CN117398991A - Solid catalyst, preparation method thereof and method for co-producing butenol and butadiene - Google Patents
Solid catalyst, preparation method thereof and method for co-producing butenol and butadiene Download PDFInfo
- Publication number
- CN117398991A CN117398991A CN202210730466.1A CN202210730466A CN117398991A CN 117398991 A CN117398991 A CN 117398991A CN 202210730466 A CN202210730466 A CN 202210730466A CN 117398991 A CN117398991 A CN 117398991A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- butene
- slurry
- butadiene
- butenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 121
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 54
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 20
- 239000011029 spinel Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 5
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000009718 spray deposition Methods 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 4
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract description 23
- 230000004913 activation Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 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 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000004537 pulping Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ZZCONUBOESKGOK-UHFFFAOYSA-N aluminum;trinitrate;hydrate Chemical compound O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZZCONUBOESKGOK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OMUMHHURKXLMEO-UHFFFAOYSA-N barium(2+) dinitrate hydrate Chemical compound O.[Ba++].[O-][N+]([O-])=O.[O-][N+]([O-])=O OMUMHHURKXLMEO-UHFFFAOYSA-N 0.000 description 1
- JJIQGEZLLWXYKV-UHFFFAOYSA-N calcium;dinitrate;hydrate Chemical compound O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JJIQGEZLLWXYKV-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 description 1
- ZVLZZJUHYPMZAH-UHFFFAOYSA-L cobalt(2+) dinitrite Chemical compound [Co+2].[O-]N=O.[O-]N=O ZVLZZJUHYPMZAH-UHFFFAOYSA-L 0.000 description 1
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YISKQXFNIWWETM-UHFFFAOYSA-N magnesium;dinitrate;hydrate Chemical compound O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YISKQXFNIWWETM-UHFFFAOYSA-N 0.000 description 1
- HBTFASPVVFSRRI-UHFFFAOYSA-N manganese(2+);dinitrate;hydrate Chemical compound O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HBTFASPVVFSRRI-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- IUDWCJPOHVCDPQ-UHFFFAOYSA-N strontium dinitrate hydrate Chemical compound O.[Sr++].[O-][N+]([O-])=O.[O-][N+]([O-])=O IUDWCJPOHVCDPQ-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 description 1
- XBMSSMOTGOJLBZ-UHFFFAOYSA-N zirconium(4+) tetranitrate hydrate Chemical compound O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XBMSSMOTGOJLBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The invention relates to the field of catalysts, in particular to a solid catalyst for preparing butadiene and butenol by using a butene raw material, a preparation method thereof and a method for co-producing butenol and butadiene. The catalyst contains spinel phase, silicate crystal phase of IIA metal and metal auxiliary agent, wherein the metal element of the metal auxiliary agent is selected from one or more of IVB, VB, VIB and lanthanide series metal elements. The invention reduces the proportion of the butene oxidative dehydrogenation reaction route on the surface of the butene reaction molecular catalyst by adopting the method of introducing relatively inert silicate components to dilute the butene oxidative dehydrogenation active sites on the surface of the original spinel catalytic material. Meanwhile, a metal auxiliary agent capable of increasing the density of the alkali center on the surface of the catalyst is introduced into the spinel catalyst, so that the activation probability of alpha-hydrogen or beta-hydrogen in butene molecules is increased, and butadiene and butenol products can be simultaneously generated. Has very practical value and wide application prospect in industrial production.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a solid catalyst for preparing butadiene and butenol by using a butene raw material, a preparation method thereof and a method for co-producing butenol and butadiene.
Background
Butadiene is an important monomer for petrochemical basic raw material and high-molecular synthetic material production, and can be copolymerized with various compounds to prepare various synthetic rubbers and synthetic resins. At present, butadiene is mainly produced by two methods of refinery steam cracking ethylene co-production carbon four extraction separation and butene oxidation. Butadiene in China is almost completely obtained from four carbon extractions, and the process is economically advantageous, but is obtained as a byproduct of a refinery cracking device, and as the demand of the rubber industry for butadiene output increases, the production of butadiene by the cracking device is difficult to meet the demand. The butene oxidative dehydrogenation process is a process taking butadiene as a target product, and can convert butene used by domestic fuel into butadiene with high added value, and the production technology route has become an increasingly important butadiene production route.
The butenol is an important intermediate of organic chemical industry, has active properties due to double bonds and alcoholic hydroxyl groups in molecules, can be widely used for synthesizing medicines and agricultural chemicals, and has rapid increase in demand for butenol in recent years in the fine chemical industry market.
