fig. 1：
● it is α-Fe2O3, ■ Fe3O4, ▲ be CoO.
Symbol description in Fig. 2：
● it is α-Fe2O3, ■ Fe3O4, ☆ CoFe2O4。
Symbol description in Fig. 3：
■ is Fe3O4, ★ is α-Fe, ◆ it is Co.
Fig. 1 is to prepare catalyst XRD spectra after carrying out reduction, wherein α-Fe using the method for the present invention2O3Relative amount
9.45%, also a small amount of Fe3O4, component is helped to exist in the form of CoO.Catalyst shows good activity and selectivity, adds
Coking generation is seldom during hydrogen.
XRD diffraction spectrograms of the Fig. 2 for comparative catalyst after high-temperature activation, reduction, wherein α-Fe2O3Relative amount
14.1%, second of component is combined to form CoFe with Fe2O4, there is Fe3O4Mutually exist.
Fig. 3 is XRD diffraction spectrogram of the comparative catalyst after high temperature reduction, wherein without α-Fe2O3Phase, Fe3O4It is opposite to contain
6.92%, α-Fe relative amounts 4.31% are measured, component is helped to be reduced into elemental form.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Analysis test method：
Specific surface：GB/T-5816
Kong Rong：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 × △ ethylene/△ 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 appropriate nitre
Sour iron is dissolved by heating in 60ml deionized waters, adjusts pH value 2.5, maceration extract temperature 50 C, incipient impregnation is in carrier table
Face, it is rapid to shake carrier impregnation 6min, 30min is stood to adsorption equilibrium, beaker mouth is fully sealed with preservative film, in 60 DEG C of water-baths
30min is aged, then in an oven according to program：
Catalyst is moved into evaporating dish, activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： Weigh appropriate nitric acid
Cobalt is impregnated according to above-mentioned preparation process.Physical index and catalyst components content are shown in Table 12.
Evaluation method：
Catalyst performance evaluation is carried out on 10ml micro-reactors, catalyst crushes in mortar, and 10~20 mesh is taken to sieve
3ml is diluted to 5ml with 20 mesh beades and is loaded.
Catalyst is first restored with+60% nitrogen of 40% hydrogen, 300 DEG C, pressure 0.5MPa of reduction temperature, the recovery time
4h。
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas, and composition is as shown in table 1：
Table 1 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 2
At 50 DEG C, by a certain amount of NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with salpeter solution, stirring
10h, co-precipitation generate uniform Al-Zr particles.Product is filtered, Na therein is washed with deionized+And Cl-Ion, so
Add in afterwards appropriate mass concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C of dry 2h, 650 DEG C of roasting 4h
Obtain Zr-Al complex carriers, aluminium oxide and zirconium oxide mass ratio are 4 in carrier:1.
Complex carrier 100ml is weighed, is placed in 1000ml large beakers.Take appropriate iron chloride and cobalt chloride, dissolve by heating in
In 100ml deionized waters, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shakes beaker dipping
10min filters out extra maceration extract, and catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program： Catalyst is moved into evaporating dish, in Muffle furnace
Activation of catalyst, activation procedure are carried out using programmed temperature method： Physical index and catalyst components content are shown in Table 12.
Evaluating catalyst is carried out using 1 same procedure of embodiment, is restored with 30% hydrogen, 250 DEG C of reduction temperature, is 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 uses calibrating gas, and composition is as shown in table 2：
Table 2 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Appropriate ferric nitrate is taken to be dissolved in 40ml deionized waters, adjusts 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, loading process
Control is completed in 6min, then in an oven according to program：
Catalyst is moved into evaporating dish, activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace：A leaching is obtained to urge
Agent.
Using first step same procedure, appropriate cobalt nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried,
Roasting, obtains final catalyst.Drying program： Calcination procedure： Restore rear catalyst
XRD analysis is as shown in Figure 1.Physical index and catalyst components content are shown in Table 12.
It is evaluated using 1 same procedure of embodiment, catalyst is restored with 20% hydrogen, 280 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 uses calibrating gas, and composition is as shown in table 3：
Table 3 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 4
Ball-aluminium oxide-titanium dioxide carrier of the Φ 2.0mm of 50ml is weighed, is placed in rotary evaporator.Take a certain amount of nitre
It is spare to adjust pH value 3.5 in 15ml deionized waters for sour dissolved ferric iron.Rotary evaporator vacuum pumping pump is opened, until vacuum degree
Then 0.1mmHg is slowly added to prepared maceration extract from charge door, 5min is added, the rotary evaporation under 60 DEG C of heating water baths
It is completely disappeared to catalyst surface mobile moisture, completes load, the catalyst loaded is removed into rotary evaporator, in an oven
According to program：In Muffle furnace according to： A leaching is obtained to urge
Agent.
