CN106928006A - Method for preparing polymer-grade ethylene by hydrogenation - Google Patents
Method for preparing polymer-grade ethylene by hydrogenation Download PDFInfo
- Publication number
- CN106928006A CN106928006A CN201511032664.7A CN201511032664A CN106928006A CN 106928006 A CN106928006 A CN 106928006A CN 201511032664 A CN201511032664 A CN 201511032664A CN 106928006 A CN106928006 A CN 106928006A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- temperature
- carrier
- hydrogenation
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 66
- 239000005977 Ethylene Substances 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 155
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000000284 extract Substances 0.000 claims description 11
- 238000002803 maceration Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
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- 238000005245 sintering Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- 239000001301 oxygen Substances 0.000 claims 1
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- 239000007921 spray Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
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- 238000001994 activation Methods 0.000 description 14
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- 150000001345 alkine derivatives Chemical class 0.000 description 10
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- 239000000463 material Substances 0.000 description 9
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- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 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
- 229920002521 macromolecule Polymers 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910021304 Co4Al13 Inorganic materials 0.000 description 5
- 102000002322 Egg Proteins Human genes 0.000 description 5
- 108010000912 Egg Proteins Proteins 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000010970 precious metal Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 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
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- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001361 allenes 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
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 150000002602 lanthanoids Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 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
- 238000006384 oligomerization reaction Methods 0.000 description 1
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- 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
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
A method for preparing polymer-grade ethylene by hydrogenation comprises the following raw materials: ethylene is more than or equal to 99.99 percent (phi), and acetylene is 5-100 ppm. The reaction conditions are that the inlet temperature of the adiabatic bed reactor is 30-50 ℃, the reaction pressure is 1.5-2.5 MPa, and the volume space velocity is 2000-10000 h-1. The hydrogenation catalyst is a Fe selective hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, and the catalyst contains 1-8% of Fe and 0-1% of X by 100% of the mass of the catalyst, wherein X is selected from one or more of K, La and Ce, and the preferable content of X is 0.5-1.2%; the specific surface of the catalyst is 10-200 m2The pore volume is 0.2 to 0.63 ml/g. The catalyst has mild reaction activity, good operation flexibility, low ethylene loss rate, even no ethylene loss, and the green oil generation amount is far lower than that of a noble metal catalyst.
Description
Technical field
The method for producing polymer grade ethylene is hydrogenated with the present invention relates to a kind of, particularly a kind of Fe series catalysts are by ethylene feed
In contained trace acetylene hydro-conversion for ethene method.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device
This raw material.The selection hydrogenation of wherein acetylene has extremely important influence to ethene processing industry, except ensureing going out for hydrogenation reactor
Mouth acetylene content is up to standard outer, and the selectivity of catalyst is excellent, can make the generation ethane that ethene is as few as possible, to improving whole work
The yield of ethene of skill process, improves device economic benefit significant.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%-2.5%, when polyethylene is produced, lacking in ethene
Amount acetylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so must be by the acetylene in ethene
Content drops to certain limit, could be used as the monomer of synthetic high polymer.Therefore acetylene is separated and during conversion is ethylene unit flow
One of important process.
Catalysis selective hydrogenation includes front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene adds
For domethanizing column position, hydrogenation reactor was front-end hydrogenation, hydrogenation reactor before domethanizing column to hydrogen reactor
It is back end hydrogenation after domethanizing column.In current C-2-fraction acetylene hydrogenation, more and more front-end hydrogenations of use carbon two
The characteristics of process, process was hydrogenation reactor before domethanizing column.Front-end hydrogenation is divided into predepropanization and preceding again
Two kinds of techniques of deethanization.Front-end deethanization hydrogenation technique is that hydrogenation reactor is located at after dethanizer, before domethanizing column.It is preceding de-
Propane hydrogenation technique is that hydrogenation reactor is located at after depropanizing tower, before domethanizing column.The difference of flow, brings two kinds of hydrogenation
The difference of material composition.Contain methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethene, second in front-end deethanization hydrogenation material
Alkane)；Evaporated containing methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethene, ethane), carbon three in predepropanization hydrogenation material
Divide (propine, allene, propylene, propane).
