CN108250020A - A kind of selection method of hydrotreating of C3 fraction - Google Patents
A kind of selection method of hydrotreating of C3 fraction Download PDFInfo
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- CN108250020A CN108250020A CN201611245818.5A CN201611245818A CN108250020A CN 108250020 A CN108250020 A CN 108250020A CN 201611245818 A CN201611245818 A CN 201611245818A CN 108250020 A CN108250020 A CN 108250020A
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- catalyst
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- temperature
- selection method
- hydrogen
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- 238000010187 selection method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 154
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 15
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001361 allenes Chemical class 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017061 Fe Co Inorganic materials 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 62
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002803 maceration Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 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
- -1 propine allene Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- 239000003426 co-catalyst Substances 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 238000001994 activation Methods 0.000 description 15
- 230000004913 activation Effects 0.000 description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000012856 packing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 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 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000004332 silver Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000010354 integration 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method 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
- 238000007614 solvation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003643 water by type Substances 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
- 206010013786 Dry skin Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics 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
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- 238000011068 loading method Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- 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
-
- 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
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of selection method of hydrotreating of C3 fraction, the C3 fraction as hydrogenating materials carries out selection plus hydrogen by Fe Co catalyst after matching hydrogen, propine in material (MA), allene (PD) is converted into propylene.Catalyst carrier is high-temperature inorganic oxide, and active component is at least containing Fe, Co, and in terms of catalyst quality 100%, catalyst contains Fe 9~15%, Co 3~4%；Specific surface is 10~300m20.2~0.65ml/g of/g, Kong Rongwei, wherein Fe, Co are to be loaded with by impregnation method on carrier, and fired, hydrogen atmosphere reduction is made.Reaction condition：30~50 DEG C, 1.5~3.5MPa of pressure of inlet temperature, 15~120h of liquid phase air speed‑1, hydrogen/MAPD=1~10.The catalyst has good hydrogenation activity and excellent olefine selective, and alkene increment is high, and long-term operation performance is good, and catalyst cost is far below precious metals pd catalyst.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating of C3 fraction, particularly a kind of to use Fe-Co catalyst by carbon three
The method that contained propine (MA) and allene (PD) selection are hydroconverted into propylene in fraction.
Background technology
Propylene is one of most important basic material of petrochemical industry, is the important monomer for synthesizing various polymer, exhausted big portion
Divide and be made by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel) steam cracking.Through this method obtain with
C based on propylene3In fraction, propylene content be 70~90% (mol), propane 5~10% (mol), propine (PD)+allene
(MA) it is 1.5~8.0% (mol).The presence of MAPD can influence the quality of polymerization product, generally be used in petrochemical industry at present
The method of selection plus hydrogen removes.The usual process conditions of hydrogenation reaction are：20~50 DEG C of reactor inlet temperature, reaction pressure
2.2~3.0MPa, 15~120h of liquid phase volume air speed-1, hydrogen/(MA+PD) (mol)=1~3.
It is with Al that traditional C_3 hydrogenation catalyst, which uses catalyst,2O3For carrier, using Pd as active component, adding in Ag is
Active component is helped, the specific surface area of catalyst is 15~100m2/g.The preparation method of catalyst is using infusion process.It is being catalyzed
It is influenced to be especially apparent by maceration extract surface tension and solvation effect in the dipping of agent and drying process process, metal active
Component presoma is deposited on carrier surface with aggregate form.In addition, the distribution between Pd and Ag is undesirable, catalyst is lived
Property is difficult to control, and the selectivity of catalyst relies primarily on the dispersity of catalyst aperture and active component to control, due to urging
In agent preparation process, the dispersion of active component is influenced by the quantity of carrier surface group and solvation, catalyst activity
The randomness of component dispersion is big, prepares poor repeatability, therefore the effect for being catalyzed reaction is undesirable.
