CN108250012A - A kind of method of methanol-to-olefins product selection acetylene hydrogenation - Google Patents
A kind of method of methanol-to-olefins product selection acetylene hydrogenation Download PDFInfo
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- CN108250012A CN108250012A CN201611249178.5A CN201611249178A CN108250012A CN 108250012 A CN108250012 A CN 108250012A CN 201611249178 A CN201611249178 A CN 201611249178A CN 108250012 A CN108250012 A CN 108250012A
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- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 158
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 239000001294 propane Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 230000009467 reduction Effects 0.000 claims description 27
- 150000001345 alkine derivatives Chemical class 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 238000002803 maceration Methods 0.000 claims description 11
- -1 magnesia compound Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000001994 activation Methods 0.000 description 16
- 230000004913 activation Effects 0.000 description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000012856 packing Methods 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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
- 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
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052709 silver 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 229920002521 macromolecule Polymers 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
- 238000001179 sorption measurement Methods 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 150000001361 allenes Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 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
- 238000005265 energy consumption Methods 0.000 description 2
- WZGWWPARMFQTAY-UHFFFAOYSA-N ethene;methanol Chemical group OC.C=C WZGWWPARMFQTAY-UHFFFAOYSA-N 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000010187 selection 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
- 230000000391 smoking effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003643 water by type Substances 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
- 239000004215 Carbon black (E152) Substances 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
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 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
- 229910021536 Zeolite Inorganic materials 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
- 239000003513 alkali Substances 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 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
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003034 coal gas 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
- 239000000571 coke Substances 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
- 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
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 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
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 230000002779 inactivation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 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
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Carbon in methanol-to-olefins two, three mixed material of carbon using Fe Mn hydrogenation catalysts, are carried out selection plus hydrogen, raw material composition (volume ratio) is predominantly by a kind of method of methanol-to-olefins product selection acetylene hydrogenation：H21.2~1.5%, N20.5~1.0%, O20.005~0.015%, CO 0.6~1.0%, CO20.2~0.6%, methane 6~10%, ethane 1~2%, acetylene 0~0.01%, ethylene 40~60%, propane 1.5~3%, propylene 15~40%, propine 0~0.01%.Reaction condition：25 DEG C~50 DEG C of inlet temperature, 1.5~2.5MPa of pressure, 2000~15000h of air speed‑1.Catalyst carrier is high-temperature inorganic oxide, and active component is at least containing Fe, Mn, and in terms of catalyst quality 100%, catalyst contains Fe 2~8%, Mn 0.05~0.3%；Catalyst specific surface is 10~200m20.2~0.63ml/g of/g, Kong Rongwei.The catalyst hydrogenation activity is mild, and ethylene selectivity is excellent, ethylene free of losses, and " green oil " production quantity is low, and catalyst cost is far below precious metals pd catalyst.
Description
Technical field
The present invention relates to a kind of methods of the acetylene hydrogenation of methanol-to-olefins product, particularly a kind of to add hydrogen using Fe-Mn
Catalyst agent will contained trace acetylene, propine (MA), allene (PD) hydro-conversion be second in methanol-to-olefins product
The method of alkene, propylene.
Background technology
The low-carbon alkenes such as ethylene, propylene are important basic chemical raw materials, with the development of Chinese national economy, particularly
Demand of the development of modern chemical industry to low-carbon alkene increasingly rises, and imbalance between supply and demand will also become increasingly conspicuous.So far, it produces
The important channel of the low-carbon alkenes such as ethylene, propylene, be still by naphtha, light diesel fuel (being all from oil) catalytic cracking,
Cracking, the raw material resources such as naphtha, light diesel fuel as ethylene production raw material are faced with increasingly severe short office
Face.In addition, crude oil in China import volume has accounted for half or so of processing total amount in recent years, using ethylene, propylene as raw material polyolefin
Product will maintain the quite high percentage of import.Therefore, development non-oil resource carrys out the technologies of preparing low-carbon olefins and increasingly causes
The attention of people.
