CN106928002A - Method for removing alkyne by hydrogenation after carbon dioxide - Google Patents
Method for removing alkyne by hydrogenation after carbon dioxide Download PDFInfo
- Publication number
- CN106928002A CN106928002A CN201511032200.6A CN201511032200A CN106928002A CN 106928002 A CN106928002 A CN 106928002A CN 201511032200 A CN201511032200 A CN 201511032200A CN 106928002 A CN106928002 A CN 106928002A
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- catalyst
- reactor
- temperature
- hydrogenation
- acetylene
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Links
- 238000000034 method Methods 0.000 title claims abstract description 93
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 80
- 150000001345 alkine derivatives Chemical class 0.000 title claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title 2
- 229910002092 carbon dioxide Inorganic materials 0.000 title 1
- 239000001569 carbon dioxide Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 149
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- 238000005470 impregnation Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 11
- 239000000284 extract Substances 0.000 claims description 11
- 238000002803 maceration Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 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
- 239000011148 porous material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 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
- 238000011084 recovery Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 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
- 239000011777 magnesium 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 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 230000008569 process Effects 0.000 description 23
- 238000001994 activation Methods 0.000 description 17
- 230000004913 activation Effects 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 238000012856 packing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000009826 distribution Methods 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
- 239000003795 chemical substances by application Substances 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
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 6
- 229910021304 Co4Al13 Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002386 leaching 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
- 229920000642 polymer Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 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
- 230000015572 biosynthetic process Effects 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
- 238000004939 coking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001802 infusion Methods 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
- 238000005303 weighing Methods 0.000 description 3
- 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
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 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
- 238000000926 separation method Methods 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
- 239000000126 substance Substances 0.000 description 2
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021007 Co2Al5 Inorganic materials 0.000 description 1
- 229910021214 Co2Al9 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910019108 CoAl3 Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- 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
- 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
- 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
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 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
- 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
- 239000003518 caustics Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 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
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 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
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research 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
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying Methods 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
- 238000010998 test method Methods 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/78—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 with alkali- or alkaline earth metals
-
- 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
- B01J23/83—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 with rare earths or actinides
-
- 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
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Abstract
A method for removing acetylene by hydrogenation after carbon two, the top effluent from deethanizer in hydrogenation after carbon two is sent to adiabatic reactor for selective hydrogenation to remove acetylene. The hydrogenation catalyst is a Fe selective hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, and the hydrogenation raw material mainly comprises the following components: 0.98-2.2% of acetylene, 11.2-30.3% of ethane and 65.0-85.0% of ethylene. The reaction conditions are as follows: the inlet temperature of the adiabatic bed reactor is 40-100 ℃, the reaction pressure is 1.5-2.5 MPa, and the gas volume space velocity is 2000-10000 h-1. The alkyne-removing method of the invention has moderate catalyst reaction activity, good operation elasticity, good ethylene selectivity and far lower green oil generation amountA noble metal catalyst.
Description
Technical field
Alkynes method is removed the present invention relates to a kind of back end hydrogenation of carbon two, particularly a kind of Fe series catalysts are by ethylene feed
The method that contained acetylene hydrogenation is converted into ethene.
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 being divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to second
For domethanizing column position, hydrogenation reactor was front-end hydrogenation before domethanizing column to alkynes hydrogenation reactor, and hydrogenation is anti-
Device is answered to be located at after domethanizing column as back end hydrogenation.Back end hydrogenation is order separation process, and the advantage of technique is hydrogenation process control
Means are more, are difficult temperature runaway, easy to operate, but have the disadvantage the easy coking of catalyst, and the reproduction ratio of catalyst is more frequent.Its reason be
In hydrogenation process, because the amount of allocating of hydrogen is few, the hydrogenation dimerization reaction of acetylene is susceptible to, generates 1,3-butadiene, gone forward side by side
One step generation molecular weight oligomer wider, is commonly called as " green oil ".Green oil is adsorbed in catalyst surface, and further forms coking,
Obstruction catalyst duct, declines catalyst activity and selectivity.
