CN106928013A - A kind of acetylene hydrogenation method of MTO technology ethylene feed - Google Patents
A kind of acetylene hydrogenation method of MTO technology ethylene feed Download PDFInfo
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- CN106928013A CN106928013A CN201511032469.4A CN201511032469A CN106928013A CN 106928013 A CN106928013 A CN 106928013A CN 201511032469 A CN201511032469 A CN 201511032469A CN 106928013 A CN106928013 A CN 106928013A
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- Prior art keywords
- catalyst
- temperature
- hydrogenation
- carrier
- acetylene
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- 238000000034 method Methods 0.000 title claims abstract description 62
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 48
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 31
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 150
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910002549 Fe–Cu Inorganic materials 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 32
- 150000001345 alkine derivatives Chemical class 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002803 maceration Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007789 gas 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
- 238000000926 separation method Methods 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000010970 precious metal Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 238000001994 activation Methods 0.000 description 17
- 230000004913 activation Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 238000012856 packing Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910001868 water 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
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 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
- 239000004332 silver Substances 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
- 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
- 230000033228 biological regulation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- -1 propine allene Chemical class 0.000 description 4
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002283 diesel fuel 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
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021007 Co2Al5 Inorganic materials 0.000 description 1
- 229910021214 Co2Al9 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910019108 CoAl3 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 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
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 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
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- B01J23/745—Iron
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of acetylene hydrogenation method of MTO technology ethylene feed, using Fe-Cu hydrogenation catalysts, selective hydrogenation refining is carried out by methyl alcohol ethylene product, and hydrogenation object goes out thing for methyl alcohol ethylene product deethanizer overhead stream, and raw material composition is：Ethene >=99.9% (Φ), 1~10ppm of acetylene 5~100ppm, CO.30 DEG C~80 DEG C of reactor inlet temperature, 1.5~3.0MPa of reaction pressure, 2000~10000h of air speed-1；Catalyst carrier for hydrgenating is high-temperature inorganic oxide, and active component at least contains Fe, Cu, in terms of catalyst quality 100%, Fe contents 2~8%, Cu contents 0.05~0.3%；10~200m of catalyst specific surface2/ g, 0.2~0.63ml/g of pore volume.Catalyst hydrogenation activity is gentle, and ethylene selectivity is excellent, and " green oil " growing amount is low, and catalyst cost is far below precious metals pd catalyst.
Description
Technical field
The present invention relates to a kind of acetylene hydrogenation method of MTO technology ethylene feed, particularly one kind is in methyl alcohol system
In the product of ethene, the process for selective hydrogenation of trace acetylene is carried out using Fe-Cu hydrogenation catalysts.
Background technology
The low-carbon alkenes such as ethene, propylene are important basic chemical raw materials, with the development of Chinese national economy, particularly
The development of modern chemical industry increasingly rises to the demand of low-carbon alkene, and imbalance between supply and demand will also become increasingly conspicuous.So far, produce
The important channel of the low-carbon alkenes such as ethene, propylene, be still by naphtha, the catalytic cracking of light diesel fuel (being all from oil),
Cracking, as raw material resources such as the naphtha of ethylene production raw material, light diesel fuels, is faced with increasingly severe short office
Face.In addition, crude oil in China import volume has accounted for half of processing total amount or so, the polyolefin with ethene, propylene as raw material in recent years
Product will maintain the at a relatively high percentage of import.Therefore, development non-oil resource carrys out the technology of preparing low-carbon olefins and increasingly causes
The attention of people.
The MTP techniques of methyl alcohol ethene, the MTO techniques of propylene and preparing propylene from methanol are Chemical Engineering Technologies important at present.Should
Technology produces low-carbon alkene with coal or the methyl alcohol of natural gas synthesis as raw material, is development non-oil resource production ethene, propylene etc.
The core technology of product.
MTO technology is the committed step in coal-to-olefin industrial chain, and its technological process is mainly suitably is grasping
Under the conditions of work, with methyl alcohol as raw material, suitable catalyst is chosen, by methanol dewatered in fixed bed and fluidized-bed reactor
Low-carbon alkene.According to the difference of purpose product, MTO technology is divided into methyl alcohol ethene, propylene, preparing propylene from methanol.Methyl alcohol
Entirely reaction can be divided into two stages to alkene processed：Water smoking, cracking reaction stage
1. water smoking
2CH3OH→CH3OCH3+H2O+Q
2. cracking reaction stage
The catalysis that the course of reaction is mainly dehydration reaction product dimethyl ether and a small amount of unconverted material benzenemethanol and carries out is split
Solution reaction, including：
Main reaction (generation alkene)：
nCH3OH→CnH2n+nH2O+Q
nCH3OH→2CnH2n+nH2O+Q
N=2 and 3 (main), 4,5 and 6 (secondary)
Any of the above olefin product is gaseous state.