Material in ethylene unit through ethylene distillation by after Acetylene converter, then still containing 1 again in material
The acetylene of~10ppm, micro CO, the requirement more and more higher due to polymer grade ethylene product to raw material, along with these impurity
Presence influence whether the performance of ethylene rolymerization catalyst, accordingly, it would be desirable to by way of selecting hydrogenation, before vinyl polymerization
By the selection hydrogenation and removing acetylene of trace acetylene in smart ethylene feed, its content is set to be reduced to below 1ppm.
The selection hydrogenation of trace acetylene is main in current ethylene unit, in smart ethylene feed uses single hop reactor process.
Reactor inlet material is constituted：Ethene >=99.99% (Φ), 1~10ppm of acetylene, hydrogen by the way of distribution, H2/C2H2=
2~20.1.5~2.5MPa of reaction pressure, 2000~10000h of volume space velocity-1, 25 DEG C~60 DEG C of inlet temperature.
Alkynes and diolefin hydrogenate catalyst are to be supported on porous Inorganic material carrier by by noble metal such as palladium
On (US4762956) that obtains.In order to increase the selectivity of catalyst, reduce the green oil that oligomerization is produced during by being hydrogenated with and led
The catalyst inactivation of cause, it is the method for co-catalysis component that prior art is employed and adds such as group ib element in the catalyst：
Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Cu (US3912789), or add alkali metal or alkaline-earth metal
(US5488024) etc., carrier used has aluminum oxide, silica (US5856262), the loyal green stone of honeycomb (CN1176291) etc.
Deng.
US5856262 is reported with the modified silica of potassium hydroxide (or barium, strontium, rubidium etc. hydroxide) as carrier,
The method for preparing low in acidity palladium catalyst, in volume space velocity 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction
0.71%, under conditions of hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Specially
With aluminum oxide as carrier, addition co-catalyst silver is acted on sharp US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst has reduction ethane growing amount, and it is anti-that acetylene of the suppression absorption on catalyst surface carries out partial hydrogenation dimerization
Should, suppress 1,3-butadiene generation, reduce green oil generation, improve ethylene selectivity, reduce oxygenatedchemicals growing amount the characteristics of,
It is applied widely in ethylene industry.However, above-mentioned catalyst is prepared using infusion process, limited by preparation method
System, metal dispersity is only 30% or so, and catalyst performance there is also many deficiencies, still there is further improved necessity.
CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belongs to oil
(natural gas) chemical products synthesize and new catalytic material technical field, be related to it is a kind of have to preparation of ethylene through selective hydrogenation of acetylene it is excellent
The egg-shell catalyst of good catalytic performance.It is characterized in that with aluminum oxide (Al2O3) bead be carrier, using infusion process prepare activity
The loaded catalyst that component palladium is distributed in eggshell type, and using Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd is loaded
It is 0.01~0.1wt% to measure, and Ag is 1~5 with Pd atomic ratios.The invention has the advantages that, the one kind for being provided is used for second
Alkynes selects the egg-shell catalyst of Hydrogenation ethene, can be under the conditions of conversion of alkyne high, especially in the acetylene close to 100%
During conversion ratio, ethylene selectivity high is realized.
Traditional Pd-Ag bimetallics selective hydrogenation catalyst is prepared using aqueous impregnation method.Using sub-dip method
When, what a kind of component can be more is enriched in carrier surface, and another component is enriched in outer surface, only part metals atom phase
Mutually infiltration, forms alloy structure.During using total immersion method, due to the interaction of the presoma and carrier of two metal ion species
Difference, surface tension and solvation, are hardly formed two kinds of uniform loads of component, also can only partly form alloy structure.
When this catalyst is applied to C 2 fraction selective hydrogenation, often in initial reaction stage selectivity preferably, with the extension of run time,
Selectivity constantly declines, and typically operation is accomplished by regeneration for 3~6 months, and economic loss is larger.