The MTP techniques of methanol ethylene, the MTO techniques of propylene and preparing propylene from methanol are Chemical Engineering Technologies important at present.It should
The methanol that technology is synthesized using coal or natural gas produces low-carbon alkene as raw material, is development non-oil resource production ethylene, propylene etc.
The core technology of product.
MTO technology is the committed step in coal base alkene industrial chain, and technological process is predominantly suitably being grasped
Under the conditions of work, using methanol as raw material, suitable catalyst (ZSM-5 zeolite catalyst, SAPO-34 molecular sieves etc.) is chosen, solid
Pass through preparing low-carbon olefin through methanol dehydration in fixed bed and vulcanization bed reactor.According to the difference of purpose product, MTO technology
Be divided into methanol ethylene, propylene (methanol-to-olefin, MTO), preparing propylene from methanol (methanol-to-propylene,
MTP).The representative technology of MTO techniques has AP Oil company (UOP) and Hydro company (Norsk Hydro) joint development
UOP/Hydro MTO technologies, the DMTO technologies of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's autonomous innovation research and development；MTP techniques
Representative technology have Lucci corporation (Lurgi) develop Lurgi MTP technologies and the independent research of Tsinghua University of China FMTP skills
Art.
Entirely reaction can be divided into two stages to methanol-to-olefins：Water smoking, cracking reaction stage
1. the water smoking
2CH3OH→CH3OCH3+H2O+Q
2. the cracking reaction stage
The reaction process is mainly that the catalysis that dehydration reaction product dimethyl ether and a small amount of unconverted material benzenemethanol carry 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 ... ...
More than product has gaseous state (CO, H2、H2O、CO2、CH4Wait alkane, aromatic hydrocarbons etc.) and solid-state (macromolecule hydrocarbon and coke)
Point.
Methanol is after being dehydrated, cracking, detach, the still second containing 5~100ppm in the ethylene feed of deethanizer overhead
Alkynes, it influences the polymerization process of ethylene, and product quality is caused to decline, and needs to be removed by removing the method for alkynes.Ethylene object
The selection of trace acetylene plus hydrogen have extremely important influence to the polymerization process of ethylene in material, in addition to ensure plus hydrogen have it is enough
Activity ensures that the acetylene content of reactor outlet is up to standard, reacts with good under conditions of low acetylene content except alkynes performance
The hydrogen content of device outlet is up to standard outer, and the selectivity for also requiring catalyst is excellent, can make the generation ethane that ethylene is as few as possible,
Ensure that hydrogenation process does not bring the loss of device ethylene.
The separative element of methanol-to-olefins device generally uses the sequence separation process of Lummus companies at present.Ethylene
Refine two kinds of adoptable front-end hydrogenation, back end hydrogenation techniques.It is before front-end hydrogenation that hydrogenation reactor, which is located at separative element, hydrogenation reaction
Device is back end hydrogenation after being located at separative element.Methanol-to-olefins device is generally using back end hydrogenation technique at present, i.e., by pyrolysis product
The ethylene isolated carries out hydrofinishing removing acetylene, and propylene does not set hydrofining reactor, the four mixing group of carbon isolated
Divide and carry out selective hydrogenation and removing butadiene.But there are drawbacks for the technique, and ethylene, propylene are refined respectively again using first detaching,
Plant energy consumption is relatively high.Therefore, it is proposed to before separative element, finishing reactor is set, is detached again after removing acetylene
Front-end hydrogenation process route helps to reduce plant energy consumption, improves device economic benefit.
For front-end hydrogenation technique, in methanol-to-olefins device ethylene feed the selection of trace acetylene add hydrogen mainly use single hop
Reactor process.The volume content of each substance is as follows：Acetylene 1~10ppm of 5~100ppm, CO, hydrogen are used in material in itself
The hydrogen contained, H2Content is generally 1.2%~2.5%.1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1, enter
25 DEG C~50 DEG C of temperature of mouth.Reactor content composition is complex, and concrete composition is by table 1.