Side reaction (generation alkane, aromatic hydrocarbons, oxycarbide and coking)：
(n+1)CH3OH→CnH2n+2+C+(n+1)H2O+Q
(2n+1)CH3OH→2CnH2n+2+CO+2nH2O+Q
(3n+1)CH3OH→3CnH2n+2+CO2+(3n-1)H2O+Q
N=1,2,3,4,5............
nCH3OCH3→CnH2n-6+3H2+nH2O+Q
N=6,7,8............
Methyl alcohol after dehydration, cracking, separating, the still second containing 5~100ppm in the ethylene feed of deethanizer overhead
Alkynes, it influences the polymerization process of ethene, and causes product quality to decline, it is necessary to pass through to select method of hydrotreating to be removed.Ethene
The selection hydrogenation of trace acetylene has extremely important influence to the polymerization process of ethene in material, except ensureing that it is enough that hydrogenation has
Activity, have under conditions of low acetylene content good except alkynes performance, it is ensured that the acetylene content of reactor outlet is up to standard, instead
The hydrogen content for answering device to export is up to standard outer, also requires that the selectivity of catalyst is excellent, can make the generation second that ethene is as few as possible
Alkane, it is ensured that hydrogenation process does not bring the loss of device ethene.
The selection hydrogenation of trace acetylene is main in current methanol-to-olefins device ethylene feed uses single hop reactor process.
Reactor inlet material is constituted：Ethene >=99.99% (Φ), acetylene 1~10ppm of 5~100ppm, CO, hydrogen is using distribution
Mode, H2/C2H2=2~6.1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-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..
Patent US4404124 is prepared for the selective hydrogenation catalyst that active component palladium shell is distributed by step impregnation method,
The selection hydrogenation of carbon two, C3 fraction is can be applied to, to eliminate the propine allene in acetylene and propylene in ethene.
With aluminum oxide as carrier, regulation co-catalyst silver is acted on US5587348 with palladium, adds alkali metal, the fluorine of chemical bonding to be prepared for
The C2 hydrogenation catalyst of function admirable.The catalyst has reduction green oil generation, improves ethylene selectivity, reduces oxygen-containing chemical combination
The characteristics of thing growing amount.US5519566 discloses a kind of method that wet reducing prepares silver and palladium catalyst, by maceration extract
Middle addition organic or inorganic reducing agent, prepares silver and palladium bi-component selective hydrogenation catalyst.
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 air speed 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen
Under conditions of alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
With aluminum oxide as carrier, addition co-catalyst silver is acted on 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.
Due to using precious metals pd as active component, catalyst high cost.Research and develop remarkable new of cheap, performance
C2 hydrogenation catalyst system, is always the target of field scientific research personnel effort.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst by selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium second component group
Into catalyst also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound in addition.Urge
Agent calcining, using or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably sintering temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With active, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. as active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and
The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
Described intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between described metal
Compound is prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stabilization reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provides a kind of new Fe-Cu hydrogenation catalysts and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of acetylene hydrogenation method of MTO technology ethylene feed, particularly relate to
A kind of Fe-Cu catalyst, goes out preparing light olefins from methanol technique deethanizer overhead stream trace acetylene contained in thing and is selected
Selecting property is hydrogenated with, and ethene is fully converted to, while ethene does not lose.
It is of the present invention except alkynes method, deethanizer overhead stream is gone out into thing after with hydrogen, into adiabatic reactor reactor
Selection hydrogenation is carried out, to remove trace acetylene therein.Support type Fe-Cu selection hydrogenation catalysts are loaded in adiabatic reactor reactor
Agent, carrier is high-temperature inorganic oxide, and active component at least contains Fe, Cu, and catalyst contains Fe 2~8%, containing Cu 0.05~
0.3%, preferred content is Fe 3~6%, Cu 0.08~0.15%；The specific surface of catalyst is 10~200m2/ g, preferably 30
~150m2/ g, pore volume is 0.2~0.63ml/g, preferably 0.3~0.55ml/g；Wherein Fe is loaded with load by impregnation method
On body, through 250 DEG C~600 DEG C roastings, then it is obtained with 200~400 DEG C of reduction of hydrogen atmosphere.Fe elements in catalyst are main
With α-Fe2O3Form is present.Selective hydrogenation reaction condition：30 DEG C~80 DEG C of reactor inlet temperature, reaction pressure 1.5~
3.0MPa, 2000~10000h of volume space velocity-1, H2/C2H2It is 1~20.Preferred hydroconversion condition is：Adiabatic reactor reactor inlet
40 DEG C~50 DEG C of temperature, 1.8~2.2MPa of reaction pressure, 5000~8000h of volume space velocity-1；H2/C2H2It is 2~5.