CN201110086174.0 by adsorbing specific macromolecular compound on carrier, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with the compound and high molecular weight reactive of the functional base of band, being allowed to have can be complexed with active component
Function base, there is complex reaction on carrier surface function base by active component, it is ensured that active component in order and height point
Dissipate.Using the patented method, the specific macromolecular compound of carrier adsorption carries out chemistry by the hydroxyl of aluminum oxide with macromolecule
Absorption, the amount of carrier adsorption macromolecular compound will be limited by the hydroxyl quantity of aluminum oxide；By the macromolecule of functionalization
Complexing with Pd is not strong, sometimesReachActivity component load quantity does not reach requirement, and residual fraction activearm is gone back in maceration extract
Point, cause catalyst cost to improve；C2 hydrogenation catalyst is prepared using the method and also haves the shortcomings that technological process is complicated.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst by selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium second component group
Into catalyst also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound in addition.Urge
Agent calcining, using or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably sintering temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With active, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. as active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and
The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
Described intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between described metal
Compound is prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stabilization reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provides a kind of new Fe series hydrocatalysts and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of method for being hydrogenated with and producing polymer grade ethylene, a kind of Fe systems catalysis is particularly related to
Agent, selective hydrogenation is carried out by trace acetylene contained in ethylene feed after ethylene rectifying column, is fully converted to ethene, while second
Alkene does not lose.
The present invention provides a kind of method for being hydrogenated with and producing polymer grade ethylene, and the smart ethylene feed of ethylene distillation column overhead is entered
Entering adiabatic reactor reactor carries out selection hydrogenation, to remove trace acetylene therein, adds equipped with the selection of Fe systems in adiabatic reactor reactor
Hydrogen catalyst, carrier is high-temperature inorganic oxide, and catalyst contains Fe 1~8%, preferred content be 2~6%, X 0~
1.0%, wherein X be selected from K, La, Ce in one or several, X preferred contents be 0.2~0.6%；Catalyst specific surface is 10
~200m2/ g, preferably 30~150m2/ g, pore volume is 0.2~0.63ml/g, and preferably 0.3~0.55ml/g, wherein Fe are by leaching
Stain mode is loaded with carrier, through 300 DEG C~700 DEG C roastings, system is reduced at a temperature of 250~500 DEG C with the atmosphere of hydrogen
, the Fe elements in catalyst are main with α-Fe2O3Form is present.Selective hydrogenation reaction condition：Adiabatic reactor reactor inlet temperature
30 DEG C~50 DEG C, 1.5~2.5MPa of reaction pressure, 2000~10000h of volume space velocity-1。H2/C2H2Volume ratio is 2~20, preferably
Hydroconversion condition be：35 DEG C~45 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, volume space velocity 5000
~8000h-1；H2/C2H2Volume ratio is 2~5.
Method of hydrotreating of the present invention, uses hydrogenation catalyst, and carrier is high-temperature inorganic oxide, of the invention
Key problem in technology is that, containing Fe in catalyst, and have passed through roasting and reduction process, to carrier and is had no special requirements, and such as can be
One or more in aluminum oxide, silica, zirconium oxide, magnesia etc..But but it is most common be also most preferably aluminum oxide or
Alumina series carrier, alumina series carrier refers to the complex carrier of aluminum oxide and other oxides, and wherein aluminum oxide accounts for carrier matter
More than the 50% of amount, such as can be aluminum oxide and silica, zirconium oxide, the compound of magnesia oxide, preferably aoxidize
Aluminium-zirconia composite carrier, wherein alumina content is more than 60%.Aluminum oxide can be θ, α, γ type or its various crystal formation
Mixture, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal formation aluminum oxide.
Hydrogenation of the present invention produces polymer grade ethylene method, and the Fe catalyst preparation process of use includes：
Catalyst distinguishes impregnated carrier, is aged respectively, does by preparing the Fe predecessors aqueous solution, the X predecessor aqueous solution
It is dry, roasting or with after its mixed solution impregnated carrier be aged, dry, roasting, finally restore acquisition.
Preferred condition is in the preparation method of used catalyst of the present invention：
30~60 DEG C of dipping temperature, 10~60min of dip time, maceration extract pH value 1.5~5.0, Aging Temperature 30~60
DEG C, 30~120min of digestion time, 400 DEG C~500 DEG C of sintering temperature, 180~300min of roasting time.
Dried in the present invention and be preferably temperature programming drying, drying temperature program setting is：
Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：
Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
Comprise the following steps that：
(1) carrier is weighed after measurement carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity,
According to carrier water absorption rate and dipping method, dipping solution, and regulation maceration extract pH value 1.5~5.0 on request are prepared, and by solution
Be heated to 30~60 DEG C it is standby.