1 methanol-to-olefins device front-end hydrogenation technique acetylene hydrogenation reactor entrance material of table forms
Alkynes and diolefin hydrogenate catalyst are by the way that noble metal such as palladium is supported on porous Inorganic material carrier
On obtained (US4762956).In order to increase the selectivity of catalyst, the green oil that oligomerization generates when reducing by adding hydrogen is led
The catalyst inactivation of cause, the prior art employ the method for adding that such as group ib element is co-catalysis component in the catalyst：
Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Mn (US3912789) add in alkali or alkaline earth metal
(US5488024) etc., carrier used has aluminium oxide, silica (US5856262), loyal green stone of honeycomb (CN1176291) etc.
Deng.
US5856262 is reported using the modified silica of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) 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 molar ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
Using aluminium oxide as carrier, addition co-catalyst silver acts on US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst, which has, reduces ethane production quantity, acetylene of the absorption on catalyst surface is inhibited to carry out partial hydrogenation dimerization anti-
Should, inhibit 1,3-butadiene generation, reduce green oil generation, the characteristics of improving ethylene selectivity, reduce oxygenatedchemicals production quantity,
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 there is also many deficiencies for catalyst performance, 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 to preparation of ethylene through selective hydrogenation of acetylene have it is excellent
The egg-shell catalyst of good catalytic performance.It is characterized in that with aluminium oxide (Al2O3) bead be carrier, using infusion process prepare activity
Component palladium is in the loaded catalyst of eggshell type distribution, and using Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd is loaded
It is 1~5 to measure as 0.01~0.1wt%, Ag and Pd atomic ratio.The invention has the advantages that the one kind provided is used for second
Alkynes selects the egg-shell catalyst of Hydrogenation ethylene, can be under the conditions of high conversion of alkyne, especially in the acetylene close to 100%
During conversion ratio, high ethylene selectivity is realized.
CN201110086174.0 on carrier by adsorbing specific high-molecular compound, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with compound and high molecular weight reactive with functional base, with can be complexed with active component
Function base, complex reaction is occurred on carrier surface function base by active component, ensures active component orderly and height point
It dissipates.Using the patented method, the specific high-molecular compound of carrier adsorption carries out chemistry by the hydroxyl and macromolecule of aluminium oxide
Absorption, the amount of carrier adsorption high-molecular compound will be limited by the hydroxyl quantity of aluminium oxide；By the macromolecule of functionalization
Not strong with the complexing of Pd, activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is made
It is improved into catalyst cost；Using this method prepare C2 hydrogenation catalyst also there are technological process it is complicated the shortcomings that.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst is by being selected from the first component of copper, gold, silver and selecting second of component group of nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium
Into in addition catalyst further includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.It urges
Fluorite structure is formed after agent calcining, use or regeneration.Catalyst oxide total content 0.01~50%, preferably calcination temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With activity, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. for active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several kinds, additionally include 1~10% auxiliary agent.The inventive technique is mainly used for second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, have good deep hydrogenation ability.The technology be mainly used for rich in CO and
The complete plus hydrogen of ethylene, propylene, butylene etc., is not suitable for alkynes, the selection of alkadienes adds hydrogen in the various industrial tail gas of hydrogen.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
The intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between the metal
Object is closed to be prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stablizing reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In conclusion the selective hydrogenation of low-carbon alkynes and alkadienes, at present mainly using noble metal catalyst, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provide a kind of novel Fe series hydrocatalysts and preparation method thereof.
Invention content
It is particularly a kind of the purpose of the present invention is to provide a kind of method of methanol-to-olefins product selection acetylene hydrogenation
Fe-Mn hydrogenation catalyst, by trace acetylene contained in methanol-to-olefins product, propine (MA), allene (PD) selectivity
Add hydrogen, be converted into ethylene, propylene, while alkene does not lose.