Of the present invention to use hydrogenation catalyst except alkynes method, 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 most common is also most preferably aluminum oxide or oxygen
Change aluminium system carrier, alumina series carrier refers to the complex carrier of aluminum oxide and other oxides, and wherein aluminum oxide accounts for complex carrier
More than the 50% of quality, such as can be aluminum oxide and silica, zirconium oxide, the preferably compound of magnesia oxide, oxygen
Change 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.
The present invention removes alkynes method, the preparation method of the Fe-Cu selective hydrogenation catalysts that use for：
Catalyst distinguishes impregnated carrier, is aged respectively, does by preparing the Fe predecessors aqueous solution, the Cu predecessor aqueous solution
Dry, roasting or with its mixed solution impregnated carrier, is aged, dries, roasting afterwards, and finally reduction is obtained.Sintering temperature is preferably 300
DEG C~400 DEG C；Reduced at 260~330 DEG C.
Preferred condition is in preparation method of the present invention：
30~60 DEG C of dipping temperature, 10~60min of load time, maceration extract pH value 1.5~5.0, Aging Temperature 20~60
DEG C, 30~120min of digestion time, 300~400 DEG C of sintering temperature, 180~300min of roasting time.
Dried in the present invention and be preferably temperature programming drying, drying temperature program setting is：
Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：
Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
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 Cu components are loaded using above-mentioned same steps, 250~600 DEG C of sintering temperature, preferably 300~
400 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
Catalyst of the invention needs to be reduced with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature is 200~
400 DEG C, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；The condition of recommendation is to use N2+H2Gaseous mixture is micro-
260~330 DEG C are reduced under positive pressure, and the recovery time is preferably 240~360min, the best 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
The active component of catalyst is mainly Fe in the present invention, can be non-precious metal catalyst, it might even be possible to without cobalt,
Nickel, molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.
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.
Fe elements can be with Fe, Fe in catalyst of the invention2O3、Fe3O4, the variform such as FeO exist, but wherein α-
Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for more than the 50% of Fe gross masses.
Recommend to add Cu in the activity composition of iron content in the present invention, be more beneficial for reducing activation temperature, be conducive to urging
Formation, the dispersion of agent activation phase, improve catalyst choice.The addition of Cu simultaneously contributes to the absorption of alkynes, activation, favorably
In the activity for improving catalyst.
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 the C2 hydrogenation process chart using the methyl alcohol ethene of order separation process.
1-reactor, 2-regenerator, 3-separator, 4-caustic wash tower, 5-drying tower, 6-domethanizing column, 7-de- second
Alkane tower, 8-ethylene separation tower, 9-propylene separation tower, 10-depropanizing tower, the refined adiabatic reactor reactor of 11-ethene.
Fig. 2 is XRD spectra (deduction vector background) after the catalyst reduction of the embodiment of the present invention 3.
Fig. 3 is XRD spectra (deduction vector background) after the high-temperature roasting catalyst reduction of comparative example 2.
Fig. 4 is XRD spectra (deduction vector background) after the catalyst high temperature reduction of comparative example 5.
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature
The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity
Symbol description in Fig. 2：
▲ it is α-Fe2O3, ◆ it is Cu, ■ is Fe3O4。
Symbol description in Fig. 3：
▲ it is α-Fe2O3, ● it is CuFeO3, ■ is Fe3O4。
Symbol description in Fig. 4：
★ is Fe for α-Fe, ■3O4, ◆ it is Cu.
α-Fe in Fig. 22O3Relative amount 11.20%.
Fe and second component combine to form CuFe in Fig. 32O4, help component to be sintered with active component, destroy active component
Distribution and structure.
α-Fe are free of in Fig. 42O3Phase, Fe mainly with simple substance α-Fe forms occur, relative amount 8.92%, third component with
Simple substance Cu forms occur.