(3) using incipient impregnation or when spraying method, the carrier that will can be weighed is put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, it is totally turned over carrier, the maceration extract of 30~60 for preparing DEG C is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier that will be weighed is placed in container, is subsequently adding 30~60 DEG C of preparation of dipping
Solution, the visibly moved device of Quick shaking, liberated heat discharges rapidly in making adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier that will be weighed is placed in cyclonic evaporator, is vacuumized, and adds 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst for having impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution unnecessary after dipping is leached, is then dried using the method for temperature programming in an oven, dried
Temperature program(me)：
(6) dried catalyst is calcined using temperature programming method, is calcined heating schedule：
Catalyst component X is loaded using above-mentioned same steps, 300~700 DEG C of sintering 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.
The active component of catalyst is mainly Fe in the present invention, can be non-precious metal catalyst, it might even be possible to without cobalt,
Nickel, molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.
Hydrogenation of the present invention produces polymer grade ethylene method, use in hydrogenation catalyst Fe elements can with Fe,
Fe2O3、Fe3O4, several forms are present in FeO, but wherein α-Fe2O3The Fe of form is higher than the content of other forms, best
Account for more than the 50% of Fe gross masses.Recommend in the present invention iron content activity composition in add K, La, Ce in one kind or
It is several, be conducive to activation of catalyst phase formation, dispersion, and be conducive to activate phase stabilization, improve catalyst choice and
Anticoking capability.
The activity composition of the activation temperature of catalyst and catalyst, content and carrier related, activated mistake in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be too high；On the other hand, its activation degree is again
Determine the reducing condition of catalyst, provided in the present invention in the catalyst for using still with α-Fe2O3The Fe of form for it is main into
Point, undue reduction can influence the effect of catalyst, influence selectivity, easy coking on the contrary.
Catalyst reduction of the invention refers to that catalyst uses preceding, the catalyst hydrogen-containing gas reduction after roasting, H2Body
Product content is preferably 10~50%, 250~500 DEG C of reduction temperature, 240~360min of recovery time, and volume space velocity 100~
500h-1, 0.1~0.8MPa of reduction pressure；The condition of recommendation is to use N2+H2Gaseous mixture under the conditions of pressure-fired, 300~400
Reduced at DEG C, 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.The process generally adds in selection
Carried out before hydrogen reaction, preferably carry out being carried out outside i.e. selective hydrogenation reaction device outside device.
Hydrogenation of the present invention produces polymer grade ethylene method, refers in single stage adiabatic bed reactor, by ethene thing
Trace acetylene selective hydrogenation contained in material, is converted into ethene.
Hydrogenation of the present invention produces polymer grade ethylene method, and the raw material for carrying out selective hydrogenation is ethylene rectifying column tower
The smart ethylene feed on top, raw material composition is usually：Ethene >=99.99 volume %, 5~100ppm of acetylene.
Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene loss rate is low, or even does not have
There is ethylene loss, " green oil " growing amount is far below noble metal catalyst, catalyst anticoking capability is excellent.
Brief description of the drawings
Fig. 1 is using the device ethene rectification flow figure of back end hydrogenation technological process；
Fig. 2 is using the device ethene rectification flow figure of front-end deethanization technological process；
Fig. 3 is using the device ethene rectification flow figure of predepropanization technological process；
In figure：
1-oil scrubber；2-water scrubber；3-caustic wash tower；4-drier；5-domethanizing column；6-dethanizer；7-carbon
Two hydrogenation adiabatic reactor reactors；8th, ethylene rectifying column；9th, ethene finishing reactor；10-compressor；11-front-end deethanization tower；
12nd, predepropanization tower；
Accompanying drawing 4 is using the catalyst XRD spectra of the embodiment of the present invention 3 (deduction vector background)；
Accompanying drawing 5 is the catalyst XRD spectra of comparative example 2 (deduction vector background)；
Accompanying drawing 6 is the catalyst XRD spectra of comparative example 5 (deduction vector background)；
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature
The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity
Symbol description in Fig. 4：
● it is α-Fe2O3, ▲ be Fe3O4, ◆ it is CeO；
Symbol description in Fig. 5：
● it is α-Fe2O3, ▲ be Fe3O4, ■ is LaFeO3；
Symbol description in Fig. 6：
▲ it is Fe3O4, ▼ is Ce, and ★ is α-Fe；
In Fig. 4, Fe is main with α-Fe in catalyst2O3Form occurs, relative amount 7.6%；
In Fig. 5, second component La, mainly combines to form LaFeO with ferriferous oxide in catalyst3, component is helped with activity
Component is sintered, and destroys Active components distribution and structure, catalyst activity reduction；
α-Fe are free of in Fig. 62O3Phase, Fe mainly with simple substance α-Fe forms occur, relative amount 8.92%, third component with
Simple substance Ce forms occur.