The butene oxidative dehydrogenation process is carried out under the condition of oxidization, and a Mo-Bi system, a Sn-P-Li system and an Fe acid salt system are generally adopted as the catalyst, so that organic oxygen-containing byproducts such as alcohols, aldehydes, ketones, acids and the like are inevitably generated except that the main reaction of butadiene is generated by oxidative dehydrogenation, and the types and the contents of the byproducts are related to the nature of active sites of reactants on the surface of the catalyst and the activation form of the reactants. The prior art has no description on a catalyst for producing the butenol while the butene is subjected to the oxidative dehydrogenation reaction to produce the butadiene under the condition of no new production device.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a solid catalyst for preparing butadiene and butenol from a butene feedstock, a preparation method thereof, and a method for co-producing butenol and butadiene.
In order to achieve the above object, the present invention provides in a first aspect a solid catalyst for the preparation of butadiene and 3-buten-1-ol from a butene feedstock, the catalyst comprising both a spinel phase and a silicate phase of a group IIA metal and a metal promoter selected from one or more of the group IVB, group VB, group VIB and lanthanide series metal elements.
The second aspect of the invention provides a method for synthesizing the catalyst, which comprises the following steps:
(1) Coprecipitating a solution containing inorganic salts and high molecular organics required for constituting the spinel phase with an inorganic base to form a first slurry;
(2) Aging, filtering and washing the first slurry, and dispersing the first slurry in water to form a second slurry;
(3) Mixing silica sol, a IIA metal source and a metal auxiliary agent source, and then mixing with the second slurry obtained in the step (2) to form a third slurry;
(4) Forming granular powder by a spray forming method of the third slurry obtained in the step (3);
(5) And (3) roasting the granular powder obtained in the step (4) to obtain the catalyst.
In a third aspect, the present invention provides a process for co-producing butenol and butadiene, the process comprising: the butenes are contacted to produce butadiene and butenols in the presence of a catalyst, including the catalysts of the present invention described previously, and a diluent and an oxidant.
By adopting the scheme, the invention has the following advantages:
the invention reduces the proportion of the butene oxidative dehydrogenation reaction route on the surface of the butene reaction molecular catalyst by adopting the method of introducing relatively inert silicate components to dilute the butene oxidative dehydrogenation active sites on the surface of the original spinel catalytic material. Meanwhile, a metal auxiliary agent capable of increasing the density of the alkali center on the surface of the catalyst is introduced into the spinel catalyst, so that the activation probability of alpha-hydrogen or beta-hydrogen in butene molecules is increased, and butadiene and butenol products can be simultaneously generated. Has very practical value and wide application prospect in industrial production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a solid catalyst for preparing butadiene and 3-butene-1-ol by using butene raw material, which contains spinel phase, silicate crystal phase of IIA metal and metal auxiliary agent, wherein the metal auxiliary agent is selected from one or more of IVB, VB, VIB and lanthanide series metal elements.
The invention reduces the proportion of the butene oxidative dehydrogenation reaction route on the surface of the butene reaction molecular catalyst by adopting the method of introducing relatively inert silicate components to dilute the butene oxidative dehydrogenation active sites on the surface of the original spinel catalytic material. Meanwhile, a metal auxiliary agent capable of increasing the density of the alkali center on the surface of the catalyst is introduced into the spinel catalyst, so that the activation probability of alpha-hydrogen or beta-hydrogen in butene molecules is increased, and butadiene and butenol products can be simultaneously generated.
In the present invention, the content of each substance in the catalyst is not particularly limited as long as the object of the present invention can be achieved.
According to a preferred embodiment of the invention, the content of spinel phase is 29.0 to 59.0 wt.%, preferably 35.0 to 55.0 wt.%, based on the total weight of the catalyst.
According to a preferred embodiment of the invention, the group IIA metal silicate crystalline phase is present in an amount of 40.0 to 70.0wt%, preferably 50.0 to 60.0wt%, based on the total weight of the catalyst;
according to a preferred embodiment of the invention, the metal promoter is present in an amount of 1.0 to 5.0 wt.%, preferably 2.0 to 4.0 wt.%, calculated as oxide, based on the total weight of the catalyst.
By limiting the content of each substance in the catalyst, the catalyst can have different active reaction sites, which is more beneficial to the oxidative dehydrogenation of butene and the simultaneous production of butadiene and butenol products.