CN98810096 discloses a kind of method of catalytic distillation, is to add catalysis to remove the MAPD in C3 fraction
Hydrogen and rectifying separation process are combined into one, and since heat exchange is abundant in this process, are not susceptible to temperature runaway, while in the process
A small amount of oligomer of middle generation, is also easy to be carried over, and can be reduced much in the coking degree of catalyst surface.This method is to catalysis
The filling of destilling tower is more demanding, and the distribution of fluid can have a significant impact to separating effect.This method also increases simultaneously
The difficulty of operation.
Patent CN201110086151.X discloses a kind of method of C 3 fraction selective hydrogenation, the catalysis that this method uses
Agent, using Pd as main active component, using aluminium oxide as carrier, addition co-catalyst silver.By adsorbing specific high score on carrier
Sub- compound forms macromolecule wrapped layer in carrier surface certain thickness, with compound and high molecular weight reactive with functional base,
With the function base that can be complexed with active component, complexing is occurred instead on carrier surface function base by active component
Should, ensure active component orderly and high degree of dispersion.Using the patented method, the specific high-molecular compound of carrier adsorption passes through oxygen
The hydroxyl and macromolecule for changing aluminium carry out chemisorbed, and the amount of carrier adsorption high-molecular compound will be by the hydroxyl quantity of aluminium oxide
Limitation；The complexing of macromolecule and Pd by functionalization is not strong, and sometimes up to activity component load quantity does not reach requirement,
Residual fraction active component is gone back in maceration extract, catalyst cost is caused to improve；C_3 hydrogenation catalyst is prepared also using this method
There are technological process it is complicated the shortcomings that.
Presently disclosed C_3 hydrogenation catalyst causes to be catalyzed using precious metals pd as active component, and content is higher
Agent cost remains high.Development cost is lower, and preparation process is simple and environmentally-friendly, and the propine third with excellent activity and selectivity
Diene (MAPD) selective hydrogenation catalyst has extremely important meaning.
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 copper, 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.
In conclusion the selective hydrogenation of C3 fraction, at present mainly urges base metal using noble metal catalyst
Although extensive work has been carried out in the research and development of agent, but still have far distance apart from industrial applications.It is asked to solve this
Topic, the present invention provide a kind of method for adding hydrogen using the progress C3 fraction of Fe-Co hydrogenation catalysts.
Invention content
The purpose of the present invention is to provide a kind of selection method of hydrotreating of C3 fraction, especially suitable for sequence point will be come from
Selection from the C3 fraction of depropanizing tower tower top in flow or predepropanization technique adds hydrogen, will using Fe-Co hydrogenation catalysts
Depropanizing tower tower is come from dethanizer bottom of towe carbon 3 material or predepropanization front-end hydrogenation stream in sequence separation process
Contained propine (MA), allene (PD) carry out selection plus hydrogen in the carbon 3 material of bottom, are converted to propylene.
The selection method of hydrotreating for C3 fraction after matching hydrogen, into adiabatic reactor reactor carry out selection plus hydrogen, by object
Contained propine, allene are converted into propylene in material, Fe-Co selective hydrogenation catalysts are housed in adiabatic reactor reactor, carrier is
High-temperature inorganic oxide, active component is at least containing Fe, Co, in terms of catalyst quality 100%, catalyst containing Fe 9~
15%, preferred content is 10~14%, and containing Co 3~4%, preferred content is 3.2~3.8%；Catalyst specific surface for 10~
300m2/ g, preferably 90~170m2/ g, Kong Rongwei 0.2~0.65ml/g, wherein preferably 0.45~0.60ml/g, catalyst are logical
It crosses impregnation method to load with active component on carrier, fired, hydrogen atmosphere reduction is made；Reaction condition：Reactor inlet
30~50 DEG C, 1.5~3.5MPa of reaction pressure of temperature, 15~120h of liquid phase air speed-1, hydrogen/MAPD=1~10；It is preferred to add
Hydrogen condition is：30 DEG C~45 DEG C, 2~3MPa of reaction pressure, 30~60h of liquid phase air speed of adiabatic reactor reactor inlet temperature-1, hydrogen
Gas/propine allene 1.1~3.