Specific embodiment
Analysis test method：
Specific surface：GB/T-5816
Pore volume：GB/T-5816
Different crystal forms oxide content：XRD
Active component content：Atomic absorption method
Conversion ratio and selectivity are calculated by formula below in embodiment：
Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content
Ethylene selectivity (%)=100 × △ ethene/△ acetylene
Embodiment 1
Weigh the trifolium-shaped alumina support of 4.5 × 4.5mm of Φ.Ferric nitrate is taken, heating for dissolving is in 60ml deionizations
In water, pH value 2.5 is adjusted, maceration extract temperature 50 C, incipient impregnation stirs rapidly carrier impregnation 6min in carrier surface,
To adsorption equilibrium, 60 DEG C are aged 30min to static 30min, then in an oven according to program：Drying catalyst, is then urged using programmed temperature method
Agent is activated, activation procedure： Lanthanum nitrate is weighed, is impregnated according to above-mentioned preparation process.The catalyst physical property such as institute of table 1
Show.
Catalyst is reduced, 300 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 40% hydrogen+60%
0.5MPa, recovery time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 1, reaction condition：Volume space velocity 10000h-1, pressure 1.5MPa, 40 DEG C of reaction temperature.Operation
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for result.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated
Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized+And Cl-Ion, is subsequently adding suitable
Amount mass concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-
Al complex carriers.Aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Iron chloride and potassium chloride are taken, heating for dissolving is in deionized water
In, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min, by unnecessary maceration extract
Filter, catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Drying catalyst, activation of catalyst is carried out using programmed temperature method, living
Change program：
Catalyst is reduced, 320 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 30% hydrogen+60%
0.5MPa, recovery time 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 2, reaction condition：Volume space velocity 8000h-1, pressure 2.0MPa, 45 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Embodiment 3
The ball-type aluminum oxide for weighing Φ 1.5mm prepares catalyst.Take appropriate ferric nitrate to be dissolved in deionized water, adjust pH value
3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and load 10min makes active component upload uniformly, then in an oven
According to program：Drying catalyst, catalyst work is carried out using programmed temperature method
Change, activation procedure：
Obtain a leaching catalyst.
Using first step same procedure, appropriate cerous nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried,
Roasting, obtains final catalyst.Drying program： Calcination procedure：
Catalyst is reduced, 340 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 20% hydrogen, also
Former time 4h.Reduction rear catalyst XRD analysis are as shown in Figure 4.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 3, reaction condition：Volume space velocity 6000h-1, pressure 2.5MPa, 40 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Embodiment 4
The spherical tio2 carrier of the Φ 2.0mm for weighing is placed in vacuum impregnation plant.A certain amount of ferric nitrate is taken to be dissolved in
In deionized water, regulation pH value 3.5 is standby.Vacuum impregnation plant vacuum pumping pump is opened, to vacuum 0.1mmHg, then from charging
Mouth is slowly added to the maceration extract for preparing, and 5min is added, catalyst surface mobile moisture is evaporated at 60 DEG C and is wholly absent, and completes
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.