The current back end hydrogenation of carbon two mainly uses two sections or three sections of reactor tandem process, and volume space velocity is relatively low or alkynes content is low
Device, can be connected using two reactor.Current commercial plant, mainly based on three sections of reactor tandem process.
Back end hydrogenation material is typically constituted：The acetylene of 1.0~2.2% (v), 65~85% ethene, remaining is ethane, hydrogen
Gas is allocated into by after metering.
The reaction is exothermic reaction, but temperature rise is relatively low, and according to volume space velocity size, single reactor maximum temperature rise is from 30
~60 DEG C, so using adiabatic reactor substantially.
To two reactor, the acetylene of first paragraph reactor requirement conversion more than 70%, second segment reactor will be remaining
Acetylene is converted to its content and is less than 1 μ L/L.
Or acetylene content higher device higher to volume space velocity, typically uses three sections of reactor process, first paragraph conversion
50% or so, remaining the two sections remaining acetylene of conversion, three sections of reactor outlet acetylene contents are less than 1 μ L/L.
The amount of allocating of hydrogen is relevant with acetylene content and using technique.To three sections of reactor process, general first paragraph reaction
Device hydrogen/acetylene is 0.8~1.2, and second segment reactor hydrogen/acetylene is 1~1.5, and the 3rd section of reactor hydrogen/acetylene is
1.5~3.
To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1~1.5, second segment reactor hydrogen/
Acetylene is 2~4.
The reaction mechanism is as follows：
Main reaction C2H2+H2→C2H4Δ H=-175.7kJ/mol (1)
Side reaction
C2H4+H2→C2H6Δ H=-138.1kJ/mol (2)
C2H2+2H2→C2H6 (3)
2C2H2+H2→C4H6 (4)
C2H2+nC2H2+H2→C2n+2H2n+4 (5)
In these are answered, reaction (1) is acetylene hydrogenation, and reaction (2) and (3) is ethylene hydrogenation.Reaction (4) is that acetylene adds
Hydrogen dimerization, there is important contribution to generation green oil, and reaction (5) is the General reactions formula for generating green oil.
In these reactions, the reaction that (1) is desirable to occur only is reacted, remaining is undesirable reaction.
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.
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.Meanwhile, using total immersion method, because the presoma of two metal ion species is mutual with carrier
Effect is different, and surface tension and solvation, is 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 run time
Extension, 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, and activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, makes
Improved into catalyst cost；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
Alkynes method is removed it is an object of the invention to provide a kind of back end hydrogenation of carbon two.A kind of Fe systems selection hydrogenation is particularly related to urge
Agent, contained selective hydrogenation of acetylene, is fully converted to ethene in it will go out thing from deethanizer overhead stream, while ethene
Without loss.
The present invention provides a kind of back end hydrogenation of carbon two and removes alkynes method, and the effluent of deethanizer overhead is reacted into adiabatic reactor
Device carries out selection hydrogenation, to remove trace acetylene therein, Fe systems selective hydrogenation catalyst, carrier is housed in adiabatic reactor reactor
It is high-temperature inorganic oxide, in terms of catalyst quality 100%, catalyst contains Fe 2~12%, and preferred content is 4~10%, X
0~1.6%, wherein X be selected from K, La, Ce in one or several, X preferred contents be 0.5~1.0%；The ratio table of catalyst
Face is 10~200m2/ g, preferably 30~100m2/ g, pore volume is 0.2~0.63ml/g, preferably 0.35~0.49ml/g；Wherein Fe
It is to be loaded with carrier, through 300 DEG C~700 DEG C roastings, with the atmosphere of hydrogen in 250~500 DEG C of temperature by impregnation method
Lower reduction is obtained, and the Fe elements in catalyst are main with α-Fe2O3Form is present.Selective hydrogenation reaction condition：Adiabatic reactor reactor
40~100 DEG C of inlet temperature, 1.5~2.5MPa of reaction pressure, 2000~10000h of gas volume air speed-1, H2/C2H2Volume ratio
It is 1~20.Preferred hydroconversion condition is：45~55 DEG C of adiabatic reactor reactor inlet temperature, 1.8~2.2MPa of reaction pressure, gas
5000~8000h of body volume space velocity-1, H2/C2H2Volume ratio is 1.2~5.