Appropriate cobalt nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, roasts, obtains final catalyst.Dry journey
Sequence：Calcination procedure：
Physical index and catalyst components content are shown in Table 12.
It is evaluated using 1 same procedure of embodiment, catalyst is restored with 15% hydrogen, 330 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 uses calibrating gas, and composition is as shown in table 4：
Table 4 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using 3 same procedure of embodiment.Activation temperature
550℃。
It obtains physical index and catalyst components content is shown in Table 12.
Catalyst is restored with 25% hydrogen, 300 DEG C, pressure 0.5MPa, soak time 4h of temperature.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane Balance Air), and composition is as shown in table 5：
Table 5 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are uniformly mixed according to a certain percentage, Ran Hou
Extruded moulding on banded extruder, 120 DEG C of dryings, 420 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 4 same procedure of embodiment.
It obtains physical index and catalyst components content is shown in Table 12.
Catalyst carries out high-temperature activation in tube furnace, and activation phenomenon is+55% nitrogen of 45% hydrogen, and 220 DEG C of temperature is pressed
Power 0.5MPa, soak time 4h.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 6：
Table 6 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Embodiment 7
The aluminium oxide of Φ 4.0mm is taken to make carrier, catalyst is prepared using 1 same procedure of embodiment, is lived at 480 DEG C
Change.It obtains physical index and catalyst components content is shown in Table 12.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 350 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.It is evaluated using 1 same procedure of embodiment and unstripped gas.
Reaction condition：Air speed 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
Reaction result is as shown in table 13.
Comparative example 1
Take Φ 4.0mm alumina supports, specific surface 4.5m2/ g, Kong Rongwei 0.32ml/g.Using equi-volume impregnating,
By on a certain amount of silver nitrate solution incipient impregnation to carrier, ageing-drying-roasting obtains a leaching catalyst, then by one
Quantitative palladium bichloride dissolving, incipient impregnation, ageing-drying-roasting, obtaining final catalyst, (petrochemical industry research institute PAH-01 adds
Hydrogen catalyst).Catalyst Pd contents are that 0.050%, Ag contents are 0.20%.Physical index and catalyst components content are shown in Table
12。
Catalyst is at 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1。
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 7：
Table 7 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Comparative example 2
Carrier is made with Φ 4.0mm aluminium oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃.It obtains physical index and catalyst components content is shown in Table 12.
Catalyst is restored with 25% hydrogen, 200 DEG C, pressure 0.5MPa, time 4h of temperature.Restore rear catalyst
XRD diffraction spectrograms are as shown in Figure 2.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 8：
Table 8 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Comparative example 3
The alumina support of Φ 4.0mm is weighed, low iron content catalyst, activation temperature are prepared using 1 same procedure of embodiment
450 DEG C of degree.It obtains physical index and catalyst components content is shown in Table 12.
Catalyst is restored with 35% hydrogen, 300 DEG C, pressure 0.5MPa, soak time 4h of temperature.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 9：
Table 9 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Comparative example 4
1 same catalyst of Example is directly driven after 450 DEG C of activation, is restored without hydrogen.
It obtains physical index and catalyst components content is shown in Table 12.
Catalyst is restored with 20% hydrogen, 450 DEG C, pressure 0.5MPa, soak time 4h of temperature.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 10：
Table 10 evaluates unstripped gas composition
Reaction result is as shown in table 13.
Comparative example 5
1 same catalyst of Example, in 450 DEG C of activation.It obtains physical index and catalyst components content is shown in Table 12.
Catalyst is restored in tube furnace, atmosphere be+70% nitrogen of 30% hydrogen, 400 DEG C of temperature, pressure
0.5MPa, soak time 4h.The XRD diffraction spectrograms for restoring rear catalyst are as shown in Figure 3.
It is evaluated using 1 same procedure of embodiment.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas uses calibrating gas (ethane is Balance Air), and composition is as shown in table 11：
Table 11 evaluates unstripped gas composition
Reaction result is as shown in table 13.
12 embodiment of table and comparative example carrier, catalyst physical property and catalyst reaction performance
13 embodiment of table and comparative example carrier, catalyst physical property and catalyst reaction performance
Note：Acetylene and ethylene gather and generate n-butene, further gather and generate " green oil ", are usually given birth in analysis with n-butene
Catalyst " green oil " production quantity is levied into scale.