Appropriate cerous nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, be finally catalyzed
Agent.Drying program：Calcination procedure：
Catalyst is reduced, 360 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 15% hydrogen, also
Former time 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 1, reaction condition：Volume space velocity 4000h-1, pressure 1.8MPa, 45 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature
650℃。
Catalyst is reduced, 380 DEG C of temperature, pressure 0.5MPa, during reduction in reduction furnace using preceding with 25% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 3, reaction condition：Volume space velocity 3000h-1, pressure 2.0MPa, 45 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are pressed according to aluminum oxide：Silica：Zirconium oxide
=8:1:3 ratios are well mixed, then the extruded moulding on banded extruder, 120 DEG C of dryings, and 550 DEG C of roasting 3h, obtain in Muffle furnace
To Zr-Si-Al composite oxide carriers.Catalyst is prepared using the same procedure of embodiment 4.
Using preceding, with the nitrogen of 45% hydrogen+55% in reduction furnace, 400 DEG C of temperature, pressure 0.5MPa is activated catalyst
Time 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 2, reaction condition：Volume space velocity 2000h-1, pressure 2.5MPa, 30 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Embodiment 7
The aluminum oxide for taking Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C
Change.
Catalyst is reduced, 270 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 20% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 2, reaction condition：Volume space velocity 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
Catalyst physical property such as table 1, operation result is as shown in table 2.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 4.5m2/ g, pore volume is 0.32ml/g.Using equi-volume impregnating,
By on a certain amount of silver nitrate solution incipient impregnation to carrier, ageing-dry-roasting obtains a leaching catalyst, then by one
Quantitative palladium bichloride dissolving, incipient impregnation, ageing-dry-roasting, (petrochemical industry research institute PAH-01 adds to obtain final catalyst
Hydrogen catalyst).Catalyst Pd contents are that 0.050%, Ag contents are 0.20%.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen volume air speed 100h at 100 DEG C-1。
Using technique shown in Fig. 2, reaction condition：Volume space velocity 10000h-1, pressure 1.5MPa, 35 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Comparative example 2
Carrier is made with Φ 4.0mm aluminum oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃。
Catalyst is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 25% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.The XRD diffraction spectrograms for reducing rear catalyst are as shown in Figure 5.
Using technique shown in Fig. 1, reaction condition：Volume space velocity 8000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Comparative example 3
The aluminum oxide for weighing Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C
Change.
Catalyst is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 45% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.
Using technique shown in Fig. 3, reaction condition：Volume space velocity 3000h-1, pressure 2.5MPa, 60 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Comparative example 4
The same procedure of Example 1 prepares catalyst, is directly driven after being activated at 450 DEG C, is reduced without hydrogen.
Using technique shown in Fig. 2, reaction condition：Volume space velocity 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
Comparative example 5
The same procedure of Example 1 prepares catalyst, in 450 DEG C of activation.
Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 850 DEG C of temperature, pressure
0.5MPa, soak time 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.It is catalyzed after reduction
The XRD diffraction spectrograms of agent are as shown in Figure 6.
Reaction condition：Volume space velocity 5000h-1, pressure 2.0MPa, 70 DEG C of reaction temperature.
As shown in table 1, catalyst and carrier physical property are as shown in table 2 for operation result.
The catalyst methyl alcohol ethylene product of table 1 selection hydrogenation result
Note：Acetylene and ethene gather and generation n-butene, further gather and generate " green oil ", are generally given birth to n-butene in analysis
Catalyst green oil is levied into scale " growing amount.
The catalyst preparation of table 2 uses carrier physical property
Claims (11)
1. it is a kind of to be hydrogenated with the method for producing polymer grade ethylene, the smart ethylene feed of ethylene distillation column overhead is reacted into adiabatic reactor
Device carries out selection hydrogenation, to remove trace acetylene therein；It is characterized in that：In adiabatic reactor reactor hydrogenation is selected equipped with Fe systems
Catalyst, carrier is high-temperature inorganic oxide, and in terms of catalyst quality 100%, catalyst contains Fe 1~8%, preferred content
It is 2~6%, X 0~1.0%, wherein X is selected from one or several in K, La, Ce, and X preferred contents are 0.2~0.6%；Urge
Agent specific surface is 10~200m2/ g, preferably 30~150m2/ g, pore volume be 0.2~0.63ml/g, preferably 0.3~0.55ml/g,
Wherein Fe is loaded with carrier, through 300 DEG C~700 DEG C roastings, with the atmosphere of hydrogen 250~500 by impregnation method
Reduced at a temperature of DEG C and be obtained；In catalyst, Fe is mainly with α-Fe2O3Form is present；Selective hydrogenation reaction condition：Adiabatic reactor reacts
30 DEG C~50 DEG C of device inlet temperature, 1.5~2.5MPa of reaction pressure, 2000~10000h of volume space velocity-1, H2/C2H2Volume ratio is
2~20, preferred hydroconversion condition is：35 DEG C~45 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, body
5000~8000h of product air speed-1, H2/C2H2Volume ratio is 2~5.