The method of a kind of methanol-to-olefins product selection acetylene hydrogenation of the present invention, from dry in methanol-to-olefins device
Carbon two, three mixed material of carbon of dry tower bottom of towe carry out selection plus hydrogen into adiabatic reactor reactor, are equipped in adiabatic reactor reactor
Fe-Mn selective hydrogenation catalysts, carrier are high-temperature inorganic oxide, and active component is at least containing Fe, Mn, with catalyst quality
100% meter, catalyst contain Fe 2~6 (wt) %, and preferred content is 3~5%, Mn 0.5~1.0%, preferred content for 0.6~
0.9%；Catalyst specific surface is 10~200m2/ g, preferably 30~150m2/ g, Kong Rongwei 0.2~0.63ml/g, preferably 0.3~
0.55ml/g；Wherein catalyst is to be loaded with active component on carrier by impregnation method, and fired, hydrogen atmosphere reduction is made
；Reaction condition is：25~50 DEG C, 1.5~2.5MPa of reaction pressure, 2000~15000h of air speed of reactor inlet temperature-1。
Of the present invention to use hydrogenation catalyst except the method for alkynes, carrier is high-temperature inorganic oxide, is such as aoxidized
One or more of aluminium, silica, zirconium oxide, magnesia etc..It is preferred that aluminium oxide or alumina series carrier, alumina series
Carrier refers to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for more than the 50% of carrier quality, such as can be
The compound of the oxides such as aluminium oxide and silica, zirconium oxide, magnesia, preferably alumina-zirconia composite carrier, wherein
Alumina content is more than 60%.Aluminium oxide can be θ, α, γ type or the mixture of its a variety of crystal form, preferably α-Al2O3Or
- the Al containing α2O3Mixing crystal form aluminium oxide.
The method that the present invention removes alkynes, uses the preparation process of Fe-Mn selective hydrogenation catalysts to include：
Catalyst is aged by preparing Fe predecessors aqueous solution, Mn predecessor aqueous solutions, difference impregnated carrier, is dry respectively
Dry, roasting or with its mixed solution impregnated carrier, obtains after rear ageing, dry, roasting.
The present invention use hydrogenation catalyst preparation condition for：
30~60 DEG C, 10~60min of load time of dipping temperature, maceration extract pH value 1.5~5.0, Aging Temperature 30~60
DEG C, 30~120min of digestion time, 300~600 DEG C of calcination temperature, preferably 400~500 DEG C, 240~300min of roasting time.
Dry in the present invention is preferably temperature programming drying, and drying temperature program setting is：
Roasting is activation process in the present invention, and preferably temperature-programmed calcination, calcination temperature program setting is：
Incipient impregnation may be used in heretofore described catalyst, excessive dipping, surface spray, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
It is as follows：
(1) carrier is weighed after measuring carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity,
According to carrier water absorption rate and dipping method, dipping solution is prepared, and adjust maceration extract pH value 1.5~5.0 as required, and by solution
Be heated to 30~60 DEG C it is spare.
(3) using incipient impregnation or when spraying method, the carrier weighed can be put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, carrier is totally turned over, prepared 30~60 DEG C of maceration extract is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier weighed is placed in container, then adds in 30~60 DEG C of dipping of preparation
Solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier weighed is placed in cyclonic evaporator, is vacuumized, add in 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution extra after dipping is filtered out, is then dried in an oven using the method for temperature programming, it is dry
Temperature program(me)：
(6) dried catalyst using temperature programming method is roasted, roasts temperature program：
Catalyst Mn components are loaded using above-mentioned same steps, 300~600 DEG C of calcination temperature, preferably 400~
500 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
It can also contain other active components in addition to containing Fe, Mn in catalyst composition in the present invention.