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 carrier quality
More than 50%, such as can be aluminum oxide and silica, zirconium oxide, the compound of magnesia oxide, preferably aluminum oxide-
Zirconia composite carrier, wherein alumina content is more than 60%.Aluminum oxide can be the mixed of θ, α, γ type or its various crystal formation
Compound, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal formation aluminum oxide.
The present invention removes alkynes 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 after obtain.
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, 300 DEG C~700 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.
Method of hydrotreating of the present invention, Fe elements can be with Fe, Fe in using hydrogenation catalyst2O3、Fe3O4、FeO
In several forms exist, but wherein α-Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for Fe gross masses
More than 50%.Recommend one or several in K, La, Ce is added during the activity of iron content is constituted in the present invention, be conducive to urging
Formation, the dispersion of agent activation phase, and be conducive to activating the stabilization of phase, 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 of the invention needs to be reduced with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature 250~
500 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-
300~400 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 process is generally carried out before selective hydrogenation reaction, is preferably outside device
Carried out outside selective hydrogenation reaction device.
The back end hydrogenation of carbon of the present invention two removes alkynes method, refers in two sections or three sections of series connection adiabatic reactors, to incite somebody to action
Deethanizer overhead stream goes out contained acetylene in material carries out selective hydrogenation, is converted into ethene.
The back end hydrogenation of carbon of the present invention two removes alkynes method, and when adiabatic reactor reactor is three sections of series connection, first stage reactor enters
40~50 DEG C of temperature of mouth, hydrogen/acetylene volume ratio is 0.8~1.2,45~55 DEG C of second stage reactor inlet temperature, hydrogen/acetylene
Volume ratio is 1~1.5, three sections of 50~60 DEG C of reactor inlet temperatures, and hydrogen/acetylene volume ratio is 1.5~3.0.
The back end hydrogenation of carbon of the present invention two removes alkynes method, when adiabatic reactor reactor is instead for two sections of series connection, first paragraph reaction
40~50 DEG C of device inlet temperature, hydrogen/acetylene volume ratio is 1~1.5,50~60 DEG C of second segment reactor inlet temperature, hydrogen/
Acetylene volume ratio is 2~4.
The back end hydrogenation of carbon of the present invention two removes alkynes method, and hydrogenation material is deethanizer overhead distillate, raw material composition
Predominantly：Acetylene 0.98~2.2%, ethane 11.2~30.3%, ethene 65.0~85.0%.
Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, green oil life
Noble metal catalyst is far below into amount.
Brief description of the drawings
Accompanying drawing 1 is to select hydrogenation technique flow chart using the carbon two of order separation process.Oil scrubber；2-water scrubber；3—
Caustic wash tower；4-drier；5-domethanizing column；6-dethanizer；7-C2 hydrogenation adiabatic reactor reactor；8-heat exchanger.
Accompanying drawing 2 is using the catalyst XRD spectra of the embodiment of the present invention 3 (deduction vector background).
Accompanying drawing 3 is the catalyst XRD spectra of comparative example 2 (deduction vector background).
Accompanying drawing 4 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. 2：
● it is α-Fe2O3, ▲ be Fe3O4, ◆ it is CeO.
Symbol description in Fig. 3：
● it is α-Fe2O3, ▲ be Fe3O4, ■ is LaFeO3。
Symbol description in Fig. 4：
▲ it is Fe3O4, ▼ is Ce, and ★ is α-Fe.