2. method according to claim 1, it is characterised in that：In used hydrogenation catalyst, α-Fe2O3The Fe of form will
Account for more than the 50% of Fe gross masses.
3. method according to claim 1, it is characterised in that：The carrier of catalyst be aluminum oxide, or aluminum oxide and other
The complex carrier of oxide, best aluminum oxide accounts for more than the 50% of carrier quality, and other oxides are silica, zirconium oxide, oxygen
Change the preferred alumina-zirconia composite carrier of complex carrier of magnesium or titanium oxide, aluminum oxide and other oxides；Aluminum oxide can be with
It is θ, α, γ type, preferably α-Al2O3。
4. method according to claim 1, it is characterised in that：The impregnation method is incipient impregnation, excessive dipping, table
Face sprays, vacuum impregnation or repeatedly dipping.
5. method according to claim 1, it is characterised in that：Catalyst is by preparing the Fe predecessors aqueous solution, X predecessors
The aqueous solution, respectively impregnated carrier, respectively be aged, dry, roasting or with after its mixed solution impregnated carrier be aged, dry, roasting,
Obtained after finally restoring.
6. method according to claim 5, it is characterised in that：30~60 DEG C of dipping temperature, 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~700 DEG C of sintering temperature,
180~300min of roasting time, preferably 400~500 DEG C of sintering temperature.
7. method according to claim 5, it is characterised in that：Dry as temperature programming is dried, drying temperature program setting
For：
8. method according to claim 1 or 5, it is characterised in that：Temperature-programmed calcination is roasted to, is roasted
Temperature program(me) is burnt to be set as：
9. method according to claim 1 or 5, it is characterised in that：Catalyst reduction refer to catalyst use it is preceding, after roasting
Catalyst with hydrogen-containing gas reduce, H2Volume content is preferably 10~50%, 250~500 DEG C of reduction temperature, recovery time
240~360min, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to use N2+H2Gaseous mixture enters
Row reduction, 300~400 DEG C of reduction temperature, 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
10. method according to claim 1, it is characterised in that：It is single hop reactor to use adiabatic reactor reactor.
11. methods according to claim 1, it is characterised in that：The raw material for carrying out selective hydrogenation is ethylene rectifying column tower
The smart ethylene feed on top, raw material composition is mainly：Ethene >=99.99 volume %, 5~100ppm of acetylene.
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|---|---|---|---|---|
| CN1640541A (en) * | 2004-01-12 | 2005-07-20 | 四川大学 | Palladium-carrying catalyst using titanium dioxide as carrier for acetylene hydrocarbon selective hydrogenation |
| CN101402541A (en) * | 2008-11-21 | 2009-04-08 | 清华大学 | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation |
| CN101432247A (en) * | 2004-10-20 | 2009-05-13 | 催化蒸馏技术公司 | Selective hydrogenation process and catalyst |
| CN102649678A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for removing phenylacetylene through highly selective hydrogenation in presence of styrene |
| CN105152842A (en) * | 2015-08-07 | 2015-12-16 | 北京神雾环境能源科技集团股份有限公司 | Reaction system and method for preparing ethylene through acetylene hydrogenation |
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2015
- 2015-12-31 CN CN201511032664.7A patent/CN106928006B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640541A (en) * | 2004-01-12 | 2005-07-20 | 四川大学 | Palladium-carrying catalyst using titanium dioxide as carrier for acetylene hydrocarbon selective hydrogenation |
| CN101432247A (en) * | 2004-10-20 | 2009-05-13 | 催化蒸馏技术公司 | Selective hydrogenation process and catalyst |
| CN101402541A (en) * | 2008-11-21 | 2009-04-08 | 清华大学 | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation |
| CN102649678A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for removing phenylacetylene through highly selective hydrogenation in presence of styrene |
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