According to a preferred embodiment of the invention, the metal promoter is selected from one or more of the elements Mo, nb, W, zr and Ce, preferably from one or more of the elements Nb, mo and Ce. By adopting the preferable scheme, the density of the alkali center on the surface of the catalyst can be increased, the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules is increased, and the oxidative dehydrogenation of butene is facilitated, and butadiene and butenol products are simultaneously produced.
According to a preferred embodiment of the invention, the spinel phase has a structure satisfying the formula: AB (AB) 2 O 4 Wherein A is 2 + Selected from Ca 2+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Hg 2+ And Sn (Sn) 2+ One or more of the following; b (B) 3+ Selected from Al 3+ 、Co 3+ 、Bi 3 + 、Fe 3+ 、Ti 3+ 、V 3+ And In 3+ One or more of the following. By adopting the foregoing preferred scheme, the catalyst can be made more conducive to oxidative dehydrogenation of butene while producing butadiene and butenol products.
According to a preferred embodiment of the invention, the group IIA metal is selected from one or more of Be, mg, ca, sr and Ba. By adopting the preferable scheme, the catalyst can reduce the surface acid sites, plays a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol products.
In the present invention, the pore volume of the catalyst is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the pore volume of the catalyst is 0.2 to 6.0ml/g, preferably 1.0 to 5.0ml/. By adopting the catalyst with the pore volume, the catalyst has a larger inner surface, plays a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol products.
In the present invention, the pore diameter of the catalyst is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the average pore diameter of the catalyst is 200 to 600nm, preferably 300 to 500nm. By adopting the catalyst with the pore diameter, the catalyst can play a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol products.
In the present invention, as long as the object of the present invention can be achievedThe specific surface area of the catalyst is not particularly limited, and according to a preferred embodiment of the present invention, the specific surface area of the catalyst is 5 to 60m 2 Preferably 10 to 30m 2 And/g. By adopting the catalyst with the specific surface area, the catalyst can play a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol products.
The invention provides a method for synthesizing the catalyst, which comprises the following steps:
(1) Coprecipitating a solution containing inorganic salts and high molecular organics required for constituting the spinel phase with an inorganic base to form a first slurry;
(2) Aging, filtering and washing the first slurry, and dispersing the first slurry in water to form a second slurry;
(3) Mixing silica sol, a IIA metal source and a metal auxiliary agent source, and then mixing with the second slurry obtained in the step (2) to form a third slurry;
(4) Forming granular powder by a spray forming method of the third slurry obtained in the step (3);
(5) And (3) roasting the granular powder obtained in the step (4) to obtain the catalyst.
Alternatively, the catalyst of the present invention may be shaped into spheres, cylinders, rings, clover, etc. and then calcined, wherein the shaping method may be a conventional choice in the art, such as extrusion, compression.
The catalyst obtained by the method is especially suitable for preparing butadiene and butenol products from butene raw materials.
According to a preferred embodiment of the invention, the inorganic salt required for constituting the spinel phase comprises a salt containing A 2+ Inorganic salts of (C) and B-containing 3+ Inorganic salt of A) 2+ Selected from Ca 2+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Hg 2+ And Sn (Sn) 2+ One or more of the following; b (B) 3+ Selected from Al 3+ 、Co 3+ 、Bi 3+ 、Fe 3+ 、Ti 3+ 、V 3+ And In 3+ One or more of (A), e.g. containing A 2+ The inorganic salt of (a) may be one or more of manganese nitrate, manganese nitrate hydrate, cobalt nitrate hydrate, zinc nitrate hydrate, nickel nitrate and nickel nitrate hydrate; containing B 3+ The inorganic salt of (a) may be one or more of aluminum nitrate, aluminum nitrate hydrate, iron nitrate and iron nitrate hydrate.
In the present invention, the polymer organic matter may be selected conventionally in the art, and according to a preferred embodiment of the present invention, the polymer organic matter is at least one of polyethylene glycol, starch, sodium carboxymethyl cellulose and sucrose, and the amount of the polymer organic matter added is 0.1wt% to 5wt%, preferably 0.6wt% to 3.0wt% of the total amount of each substance added to synthesize the catalyst. By adopting the preferable scheme, the catalyst can play a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol.
In the present invention, the inorganic base may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the inorganic base is selected from one or more of sodium carbonate, sodium hydroxide, urea, ammonia, diamine, and potassium hydroxide, and preferably the inorganic base concentration is 10 to 20wt%. By adopting the preferable scheme, the catalyst can play a role in increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules, and is more beneficial to oxidative dehydrogenation of butene and simultaneous production of butadiene and butenol.