Method of hydrotreating of the present invention uses hydrogenation catalyst, and carrier is high-temperature inorganic oxide, such as aoxidizes
One or more of aluminium, silica, zirconium oxide, magnesia etc..It is preferred that aluminium oxide or alumina series carrier, alumina series
Carrier refers to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for more than the 50% of complex carrier quality, such as may be used
To be the compound of the oxides such as aluminium oxide and silica, zirconium oxide, magnesia, 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.
The present invention uses the preparation process of Fe-Co selective hydrogenation catalysts to include except alkynes method：
Prepare Fe predecessors aqueous solutions, Co predecessor aqueous solutions, respectively impregnated carrier, be aged respectively, be dry, roasting or with
Its mixed solution impregnated carrier obtains after rear ageing, dry, roasting.
The present invention use hydrogenation catalyst preparation condition for：
30~60 DEG C, 10~60min of dip time of dipping temperature, maceration extract pH value 1.5~5.0；Aging Temperature 30~60
DEG C, 30~120min of digestion time；300~600 DEG C of calcination temperature, preferably 400~500 DEG C, 240~300min of roasting time.
Dry in the present invention is preferably temperature programming drying, and drying temperature program setting is：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.
It 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 is placed in container, then adds in 30~60 DEG C of dipping of preparation
Solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in 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 weighed is placed in cyclonic evaporator, is vacuumized, add in 30~60 DEG C
Maceration extract impregnates 5~10min, and 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 30~60 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 using temperature programming method is roasted, roasts temperature program：
Catalyst Co components are loaded using above-mentioned same steps, 300~600 DEG C of calcination temperature, preferably 400~
500 DEG C, 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.
The catalyst of the present invention needs to be restored with hydrogen-containing gas, H2Volume content is preferably 10~50%, reduction temperature 200
~350 DEG C, 240~360min of recovery time, 60~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is
It is restored at 250~335 DEG C, 200~400h 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, preferably mainly
With α-Fe2O3Form exist, more preferably also contain a certain amount of Fe3O4.Recommend in the present invention in iron-containing activity composition at least
Co is added, and preferably Co mainly exists in the form of CoO, be conducive to formation, the dispersion of catalyst activity phase, and be conducive to
The stabilization of active phase improves 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, over reduction can influence the effect of catalyst instead, reduce activity, selectivity, easy coking.
The selection method of hydrotreating of C3 fraction of the present invention, hydrogenating materials come from Front-end depropanization and front-end hydrogenation, object
Material forms：Propylene 70~90%, propane 10~30%, propine (MA) 0.05~0.2%, allene (PD) 0.05~0.2%,
Using single stage adiabatic reactor reaction device.
The selection method of hydrotreating of C3 fraction of the present invention, hydrogenating materials come from sequence separation process, material composition
For：Propylene 70~90%, propane 10~30%, propine (MA)+allene (PD) 0.5~8.0%.Propine (MA)+allene
(PD)≤4.0% it is exhausted using two sections of series connection during propine (MA)+allene (PD) ＞ 4.0% using single stage adiabatic reactor when
Thermal reactor.
The selection method of hydrotreating of C3 fraction of the present invention, during using two sections of series connection adiabatic reactors, first segment is anti-
Answer 30~40 DEG C of device inlet temperature, 40~50 DEG C of second segment reactor inlet temperature.
The selection method of hydrotreating of C3 fraction using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, ethylene
Loss late is low, and even without ethylene loss, " green oil " production quantity is far below noble metal catalyst, and catalyst anticoking capability is excellent
It is different, and using this method, there is preferable anti-N, S, As, O performance.
Description of the drawings
Fig. 1 is using the C_3 hydrogenation flow chart without pre- hydrogenation technique.