In Fig. 2, Fe is main with α-Fe in catalyst2O3Form occurs, relative amount 7.6%.
In Fig. 3, 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. 42O3Phase, 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 Fe oxide contents：XRD
Catalyst activity component content：GB/T 1537-94
Conversion of alkyne (C)
It is hydrogenated to the selectivity (S) of ethene
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, quiet
Only to adsorption equilibrium, 60 DEG C are aged 30min to 30min, then in an oven according to program：Drying
Catalyst, then carries out activation of catalyst, activation procedure using programmed temperature method： Lanthanum nitrate is weighed, is impregnated according to above-mentioned preparation process.
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.Catalyst packing is in adiabatic bed reaction device.
Using back end hydrogenation technique, as shown in Figure 1, raw material composition is its process chart：
C2H2：1.6% (Φ), C2H475.3% (Φ), C2H623.1% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade reactions, i.e. first stage reactor outlet material enters second stage reactor.
Every section of reactor has independent air distribution system.
Material gas volume air speed：2000h-1, operating pressure：2.5MPa.First stage reactor H2/C2H2=1.5：1 (mole
Than)；Second stage reactor H2/C2H2=3：1 (mol ratio), catalyst physical property such as table 1, reaction result is as shown in table 2.
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 the filter of unnecessary maceration extract
Remove, catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Dry
Dry catalyst, activation of catalyst, activation procedure are carried out using programmed temperature method：
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 back end hydrogenation technique, as shown in Figure 1, raw material composition is its process chart：
C2H2：1.4% (Φ), C2H480.0% (Φ), C2H618.6% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade reactions, i.e. first stage reactor outlet material enters second stage reactor.
Every section of reactor has independent air distribution system.
Material gas volume air speed：5000h-1, operating pressure：2.2MPa.First stage reactor H2/C2H2=1.5：1 (mole
Than)；Second stage reactor H2/C2H2=4：1 (mol ratio), catalyst physical property such as table 1, reaction result is as shown in table 2.
Embodiment 3
The ball-type aluminum oxide for weighing Φ 1.5mm prepares catalyst.Take 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, activation of catalyst is carried out using programmed temperature method,
Activation procedure：
To a leaching catalyst.
Using first step same procedure, cerous nitrate is taken, sprayed after dissolving to a leaching catalyst surface, then dried, be calcined, obtain 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 2.Catalyst packing is in adiabatic bed reaction device.
Using back end hydrogenation technique, reaction raw materials are：
C2H2：2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition：Three sections of bed adiabatic reactor reactor tandem process, i.e. first stage reactor outlet material enters second-stage reaction
Device, second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas volume air speed：7000h-1, operating pressure：1.8MPa.First stage reactor H2/C2H2=1：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio), catalyst physical property
Such as table 1, reaction result is as shown in table 2.
Embodiment 4
The spherical tio2 carrier of the Φ 2.0mm for weighing is placed in vacuum impregnation plant.Take ferric nitrate be dissolved in from
In sub- water, regulation pH value 3.5 is standby.Vacuum impregnation plant vacuum pumping pump is opened, to vacuum 0.1mmHg, then from charge door
The maceration extract for preparing is slowly added to, 5min is added, catalyst surface mobile moisture is evaporated at 60 DEG C and is wholly absent, completed
Load, the catalyst that will have been loaded, in an oven according to program：Drying, in Muffle furnace
According to： Roasting.
Obtain a leaching catalyst.
Cerous nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Dry journey
Sequence：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 back end hydrogenation technique, reaction raw materials are：
C2H2：2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition：Three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enters second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas volume air speed：10000h-1, operating pressure：1.5MPa.First stage reactor H2/C2H2=1：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).Catalyst physical property
Such as table 1, reaction result is as shown in table 2.