In the present invention, the metal auxiliary source may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the metal auxiliary source contains group IVB, group VB, group VIB and lanthanide metal elements, preferably one or more of Mo, nb, W, zr and Ce elements, more preferably one or more of Nb, mo and Ce elements, and for example, the metal auxiliary source may be one or more of zirconium nitrate, zirconium nitrate hydrate, ammonium molybdate hydrate, niobium pentachloride, cerium nitrate hydrate, sodium tungstate and sodium tungstate hydrate.
According to a preferred embodiment of the present invention, the group IIA metal element in the group IIA metal source is selected from one or more of Be, mg, ca, sr and Ba. For example, the group IIA metal source can be one or more of calcium nitrate, calcium nitrate hydrate, barium nitrate hydrate, strontium nitrate hydrate, magnesium nitrate, and magnesium nitrate hydrate.
In the present invention, there is no particular limitation on the particle diameter of the silica sol in the step (3) as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the most probable distribution of the particle diameter of the silica sol in the step (3) is 20 to 200nm, preferably 80 to 160nm. By adopting the preferable scheme, the silicon component can be better dispersed in the catalyst, the effect of increasing the activation probability of alpha-hydrogen and beta-hydrogen in butene molecules is achieved, and the oxidative dehydrogenation of butene is facilitated, and butadiene and butenol are simultaneously produced.
In the present invention, the purity of the silica sol in the step (3) is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the purity of the silica sol in the step (3) is 20 to 40%.
In the invention, the mode of mixing the silica sol, the IIA metal source and the metal auxiliary agent source in the step (3) is to firstly dilute the silica sol, then add the IIA metal source and the metal auxiliary agent source for mixing.
According to a preferred embodiment of the invention, the catalyst obtained after calcination in step (5) has a lateral pressure strength higher than 160N/cm and a particle size of 20 to 160. Mu.m, preferably 30 to 120. Mu.m.
In the present invention, the conditions for the co-precipitation in step (1) may be conventional in the art, and according to a preferred embodiment of the present invention, the conditions for the co-precipitation in step (1) include: the temperature is 10-50 ℃, the pH value is 8.0-11.0, preferably 8.2-9.8, and the stirring is carried out.
In the present invention, the conditions for aging in step (2) may be conventional in the art, and according to a preferred embodiment of the present invention, the conditions for aging in step (2) include: the aging temperature is 10-50 ℃ and the aging time is 0.5-4 hours.
In the present invention, the conditions for spray-drying in step (3) may be conventional in the art, and according to a preferred embodiment of the present invention, the conditions for spray-drying in step (3) include: the inlet temperature is 260-300 ℃, the outlet temperature is 150-200 ℃, the rotating speed is 6000-15000 rmp/min, and the air flow is 2.8-5.0 m 3 /h。
In the present invention, the conditions for firing in step (5) may be conventional choices in the art, and according to a preferred embodiment of the present invention, the conditions for firing in step (5) include: the baking is carried out in air atmosphere at 550-750 deg.c, preferably 620-690 deg.c for 4-12 hr.
The catalyst prepared by using the preferred conditions described above is particularly useful in the production of simultaneous conversion of butenes to butadiene and butenols.
According to a preferred embodiment of the invention, the solids content of the first slurry is 1.5-8.0% by weight.
According to a preferred embodiment of the invention, the solids content of the second slurry is 20-40% by weight.
The invention provides a method for co-producing butenol and butadiene, which comprises the following steps: the butenes are contacted to produce butadiene and butenols in the presence of a catalyst, including the catalysts of the present invention described previously, and a diluent and an oxidant.
According to a preferred embodiment of the invention, the diluent is water and the oxidant is an oxygen-containing gas, such as air, and the reaction conditions include: the reaction temperature is 320-600 ℃, the reaction pressure is 0-0.4MPa, and the butene volume space velocity is 200-500 hours -1 ，H 2 The volume ratio of O/butene is 6-20, O 2 The volume ratio of the butene is 0.4-1.0.
In the invention, the pressure is gauge pressure.