Fig. 2 is the C_3 hydrogenation flow chart using pre- hydrogenation technique.
In figure：1-oil scrubber；2-water scrubber；3-heat exchanger；4-caustic wash tower；5-domethanizing column；6-dethanizer；
7-depropanizing tower；8-C_3 hydrogenation reactor；9-predepropanization tower；10-Acetylene converter；11-compressor.
Fig. 3 restores rear catalyst XRD spectra for embodiment 1.
Fig. 4 restores rear catalyst XRD spectra for comparative example 2.
Fig. 5 restores rear catalyst XRD spectra for 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 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. 3：
● it is α-Fe2O3, ▲ be CoO, ■ Fe3O4。
Symbol description in Fig. 4：
● it is α-Fe2O3, ■ Fe3O4, ◆ it is Co.
Symbol description in Fig. 5：
■ is Fe3O4, ☆ CoFe2O4, ◆ for Co, ★ is α-Fe.
Fig. 3 is using XRD diffraction spectrograms after the technology of the present invention preparation catalyst reduction, wherein middle α-Fe2O3Relative amount
9.29%, part Fe is reduced to Fe3O4, Co exists in the form of CoO.
Fig. 4 is XRD diffraction patterns, wherein α-Fe after the low Co contents catalyst reduction of comparative example2O3Content is 8.79%, is had
Fe3O4Mutually exist, Co is reduced to simple substance.
Fig. 5 XRD spectras after 380 DEG C of reduction for comparative example high-temperature roasting catalyst, Fe is mainly with Fe3O4Phase morphology exists,
Relative amount 8.69%, with the presence of α-Fe, the second component Co is mainly with CoFe2O4In the presence of, have simple substance Co appearance.
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：
Compare table：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：
MAPD conversion ratios (%)=100 × △ MAPD/ entrance MAPD contents
Propylene Selectivity (%)=100 × △ propylene/△ MAPD
Embodiment 1
Weigh the trifolium-shaped alumina support of 4.5 × 4.5mm of Φ.Ferric nitrate is taken, is dissolved by heating in 60ml deionized waters
In, adjust pH value 2.5, maceration extract temperature 50 C, incipient impregnation stirs rapidly carrier impregnation 6min in carrier surface, static
30min is to adsorption equilibrium, and 60 DEG C are aged 30min, then in an oven according to program：Catalyst is dried, activation of catalyst is then carried out using programmed temperature method,
Activation procedure：
Cobalt nitrate is weighed, is impregnated according to above-mentioned preparation process.Carrier is shown in catalyst physical index and catalyst components content
Table 1.
Catalyst in reduction furnace with+60% nitrogen of 40% hydrogen before use, restored, 420 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Restore rear catalyst XRD analysis as shown in Figure 3, using hydrogen flow is added attached drawing 1 Suo Shi, two sections are gone here and there
Join adiabatic reactor technique.
Reaction mass air volume forms：C3H4(MA)=3.3%, C3H4(PD)=2.7%, C3H8=10.5% remaining be
C3H6.Reaction result is as shown in table 2.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with salpeter solution, stirs 10h, coprecipitated
It forms sediment and generates uniform Al-Zr particles.Product is filtered, Na therein is washed with deionized+And Cl-Then ion adds in matter
A concentration of 15% polyvinyl alcohol is measured as pore creating material, it is kneaded and formed.130 DEG C of dry 2h, 650 DEG C of roasting 4h obtain Zr-Al and answer
Close carrier.Aluminium oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Iron chloride and cobalt chloride are taken, is dissolved by heating in deionized water
In, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, beaker dipping 10min is shaken, by extra maceration extract
It filters out, catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Catalyst is dried, activation of catalyst is carried out using programmed temperature method, activates journey
Sequence：
Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with+60% nitrogen of 30% hydrogen before use, restored, 400 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Using flow shown in attached drawing 2, single stage adiabatic reactor process.