Embodiment 5
The alpha-alumina supports of 100ml Φ 4.0mm are 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 back end hydrogenation technique, reaction raw materials are：
C2H2：1.2 (v%) C2H480.3 (v%), C2H618.5 (v%).
Reaction condition：Three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enters second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas volume air speed：10000h-1, operating pressure：1.5MPa.First stage reactor H2/C2H2=1：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).Catalyst physical property
Such as table 1, reaction result is as shown in table 2.
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 back end hydrogenation technique, reaction raw materials are：
C2H2：2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition：Three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enters second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas volume air speed：10000h-1, operating pressure：1.5MPa.First stage reactor H2/C2H2=1：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).Catalyst physical property
Such as table 1, reaction result is as shown in table 2.
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 30% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.
Using back end hydrogenation technique, reaction raw materials are：
C2H2：1.2 (v%) C2H479.2 (v%), C2H619.6 (v%).
Reaction condition：Two sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enters second stage reactor,
Every section of reactor has independent air distribution system.
Material gas volume air speed：12000h-1, operating pressure：1.6MPa.First stage reactor H2/C2H2=2：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio).Catalyst physical property such as table 1, reaction result is as shown in table 2.
Reaction condition：Volume space velocity 18000h-1, pressure 2.5MPa.
Catalyst physical property such as table 1, reaction result is as shown in table 2.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 22.3m2/ g, pore volume is 0.31ml/g.Using equi-volume impregnating,
By on silver nitrate solution incipient impregnation to carrier, ageing-dry-roasting obtains a leaching catalyst, then that palladium bichloride is molten
Solution, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute LY-C2-02 hydrogenation catalysts).Urge
Agent Pd contents are that 0.040%, Ag contents are 0.12%.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen volume air speed 100h at 100 DEG C-1.Catalyst packing
In adiabatic bed reaction device.
Using the same process of embodiment 1, reaction condition：Volume space velocity 6000h-1, operating pressure：2.0MPa.Catalyst thing
Property such as table 1, reaction result is as shown in table 2.
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 3.
Using the same process of embodiment 1.Raw material is constituted：
C2H2：1.4% (Φ), C2H480.0% (Φ), C2H618.6% (Φ).
Reaction condition：Volume space velocity 2000h-1, operating pressure：2.5MPa.
Catalyst physical property such as table 1, reaction result is as shown in table 2.
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.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in adiabatic bed reaction device.
Reaction condition：Three sections of bed adiabatic reactor reactor tandem process, i.e. first stage reactor outlet material enters second-stage reaction
Device, second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas volume air speed：8000h-1, operating pressure：1.5MPa.First stage reactor H2/C2H2=1：1 (mole
Than)；Second stage reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).
Catalyst physical property such as table 1, reaction result is as shown in table 2.
Comparative example 4
The same catalyst of Example 1, directly drives after being activated at 450 DEG C, is reduced without hydrogen.With the institute of accompanying drawing 1
Show hydrogenation flow, Catalyst packing is in adiabatic bed reaction device.
Using three sections of series connection adiabatic reactor techniques, raw material constitutes same as Example 1, reaction condition：Volume space velocity
3000h-1, operating pressure：2.0MPa.
Catalyst physical property such as table 1, reaction result is as shown in table 2.
Comparative example 5
The same catalyst of Example 1, 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 4.
Hydrogenating materials constitute same as Example 7, two sections of serial hydrogenations, reaction condition：Volume space velocity 15000h-1, pressure
2.0MPa。
Catalyst physical property such as table 1, operation result is as shown in table 2.