Using the C2 hydrogenation catalyst that Fe-Co is prepared as active component, industrialization Pd-Ag is reached to the hydrogenation activity of alkynes
Levels of catalysts, ethylene selectivity are apparently higher than Pd-Ag catalyst, and " green oil " production quantity is far below noble metal catalyst.Work as Fe
Mainly with α-Fe2O3In the presence of, while have a small amount of Fe3O4When, catalyst have good activity, without reduction or low-temperature reduction,
Fe is all with α-Fe2O3In the presence of catalyst is without activity；There is α-Fe, catalyst activity reduction, as Fe contains when restoring in transition
The raising of amount, catalyst activity are presented certain raising trend, selectively can accordingly reduce.The addition of Co, helps to improve work
Property component dispersion degree, catalyst activity improve, be particularly useful to improve the hydrogenation activity to MAPD, help component Co in the form of CoO
In the presence of, the dispersion of Fe and its oxide is best, and calcination temperature is excessively high to form CoFe2O4, active component is agglomerated into larger
Grain, activity reduce, the raising of " green oil " production quantity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. it is non-precious metal catalyst a kind of Fe-Co selective hydrogenation catalysts, carrier is high-temperature inorganic oxide, feature
It is, active component is at least containing Fe, Co, and in terms of catalyst quality 100%, catalyst contains Fe 2~15%, containing Co 0.5~
4.0%, preferred content is Fe 3~12%, Co 1.0~2.5%；Catalyst specific surface is 10~300m2/ g, preferably 30~
170m2/ g, Kong Rongwei 0.2~0.65ml/g, wherein preferably 0.30~0.63ml/g, Fe are to be loaded with by impregnation method in carrier
On, fired, hydrogen atmosphere reduction is made, and in catalyst, Fe is mainly with α-Fe2O3In the presence of Co mainly exists in the form of CoO.
2. Fe-Co 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 50% amount.
3. Fe-Co selective hydrogenation catalysts according to claim 1, it is characterised in that：Carrier is aluminium oxide or alumina series
Carrier, alumina series carrier refer to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for the 50% of carrier quality
More than, can be aluminium oxide with silica, zirconium oxide, magnesia compound, preferably alumina-zirconia composite carrier,
Wherein alumina content is more than 60%；Aluminium oxide can be the mixture of θ, α, γ type or its a variety of crystal form, preferably α-
Al2O3Or-the Al containing α2O3Mixing crystal form aluminium oxide.
4. a kind of preparation method of any Fe-Co selective hydrogenation catalysts of claim 1-3, it is characterised in that：Catalyst
Preparation process include：The maceration extract of the aqueous solution of predecessor containing Fe, Co predecessor aqueous solutions is prepared, respectively impregnated carrier, difference
It is restored after ageing, dry, roasting or with its mixed solution impregnated carrier, afterwards reduction acquisition after ageing, dry, roasting.
5. preparation method according to claim 4, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10~
60min, maceration extract pH value 1.5~5.0,20~60 DEG C, 30~120min of digestion time of Aging Temperature, 300 DEG C of calcination temperature~
600 DEG C, 240~300min of roasting time, preferably 400~500 DEG C of calcination temperature.
6. preparation method according to claim 4, it is characterised in that：It is dry to be dried for temperature programming, drying temperature program
It is set as：
7. preparation method according to claim 4, it is characterised in that：It is roasted to temperature-programmed calcination, calcination temperature program
It is set as：
8. preparation method according to claim 4, it is characterised in that：The dipping is incipient impregnation, excessive dipping, table
Face sprays, vacuum impregnation or repeatedly dipping.
9. preparation method according to claim 4, it is characterised in that catalyst reduction refers to catalyst before use, after roasting
Catalyst restored with hydrogen-containing gas, H2Volume content is preferably 10~50%, 200~350 DEG C of reduction temperature, preferably
250~335 DEG C, 240~360min of recovery time, 60~500h of air speed-1, 0.1~0.5MPa of reduction pressure.
10. the purposes of Fe-Co selective hydrogenation catalysts described in a kind of claim 1, it is characterised in that Fe-Co selects hydrogenation catalyst
Agent is used for contained acetylene and propine, the selective hydrogenation and removing of allene in ethylene atmosphere.
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| CN111346641A (en) * | 2020-04-14 | 2020-06-30 | 天津大学 | Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction |
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