Reactor feed gas uses calibrating gas, material air volume composition：C3H4(MA)=0.8%, C3H4(PD)=0.6%,
C3H8=29.6%, remaining is C3H6.Reaction result is as shown in table 2.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Ferric nitrate is taken to be dissolved in 40ml deionized waters, is adjusted
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 dried, catalyst is moved into evaporating dish, activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence：Room temperatureObtain a leaching
Catalyst.
Using first step same procedure, cobalt nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, is then dried, roast,
Obtain final catalyst.Drying program： Calcination procedure：
Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 400 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.Using flow shown in attached drawing 2, single stage adiabatic reactor process.Reaction raw materials air volume forms：C3H4(MA)=
0.2%, C3H4(PD)=0.1%, C3H8=4.5%, remaining is C3H6.Reaction result is as shown in table 2.
Embodiment 4
The spherical tio2 carrier of the Φ 2.0mm weighed is placed in vacuum impregnation plant.Take ferric nitrate be dissolved in from
In sub- water, it is spare to adjust pH value 3.5.Vacuum impregnation plant vacuum pumping pump is opened, until vacuum degree 0.1mmHg, then from charge door
Prepared maceration extract is slowly added to, 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is completely disappeared, and is completed
Load, the catalyst that will have been loaded, in an oven according to program：Drying,
In Muffle furnace according to： Roasting.Obtain a leaching catalyst.
Cobalt nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, roasts, obtains final catalyst.It is dry
Dry program：Calcination procedure：Room temperature
Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with 15% hydrogen before use, restored, 430 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.Catalyst packing is in fixed-bed reactor.
Using attached drawing 1 Suo Shi plus hydrogen flow, two sections of series connection adiabatic reactor techniques.
Reaction raw materials air volume forms：C3H4(MA)=2.2%, C3H4(PD)=3.2%, C3H8=14.6%, remaining is
C3H6.Reaction result is as shown in table 2.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using 3 same procedure of embodiment.Activation temperature
500℃.Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 450 DEG C, pressure 0.5MPa of temperature, during reduction
Between 4h.Catalyst packing is in fixed-bed reactor.
Using attached drawing 1 Suo Shi plus hydrogen flow, two sections of series connection adiabatic reactor techniques.
Reaction raw materials air volume forms：C3H4(MA)=1.9%, C3H4(PD)=2.2%, C3H6=81.5%, C3H8=
10.5%.Reaction result is as shown in table 2.
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, 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 4 same procedure of embodiment.It carrier and catalyst physical index and urges
Agent each component content is shown in Table 1.
Catalyst is before use, with+55% nitrogen of 45% hydrogen, 490 DEG C, pressure 0.5MPa of temperature, activation in reduction furnace
Time 4h.During use by Catalyst packing in fixed-bed reactor.
Using flow shown in attached drawing 2, single stage adiabatic reactor process.
Reaction raw materials volume forms：C3H4(MA)=1.8%, C3H4(PD)=1.2%, C3H8=29.6% remaining be C3H6。
Reaction result is as shown in table 2.
Comparative example 1
Petrochemical industry research institute LY-C3-01 catalyst, particle diameter take Φ 4.0mm, specific surface area 70m2/ g, Kong Rongwei
0.34ml/g, heap compare 0.90g/ml.Catalyst Pd contents are that 0.3%, Ag contents are 0.8%.
Catalyst in the reactor 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1。
Using attached drawing 1 Suo Shi plus hydrogen flow, two sections of series connection adiabatic reactor techniques.Unstripped gas composition is same as Example 1,
Reaction result is as shown in table 2.
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℃.Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 420 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.Catalyst packing is in fixed-bed reactor.The XRD diffraction spectrograms for restoring rear catalyst are as shown in Figure 4.
Using flow shown in attached drawing 2, single stage adiabatic reactor process.Raw material composition is same as Example 2.Reaction result is such as
Shown in table 2.