The catalyst of the present invention needs to be restored with hydrogen-containing gas, H2Volume content is preferably 10~50%, and reduction temperature is most
It is 350~490 DEG C well, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；The condition of recommendation is to use N2+H2It is mixed
It closes gas to be restored for 400~450 DEG C under the conditions of micro-positive pressure, the recovery time is preferably 240~360min, and volume space velocity is best
200~400h-1, reduction pressure is preferably 0.1~0.5MPa.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms exist in FeO, mainly with α-
Fe2O3Form exist, preferably containing a certain amount of Fe3O4.Recommend at least to add in iron-containing activity composition in the present invention
Mn exists to correspond in the form of oxidation state, is conducive to formation, the dispersion of agent activity phase, and is conducive to the stabilization of active phase, carries
High catalyst activity, selectivity and anticoking capability.
Fe, Co and its different oxide relative amounts, pass through XRD diffraction peak areas integration method approximation in catalyst of the present invention
It calculates.
The activation temperature of catalyst and activity composition, content and carrier related, the activated mistake of catalyst in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be excessively high；On the other hand, activation degree is again
It determines the reducing condition of catalyst, is provided in the catalyst used still with α-Fe in the present invention2O3The Fe of form for mainly into
Point, over reduction can influence the effect of catalyst instead, reduce activity, selectivity, easy coking.
In the present invention, hydrogenation material is reacted in single stage adiabatic bed reactor, will under Fe-Mn catalyst actions
Contained trace acetylene selective hydrogenation, is converted into ethylene in material.
Selection method of hydrotreating of the present invention adds hydrogen object for the mixed material before methanol-to-olefins separation, volume group
Into predominantly：H21.2~1.5%, N20.5~1.0%, O20.005~0.015%, CO 0.6~1.0%, CO20.2~
0.6%, H2S 0~0.0008%, methane 6~10%, ethane 1~2%, acetylene 0~0.01%, ethylene 40~60%, propane
1.5~3%, propylene 15~40%, propine 0~0.01%, carbon 4 3~6%, more than light dydrocarbon 6~10%.
In the present invention, hydrogenation material, will be in material under Fe-Mn catalyst actions in single stage adiabatic bed reactor
Contained trace acetylene, propine (MA), allene (PD) selective hydrogenation, are converted into ethylene, propylene.
Selection method of hydrotreating of the present invention, reaction condition are：25 DEG C~50 DEG C of reactor inlet temperature, reaction pressure
1.5~2.5MPa, 2000~15000h of air speed-1。
It is of the present invention to remove alkynes method, contain a certain amount of hydrogen in material, do not need in addition mend hydrogen in reaction.
Using the present invention except alkynes method, 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 " production quantity is far below noble metal catalyst, and catalyst anticoking capability is excellent, while using the present invention
Except alkynes method, the performance of the poisonous substances such as N, S, As, O greatly promotes in anti-material.
Description of the drawings
Fig. 1 is methanol-to-olefins product hydrogenation technique flow chart.
In figure：1-DME reactors；2-MTP reactors；The separation of 3-pre- chilling；4-chilling detaches；5-level Four is compressed；
6-level Four detaches；7-drying tower；8- acetylene hydrogenation reactors；9-domethanizing column；10-dethanizer.
Fig. 2 is XRD spectra after the catalyst reduction of the embodiment of the present invention 4.
Fig. 3 is 4 catalyst XRD spectra of comparative example.
Fig. 4 is the catalyst XRD spectra 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 scanning ranges, 25 DEG C of temperature
1 wavelength of Mn K α, abscissa is 2 θ of the angle of diffraction in figure, and ordinate is diffracted intensity
Different crystal forms Fe oxide contents are obtained using XRD diffraction peak areas integration method in catalyst, and benchmark is metal oxygen
Compound total amount.
Symbol description in Fig. 2：
● it is α-Fe2O3, ▲ be Mn3O4, ■ Fe3O4。
Symbol description in Fig. 3：
● it is α-Fe2O3, ☆ MnFe2O4, ■ Fe3O4。
Symbol description in Fig. 4：
■ is Fe3O4, ◆ it is Mn3O4。
Fig. 2 is that the catalyst prepared using this technology urges XRD diffraction patterns after carrying out reduction, and wherein Fe is mainly with α-Fe2O3Form
In the presence of relative amount 4.00% has on a small quantity with Fe3O4Form exists, and Mn is with Mn3O4Form exists.