Specific embodiment
Analysis test method：
Specific surface：GB/T-5816
Pore volume：GB/T-5816
Different crystal forms Fe oxide contents：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 alpha-alumina supports 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, static
To adsorption equilibrium, 60 DEG C are aged 30min to 30min, then in an oven according to program：Drying is urged
Agent, then carries out activation of catalyst, activation procedure using programmed temperature method： Copper nitrate is weighed, is impregnated according to above-mentioned preparation process.Gained catalyst
Physical index and each component content are shown in Table 1.
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 ethene finishing reactor.
Reaction condition：Air speed 10000h-1, pressure 1.5MPa, 40 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated
Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized+And Cl-Ion, is subsequently adding matter
Amount concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-Al and answer
Close carrier.Aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Take iron chloride and copper chloride, heating for dissolving in deionized water,
Regulation pH value 2.0,80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min, and unnecessary maceration extract is filtered,
Catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：
Drying catalyst, activation of catalyst, activation procedure are carried out using programmed temperature method： Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 260 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 30% hydrogen+60%
0.5MPa, recovery time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in ethene finishing reactor.
Reaction condition：Air speed 8000h-1, pressure 2.0MPa, 50 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Take ferric nitrate to be dissolved in 40ml deionized waters, adjust
PH value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly,
Loading process control is completed in 6min, then in an oven according to program：
Drying catalyst, evaporating dish is moved into by catalyst, and activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence： Obtain a leaching
Catalyst.
Using first step same procedure, copper nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, be calcined,
Obtain final catalyst.Drying program：Calcination procedure：Gained catalyst
Physical index and each component content are shown in Table 1.
Catalyst is reduced, 280 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 1.
Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in ethene finishing reactor.
Reaction condition：Air speed 6000h-1, pressure 2.5MPa, 40 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Embodiment 4
Ball-aluminium oxide-the titanium dioxide carrier of the Φ 2.0mm for weighing is placed in vacuum impregnation plant.Ferric nitrate is taken to be dissolved in
In deionized water, regulation pH value 3.5 is standby.Open vacuum impregnation plant vacuum pumping pump, to vacuum 0.1mmHg, then from plus
Material mouth is slowly added to the maceration extract for preparing, and 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is wholly absent,
Complete load, the catalyst that will have been loaded, in an oven according to program：Dry
It is dry, in Muffle furnace according to： Roasting
Burn.Obtain a leaching catalyst.
Copper nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Drying program：Calcination procedure：
Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 300 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 15% hydrogen, also
Former time 4h.Using flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.
Reaction condition：Air speed 4000h-1, pressure 1.8MPa, 45 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Embodiment 5
The magnesia-silica complex carrier of 100ml Φ 4.0mm is weighed, is prepared using the same procedure of embodiment 3 and is catalyzed
Agent.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 320 DEG C of temperature, pressure 0.5MPa, during reduction in reduction furnace using preceding with 25% hydrogen
Between 4h.When using by Catalyst packing in fixed-bed reactor.
Reaction condition：Air speed 3000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Embodiment 6
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature
650℃.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 360 DEG C of temperature, pressure 0.5MPa, during reduction in reduction furnace using preceding with 25% hydrogen
Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.
Reaction condition：Air speed 3000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 4.5m2/ g, pore volume is 0.32ml/g.Using equi-volume impregnating,
By silver nitrate solution incipient impregnation on carrier, ageing-dry-roasting obtains a leaching catalyst, then by palladium bichloride
Dissolving, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute PAH-01 hydrogenation catalysts).Urge
Agent Pd contents are that 0.050%, Ag contents are 0.20%.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h at 100 DEG C-1.Added with accompanying drawing 1 Suo Shi
Hydrogen flow, Catalyst packing is in the refined adiabatic reactor reactor of ethene.
Reaction condition and result are as shown in table 1.
Comparative example 2
Carrier is made with Φ 4.0mm aluminum oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 25% hydrogen
Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.Reduce the XRD of rear catalyst
Diffraction spectrogram is as shown in Figure 3.
Reaction condition：Air speed 8000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
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.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 45% hydrogen
Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.
Reaction condition：Air speed 3000h-1, pressure 2.5MPa, 60 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Comparative example 4
Catalyst is prepared using the identical method of embodiment 1, is directly driven after being activated at 450 DEG C, gone back without hydrogen
It is former.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.Gained catalyst physical index
And each component content is shown in Table 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 60 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
Comparative example 5
Catalyst is prepared using the identical method of embodiment 1, in 350 DEG C of activation.Gained catalyst physical index and each group
Point content is shown in Table 1.
Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 500 DEG C of temperature, pressure
0.5MPa, soak time 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in the refined adiabatic reactor reactor of ethene.Reduction
The XRD diffraction spectrograms of rear catalyst are as shown in Figure 4.
Reaction condition：Air speed 5000h-1, pressure 2.0MPa, 70 DEG C of reaction temperature.
Reaction condition and result are as shown in table 1.
The embodiment of table 1 and comparative example carrier, catalyst physical property and catalyst reaction performance
Note：Acetylene and ethene gather and generation n-butene, further gather and generate " green oil ", are generally given birth to n-butene in analysis
Catalyst green oil is levied into scale " growing amount.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
The protection domain of the claims in the present invention should all be belonged to.
Claims (11)
1. a kind of acetylene hydrogenation method of MTO technology ethylene feed, the process separation of methanol-to-olefins device product, come
The material of carbon two from deethanizer overhead is through with after hydrogen, selection hydrogenation being carried out into adiabatic reactor reactor, it is characterised in that：Absolutely
Fe-Cu selective hydrogenation catalysts are housed, carrier is high-temperature inorganic oxide, and active component at least contains in hott bed reactor
Fe, Cu, catalyst contain Fe 2~8%, and containing Cu 0.05~0.3%, preferred content is Fe 3~6%, Cu 0.08~0.15%；
The specific surface of catalyst 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 by impregnation method, through 250 DEG C~600 DEG C roastings, then uses hydrogen atmosphere
200~400 DEG C of reduction are obtained；Fe is main with α-Fe in catalyst2O3Form is present；Selective hydrogenation reaction condition：Adiabatic reactor reacts
30 DEG C~80 DEG C of device inlet temperature, 1.5~3.0MPa of reaction pressure, 2000~10000h of volume space velocity-1, H2/C2H2It is 1~20,
Preferred hydroconversion condition is：40 DEG C~50 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, volume space velocity
5000~8000h-1, H2/C2H2It is 2~5.
2. it is according to claim 1 except alkynes method, it is characterised in that in using hydrogenation catalyst, α-Fe2O3The Fe of form
Account for more than the 50% of Fe gross masses.
3. according to claim 1 except alkynes method, it is characterised in that the carrier of catalyst be aluminum oxide, or aluminum oxide and its
The complex carrier of his oxide, best aluminum oxide accounts for more than the 50% of complex carrier quality, other oxides be preferably silica,
The preferred alumina-zirconia composite carrier of complex carrier of zirconium oxide, magnesia or titanium oxide, aluminum oxide and other oxides；
Aluminum oxide is θ, α, γ type, preferably α-Al2O3。
4. according to claim 1 except alkynes method, it is characterised in that：The impregnation method is incipient impregnation, excessive leaching
Stain, surface are sprayed, vacuum impregnation or repeatedly dipping.
5. according to claim 1 except alkynes method, it is characterised in that：Catalyst is by preparing the Fe predecessors aqueous solution, Cu
The predecessor aqueous solution, respectively impregnated carrier, be aged respectively, dry, roasting or to be aged after its mixed solution impregnated carrier, it is dry
Dry, roasting, finally restores acquisition.
6. according to claim 5 except alkynes method, it is characterised in that：30~60 DEG C of dipping temperature, load time 10~
60min, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, preferably 180~300min,
250 DEG C~600 DEG C of sintering temperature, preferably 300~400 DEG C, 180~300min of roasting time.
7. according to claim 5 except alkynes method, it is characterised in that：Dry as temperature programming is dried, drying temperature program
It is set as：
8. alkynes method is removed according to claim 1 or 5, it is characterised in that：Temperature-programmed calcination is roasted to, sintering temperature program sets
It is set to：
9. alkynes method is removed according to claim 1 or 5, it is characterised in that：Catalyst reduction refers to that catalyst uses preceding, roasting
Catalyst after burning is reduced with hydrogen-containing gas, H2Volume content is preferably 10~50%, 250~400 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 to use N2+H2Gaseous mixture
Reduced, 260~330 DEG C of reduction temperature, 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
10. it is according to claim 1 except alkynes method, it is characterised in that adiabatic reactor reactor is single hop bed.
11. is according to claim 1 except alkynes method, it is characterised in that hydrogenation object is that methyl alcohol ethylene product is separated
Afterwards, deethanizer overhead stream goes out trace acetylene contained in thing, and raw material composition is：Ethene >=99.9 volume %, acetylene 5~
1~10ppm of 100ppm, CO.
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