Comparative example 3
The aluminium oxide for weighing Φ 4.0mm makees carrier, low iron content catalyst is prepared using 1 same procedure of embodiment, 450
It DEG C is activated.Carrier is shown in Table 1 with catalyst physical index and catalyst components content.
Catalyst in reduction furnace with 45% hydrogen before use, restored, 450 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.Catalyst packing is in fixed-bed reactor.
Using attached drawing 1 Suo Shi plus hydrogen flow, two sections of series connection adiabatic reactor techniques.Reaction raw materials are same as Example 3.Instead
It should the results are shown in Table 2.
Comparative example 4
1 same catalyst of Example, in 450 DEG C of activation, catalyst in reduction furnace with 45% hydrogen before use, carried out
Reduction, 100 DEG C, pressure 0.5MPa, soak time 4h of temperature.Carrier is shown in catalyst physical index and catalyst components content
Table 1.
Using attached drawing 1 Suo Shi plus hydrogen flow, two sections of series connection adiabatic reactor techniques.Reactor feed gas forms and embodiment 4
It is identical.Reaction result is as shown in table 2.
Comparative example 5
1 same catalyst of Example, in 850 DEG C of activation.Carrier contains with catalyst physical index and catalyst components
Amount is shown in Table 1.
Catalyst is restored in tube furnace, atmosphere be+70% nitrogen of 30% hydrogen, 380 DEG C of temperature, pressure
0.5MPa, soak time 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.It is catalyzed after reduction
The XRD diffraction spectrograms of agent as shown in figure 5,
Using flow shown in attached drawing 2, single stage adiabatic reactor process.Reactor feed gas composition is same as Example 2.Reaction
The results are shown in Table 2.
1 carrier of table and catalyst physical index and catalyst components content
2 catalyst reaction performance of table
Note：Acetylene and ethylene gather and generate n-butene, further gather and generate " green oil ", are usually given birth in analysis with n-butene
Into scale sign catalyst green oil " production quantity.
Fe-Co hydrogenation catalysts react for C_3 hydrogenation, to hydrogenation activity and the Pd-Ag levels of catalysts phases of MAPD
When Propylene Selectivity is slightly above Pd-Ag catalyst.Fe is mainly with α-Fe in catalyst2O3In the presence of being reduced to Fe on a small quantity3O4,
Catalyst has good activity.Catalyst must carry out reduction treatment before, not restore or low-temperature reduction, Fe all with α-
Fe2O3In the presence of, poor catalyst activity, it is impossible to meet and add hydrogen needs.Occur α-Fe when reduction temperature is excessively high, under catalyst activity
Drop.With the raising of Fe contents, raised trend is presented in catalyst activity, selectively can accordingly reduce.The addition of Co, contributes to
Improve active component dispersion degree, catalyst activity improve, be particularly useful to improve the hydrogenation activity to MAPD, help component Co with
In the presence of CoO forms, the dispersion of Fe and its oxide is best, and calcination temperature is excessively high to form CoFe2O4, active component is agglomerated into
Larger particles, 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 (11)
1. a kind of selection method of hydrotreating of C3 fraction, C3 fraction is selected after matching hydrogen into adiabatic reactor reactor
Add hydrogen, propine contained in material, allene be converted into propylene, it is characterised in that：It is selected in adiabatic reactor reactor equipped with Fe-Co
Hydrogenation catalyst is selected, carrier is high-temperature inorganic oxide, and active component is at least containing Fe, Co, with catalyst quality 100%
Meter, catalyst contain Fe 9~15%, and preferred content is 10~14%, and containing Co 3~4%, preferred content is 3.2~3.8%；It urges
Agent specific surface is 10~300m2/ g, preferably 90~170m2/ g, Kong Rongwei 0.2~0.65ml/g, preferably 0.45~0.60ml/
G, wherein catalyst are to be loaded with active component on carrier by impregnation method, and fired, hydrogen atmosphere reduction is made；Reaction
Condition：30~50 DEG C, 1.5~3.5MPa of reaction pressure of reactor inlet temperature, 15~120h of liquid phase air speed-1, hydrogen/MAPD=
1~10；Preferably hydroconversion condition is：30 DEG C~45 DEG C, 2~3MPa of reaction pressure of adiabatic reactor reactor inlet temperature, liquid phase are empty
30~60h of speed-1, hydrogen/propine allene 1.1~3.