Fig. 3 is the comparative example catalyst XRD diffraction patterns without reduction, and middle Fe is mainly with α-Fe2O3Form exists, opposite to contain
4.78%, Mn is measured with Mn2O3, form presence.
The comparative example catalyst XRD diffraction patterns of Fig. 4 high temperature reductions, Fe are reduced into Fe3O4Form and simple substance α-Fe forms,
Mn exists in the form of MnO.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
Analysis test method：
Specific surface：GB/T-5816
Kong Rong：GB/T-5816
Different crystal forms oxide content：XRD
Heap density：Q/SY142-2006
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 × △ ethylene/△ acetylene
Embodiment 1
Weigh the trifolium-shaped alumina support of 4.5 × 4.5mm of Φ.Ferric nitrate is taken, is dissolved by heating in 60ml deionized waters, is adjusted
PH value 2.5, maceration extract temperature 50 C are saved, incipient impregnation stirs rapidly carrier impregnation 6min, static 30min to suction in carrier surface
Attached balance, 60 DEG C of ageing 30min, then in an oven according to program：100 DEG C of 100 DEG C of drying catalyst of room temperature, are then adopted
Activation of catalyst, activation procedure are carried out with programmed temperature method： Manganese nitrate is weighed, is impregnated according to above-mentioned preparation process.
Catalyst in reduction furnace with+60% nitrogen of 40% hydrogen before use, restored, 420 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.React item
Part：Air speed 10000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction raw materials composition such as table 2.
2 raw material of table forms
Carrier and catalyst physical index, catalyst components content are shown in Table 3, and reaction result is as shown in table 4.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with salpeter solution, stirs 10h, coprecipitated
It forms sediment and generates uniform Al-Zr particles.Product is filtered, Na therein is washed with deionized+And Cl-Then ion adds in matter
A concentration of 15% polyvinyl alcohol is measured as pore creating material, it is kneaded and formed.130 DEG C of dry 2h, 650 DEG C of roasting 4h obtain Zr-Al and answer
Close carrier.Aluminium oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Iron chloride and manganese chloride are taken, is dissolved by heating in deionized water, is adjusted
PH value 2.0 is saved, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, is shaken beaker dipping 10min, extra maceration extract is filtered out, catalyst
50min is aged in 60 DEG C of water-baths, then in an oven according to program：
Catalyst is dried, activation of catalyst, activation procedure are carried out using programmed temperature method： Carrier and catalyst physical index, catalyst are each
Constituent content is shown in Table 3.
Catalyst in reduction furnace with+60% nitrogen of 30% hydrogen before use, restored, 400 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 50 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.Instead
It should the results are shown in Table 4.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Ferric nitrate is taken to be dissolved in 40ml deionized waters, is adjusted
PH value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly, bears
It carries process control to complete in 6min, then in an oven according to program：
Catalyst is dried, catalyst is moved into evaporating dish, activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence： Obtain one
Soak catalyst.
Using first step same procedure, manganese nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, is then dried, roast,
Obtain final catalyst.Drying program：Calcination procedure：Carrier and catalysis
Agent physical index, catalyst components content are shown in Table 3.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 400 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.
Reaction condition：Air speed 6000h-1, pressure 2.5MPa, 40 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2, instead
It should the results are shown in Table 4.
Embodiment 4
The spherical tio2 carrier of the Φ 2.0mm weighed is placed in vacuum impregnation plant.Ferric nitrate is taken to be dissolved in deionized water
In, it is spare to adjust pH value 3.5.Vacuum impregnation plant vacuum pumping pump is opened, until vacuum degree 0.1mmHg, then slowly adds from charge door
Entering prepared maceration extract, 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is completely disappeared, and completes load,
The catalyst that will have been loaded, in an oven according to program：Drying, in horse
Not in stove according to：
Roasting.Obtain a leaching catalyst.