The catalyst preparation of table 1 uses carrier physical property
The process conditions of table 2 and catalyst performance
Claims (12)
1. a kind of back end hydrogenation of carbon two removes alkynes method, by the back end hydrogenation ethylene unit of carbon two, material is gone out from deethanizer overhead stream
With selection hydrogenation is carried out into adiabatic reactor reactor after hydrogen, to remove acetylene therein；It is characterized in that：In adiabatic reactor reactor
Equipped with Fe systems selective hydrogenation catalyst, carrier is high-temperature inorganic oxide, and in terms of catalyst quality 100%, catalyst contains Fe
2~12%, preferred content be 4~10%, X 0~1.6%, wherein X be selected from K, La, Ce in one or several, X preferably contains
Measure is 0.5~1.0%；The specific surface of catalyst is 10~200m2/ g, preferably 30~100m2/ g, pore volume is 0.2~0.63ml/
G, preferably 0.35~0.49ml/g；Wherein Fe is loaded with carrier by impregnation method, through 300 DEG C~700 DEG C roastings, with containing
The atmosphere of hydrogen is reduced at a temperature of 250~500 DEG C and is obtained, and the Fe elements in catalyst are main with α-Fe2O3Form is present；Choosing
Select hydrogenation conditions：40~100 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of reaction pressure, gas volume air speed
2000~10000h-1, H2/C2H2Volume ratio is 1~20；Preferred hydroconversion condition is：Adiabatic reactor reactor inlet temperature 45~55
DEG C, 1.8~2.2MPa of reaction pressure, 5000~8000h of gas volume air speed-1, H2/C2H2Volume ratio is 1.2~5.
2. method according to claim 1, it is characterised in that：In catalyst, α-Fe2O3The Fe of form will account for Fe gross masses
More than 50%.
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 magnesium or titanium oxide, preferably alumina-zirconia composite carrier；Aluminum oxide can be θ, α, γ type, preferably α-Al2O3。
4. Fe systems selective hydrogenation catalyst according to claim 1, it is characterised in that the impregnation method be incipient impregnation,
Excessive dipping, surface are sprayed, vacuum impregnation or multiple 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, be aged respectively, dry, roasting or with its mixed solution impregnated carrier, be aged afterwards, dry, roasting
Obtained after burning, reduction.
6. method according to claim 5, it is characterised in that：30~60 DEG C of dipping temperature during catalyst preparation, during dipping
Between 10~60min, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, sintering temperature
300 DEG C~700 DEG C, preferably 400~500 DEG C；180~300min of roasting time.
7. method according to claim 5, it is characterised in that：Dried during catalyst preparation as temperature programming is dried, dried
Temperature program(me) is set as：
8. method 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. method according to claim 1 or 5, it is characterised in that：Reduction refers to use N2+H2Gaseous mixture is carried out to catalyst
Reduction, H2Volume content is preferably 10~50%, 250~500 DEG C of reduction temperature, 240~360min of recovery time, volume space velocity
100~500h-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to be reduced at 300~400 DEG C, volume space velocity 200~
400h-1, reduce pressure and be preferably 0.1~0.5MPa.
10. method according to claim 1, it is characterised in that：Adiabatic reactor reactor is three sections of series connection, and first stage reactor enters
40~50 DEG C of temperature of mouth, hydrogen/acetylene volume ratio is 0.8~1.2,45~55 DEG C of second stage reactor inlet temperature, hydrogen/acetylene
Volume ratio is 1~1.5, three sections of 50~60 DEG C of reactor inlet temperatures, and hydrogen/acetylene volume ratio is 1.5~3.0.
11. methods according to claim 1, it is characterised in that：Adiabatic reactor reactor is instead two sections of series connection, first paragraph reaction
40~50 DEG C of device inlet temperature, hydrogen/acetylene volume ratio is 1~1.5,50~60 DEG C of second segment reactor inlet temperature, hydrogen/
Acetylene volume ratio is 2~4.
12. methods according to claim 1, it is characterised in that：Selection hydrogenating materials are from de- in the back end hydrogenation technique of carbon two
Ethane tower tower top effluent；Raw material volume composition is mainly：Acetylene 0.98~2.2%, ethane 11.2~30.3%, ethene 65.0
~85.0%.
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