2. selection method of hydrotreating according to claim 1, it is characterised in that use in hydrogenation catalyst, active component Fe
Mainly with α-Fe2O3Form exists, wherein α-Fe2O3The Fe of form will account for more than 50% Fe gross masses.
3. selection method of hydrotreating according to claim 1, it is characterised in that：Carrier is aluminium oxide or alumina series carrier,
Alumina series carrier refers to the complex carrier of aluminium oxide and other oxides, wherein aluminium oxide account for the 50% of complex carrier quality with
On, complex carrier is the compound of aluminium oxide and silica, zirconium oxide or magnesia, preferably the compound load of aluminium oxide-zirconium oxide
Body, 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. selection method of hydrotreating according to claim 1, which is characterized in that the preparation process of catalyst is used to include：
The maceration extract of the aqueous solution of predecessor containing Fe, Co predecessor aqueous solutions is prepared, difference impregnated carrier is aged, is dry, respectively after roasting
It restores or with its mixed solution impregnated carrier, afterwards reduction acquisition after ageing, dry, roasting.
5. selection method of hydrotreating according to claim 4, it is characterised in that：Dipping temperature 30~60 during catalyst preparation
DEG C, 10~60min of dip time, maceration extract pH value 1.5~5.0；30~60 DEG C of Aging Temperature, 30~120min of digestion time；
300 DEG C~600 DEG C of calcination temperature, preferably 400~500 DEG C, 240~300min of roasting time.
6. selection method of hydrotreating according to claim 4, it is characterised in that：Drying is done for temperature programming during catalyst preparation
Dry, drying temperature program setting is：
7. selection method of hydrotreating according to claim 4, it is characterised in that：It is roasted to during catalyst preparation
Temperature-programmed calcination, calcination temperature program setting are：
8. the selection method of hydrotreating described in claim 4, it is characterised in that：Catalyst reduction refers to catalyst before use, roasting
Catalyst N afterwards2+H2Gaseous mixture is restored, H2Content is preferably 10~50%, 200~350 DEG C of reduction temperature, during reduction
Between 240~360min, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is at 250~335 DEG C
It is restored, 200~400h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.
9. selection method of hydrotreating according to claim 1, it is characterised in that：Dethanizer tower is come from sequence separation process
Bottom carbon 3 material volume forms：Propylene 70~90%, propane 10~30%, propine+allene 0.5~8.0%；Propine
During+allene≤4.0%, using single stage adiabatic reactor, during propine+allene ＞ 4.0%.
10. selection method of hydrotreating according to claim 1, it is characterised in that：Carry out autospasy third in predepropanization front-end hydrogenation stream
Alkane tower bottom of towe carbon 3 material volume forms：Propylene 70~90%, propane 10~30%, propine 0.05~0.2%, the third two
Alkene 0.05~0.2%.
11. selection method of hydrotreating according to claim 1, it is characterised in that adiabatic reactor reactor is single hop or two sections of strings
Join adiabatic reactor.
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| CN112939718A (en) * | 2019-11-26 | 2021-06-11 | 中国石油天然气股份有限公司 | Alkyne removing method for pre-depropanization and pre-hydrogenation process |
| CN112939723A (en) * | 2019-11-26 | 2021-06-11 | 中国石油天然气股份有限公司 | Alkyne removing method for carbon three-fraction selective hydrogenation process |
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