Manganese nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, roasts, obtains final catalyst.Dry journey
Sequence：
Calcination procedure：
Restore rear catalyst XRD analysis as shown in Figure 1.Carrier and catalyst physical index, catalyst components content are shown in Table 3.
Catalyst in reduction furnace with 15% hydrogen before use, restored, 430 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 4000h-1, pressure 1.8MPa, 45 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2, instead
It should the results are shown in Table 4.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using 3 same procedure of embodiment.Activation temperature
500℃.Carrier and catalyst physical index, catalyst components content are shown in Table 3.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 450 DEG C, pressure 0.5MPa of temperature, during reduction
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 13000h-1, pressure 2.5MPa, 30 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.Instead
It should the results are shown in Table 4.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are pressed according to aluminium oxide：Silica：Zirconium oxide
=8:1:3 ratios are uniformly 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 4 same procedure of embodiment.Carrier and catalyst physical index,
Catalyst components content is shown in Table 3.
Catalyst is before use, with+55% nitrogen of 45% hydrogen, 490 DEG C, pressure 0.5MPa of temperature, activation in reduction furnace
Time 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 5000h-1, pressure 2.5MPa, 40 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.Instead
It should the results are shown in Table 4.
Comparative example 1
Take Φ 4.0mm alumina supports, specific surface 4.5m2/g, Kong Rongwei 0.32ml/g.Using equi-volume impregnating,
By silver nitrate solution incipient impregnation to carrier on, ageing-drying-roasting obtains a leaching catalyst, then by palladium bichloride
Dissolving, incipient impregnation, ageing-drying-roasting obtain final catalyst (petrochemical industry research institute PAH-01 hydrogenation catalysts).It urges
Agent Pd contents are that 0.050%, Ag contents are 0.20%.
Catalyst is at 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1.Added with attached drawing 1 Suo Shi
Hydrogen flow, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 10000h-1, pressure 1.5MPa, 35 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.Instead
It should the results are shown in Table 4.
Comparative example 2
Carrier is made with Φ 4.0mm aluminium oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃.Carrier and catalyst physical index, catalyst components content are shown in Table 3.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 420 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 8000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.Instead
It should the results are shown in Table 4.
Comparative example 3
The aluminium oxide for weighing Φ 4.0mm makees carrier, prepares catalyst using 1 same procedure of embodiment, lives at 450 DEG C
Change.Carrier and catalyst physical index, catalyst components content are shown in Table 3.
Catalyst in reduction furnace with 45% hydrogen before use, restored, 450 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 3000h-1, pressure 1.5MPa, 50 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.
Reaction result is as shown in table 4.
Comparative example 4
Prepared by 1 same procedure of Example, directly drive after 450 DEG C of activation, restored without hydrogen.Catalyst
XRD diffraction spectrograms are as shown in Figure 3.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.Reaction raw materials composition is as shown in table 2.
Reaction result is as shown in table 4.
Comparative example 5
1 same procedure of Example prepares catalyst, and in 450 DEG C of activation, carrier and catalyst physical index, catalyst are each
Constituent content is shown in Table 3.
Catalyst is restored in tube furnace, atmosphere be+55% nitrogen of 30% hydrogen, 500 DEG C of temperature, pressure
0.5MPa, soak time 4h.The XRD diffraction spectrograms for restoring rear catalyst are as shown in Figure 4.With hydrogen flow is added attached drawing 1 Suo Shi, it is catalyzed
Agent is loaded in fixed-bed reactor.
Reaction result is as shown in table 4.
Carrier and catalyst physical index, catalyst components content are as shown in table 3.
3 carrier of table, catalyst physical property and catalyst components content
Reaction result is as shown in table 4.
The selection of 4 catalyst methanol-to-olefins product of table plus hydrogen result
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of method of methanol-to-olefins product selection acetylene hydrogenation, the carbon from drying tower bottom of towe in methanol-to-olefins device
2nd, three mixed material of carbon carries out selection plus hydrogen into adiabatic reactor reactor, it is characterised in that：Fe- is housed in adiabatic reactor reactor
Mn selective hydrogenation catalysts, carrier are high-temperature inorganic oxide, and active component is at least containing Fe, Mn, with catalyst quality
100% meter, catalyst contain Fe 2~6%, and preferred content is 3~5%, Mn 0.5~1.0%, preferred content for 0.6~
0.9%；Catalyst specific surface is 10~200m2/ g, preferably 30~150m2/ g, Kong Rongwei 0.2~0.63ml/g, preferably 0.3~
0.55ml/g；Wherein catalyst is to be loaded with active component on carrier by impregnation method, and fired, hydrogen atmosphere reduction is made
；Reaction condition is：25~50 DEG C, 1.5~2.5MPa of reaction pressure, 2000~15000h of air speed of reactor inlet temperature-1。
It is 2. according to claim 1 except the method for alkynes, it is characterised in that：In used hydrogenation catalyst, active component Fe
With α-Fe2O3Form exists, wherein α-Fe2O3The Fe of form will account for more than 50% Fe gross masses.
It is 3. according to claim 1 except the method for alkynes, it is characterised in that：Catalyst carrier is that aluminium oxide or alumina series carry
Body, alumina series carrier refer to the complex carrier of aluminium oxide and other oxides, wherein aluminium oxide account for the 50% of carrier quality with
On, complex carrier be aluminium oxide with silica, zirconium oxide, magnesia compound, the preferably compound load of aluminium oxide-zirconium oxide
Body, wherein alumina content is more than 60%；Mixture of the aluminium oxide for θ, α, γ type or its a variety of crystal form, preferably α-Al2O3
Or-the Al containing α2O3Mixing crystal form aluminium oxide.
It is 4. according to claim 1 except the method for alkynes, it is characterised in that：Used Fe-Mn selective hydrogenation catalysts pass through
Fe predecessors aqueous solution, Mn predecessor aqueous solutions are prepared, respectively impregnated carrier, respectively ageing, dry, roasting or molten with its mixing
Liquid impregnated carrier obtains after rear ageing, dry, roasting.
It is 5. according to claim 4 except the method for alkynes, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10~
60min, maceration extract pH value 1.5~5.0,30~60 DEG C, 30~120min of digestion time of Aging Temperature, calcination temperature 300~600
DEG C, preferably 400~500 DEG C, 240~300min of roasting time.
It is 6. according to claim 4 except the method for alkynes, it is characterised in that：It is dry to be dried for temperature programming, drying temperature journey
Sequence is set as：
It is 7. according to claim 4 except the method for alkynes, it is characterised in that：It is roasted to temperature-programmed calcination,
Calcination temperature program setting is：
8. described in claim 4 except the method for alkynes, it is characterised in that：Catalyst reduction refers to use N2+H2Gaseous mixture is to catalyst
It is restored, H2Volume content is preferably 10~50%, 350~490 DEG C, 240~360min of recovery time of reduction temperature, volume
100~500h of air speed-1, 0.1~0.8MPa of reduction pressure；Optimum condition is is restored at 400~450 DEG C, volume space velocity
200~400h-1, reduction pressure is preferably 0.1~0.5MPa.
It is 9. according to claim 1 except the method for alkynes, it is characterised in that：Carbon two, carbon three from drying tower bottom of towe mix
Volume of material forms：H21.2~1.5%, N20.5~1.0%, O20.005~0.015%, CO 0.6~1.0%, CO2
0.2~0.6%, H2S 0~0.0008%, methane 6~10%, ethane 1~2%, acetylene 0~0.01%, ethylene 40~60%,
Propane 1.5~3%, propylene 15~40%, propine 0~0.01%, carbon 4 3~6%, more than light dydrocarbon 6~10%.
It is 10. according to claim 1 except the method for alkynes, it is characterised in that：Adiabatic reactor reactor is single hop reactor.
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| CN109264740A (en) * | 2018-09-30 | 2019-01-25 | 厦门大学 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
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