The method of the invention mainly uses a large amount of water vapor introduced in the process of preparing butadiene by oxidative dehydrogenation of butene, and controls the temperature rise of the reactor by using larger specific heat of water; from the perspective of surface catalytic reaction, the presence of water vapor can promote the desorption of butadiene products, and deep oxidative dehydrogenation and polymerization are avoided to form carbon deposit, so that the selectivity and stability of the catalyst are improved; from the standpoint of byproduct butenol, alpha-hydrogen or beta-hydrogen of butene molecules activated on the surface of the catalyst can be abstracted by an alkaline center on the surface of the catalyst, and the catalyst can generate hydration reaction to generate butenol in the presence of a large amount of steam molecules in a reaction system, so that co-production of butadiene products is realized.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
271.7g of aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O), 108.1g of manganese nitrate (Mn (NO) 3 ) 2 ) 13.4g of sodium carboxymethyl cellulose is added into 800ml of deionized water, then coprecipitation is carried out by using 15wt% ammonia water at room temperature and pH value of 8.2, the slurry (solid content of 3.0 wt%) obtained by precipitation is aged for 3 hours at 20 ℃, and after filtration, the slurry is respectively pulped and washed twice by using 800ml of deionized water, and 200ml of deionized water is pulped and dispersed into slurry (solid content of 31 wt%) for standby;
42.0g of silica sol (30%, 95 nm) was diluted with 300ml of water, and 164.3g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O) and 7.2g of ammonium molybdate ((NH) 4 ) 6 Mo 7 O 4 ·4H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture at the inlet temperature of 280 ℃ and the outlet temperature of 180 ℃ of a dryer at the rotating speed of 11000rmp/min and the air of 3.2m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 7 hours at the temperature of 630 ℃ in an air atmosphere to obtain the composite oxide catalyst A. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 2
249.1g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 131.6g of magnesium nitrate (Mg (NO) 3 ) 2 6H 2 O), 19.5g of sucrose were added to 800ml of deionized water, and coprecipitation was carried out at room temperature with pH 9.2 using 13% aqueous ammonia to obtain a slurry (solid content2.9 wt%) at 26 deg. C for 1.5h, filtering, respectively washing with 800ml deionized water twice, and pulping with 200ml deionized water to obtain slurry (solid content is 30 wt%) for use.
43.0g of silica sol (25%, 110 nm) was diluted with 300ml of water, and 168.0g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O) and 13.6g of zirconium nitrate (Zr (NO) 3 ) 4 .5H 2 O) and the 200ml of slurry are evenly mixed, and then the mixture is dried at the inlet temperature of 260 ℃ and the outlet temperature of 180 ℃ and the rotating speed of 10000r/min and the air of 3.2m 3 And (3) spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 7 hours at 660 ℃ in an air atmosphere to obtain the composite oxide catalyst B. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 3
255.6g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 135.0g of cobalt nitrite (Co (NO) 3 ) 2 6H 2 O), 121.9g of starch slurry (21.9 g of starch and 100ml of deionized water are boiled) are added into 800ml of deionized water, then coprecipitation is carried out at room temperature and pH value of 9.6 by using 17% ammonia water, the slurry (solid content of 3.6% by weight) obtained by precipitation is aged for 2 hours at 32 ℃, and after filtration, the slurry is respectively pulped and washed twice by 800ml of deionized water, and 200ml of deionized water is pulped and dispersed into slurry (solid content of 32% by weight) for later use.
42.0g of silica sol (30%, 140 nm) was diluted with 300ml of water, and 164.3g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O) and 5.0g of ammonium molybdate ((NH) 4 ) 6 Mo 7 O 4 ·4H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture in a dryer at an inlet temperature of 260 ℃ and an outlet temperature of 190 ℃ at a rotating speed of 10000r/min and air of 3.5m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 6 hours at 660 ℃ in air atmosphere to obtain the composite oxide catalyst C. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 4
303.9g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 160.5g of zinc nitrate (Zn (NO 3) 2.6H2O) and 20.2g of polyethylene glycol (mass average molecular weight 120000) are added into 800ml of deionized water, then coprecipitation is carried out at room temperature and pH value of 9.5 by using 20% ammonia water, the slurry (solid content of 5.1 weight percent) obtained by precipitation is aged for 2 hours at 30 ℃, and after filtration, the slurry is respectively pulped and washed twice by 800ml of deionized water, and 200ml of deionized water is pulped and dispersed into slurry (solid content of 33 weight percent) for later use.
35g of silica sol (33%, 128 nm) was diluted with 300ml of water and 82.9g of barium nitrate (Ba (NO) 3 ) 2 ) And 3.0g of ammonium molybdate ((NH) 4 ) 6 Mo 7 O 4 ·4H 2 O), 8.6g zirconium nitrate (Zr (NO) 3 ) 4 .5H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture at the inlet temperature of 250 ℃ and the outlet temperature of 180 ℃ of a dryer at the rotating speed of 9000r/min and the air of 4.3m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 8 hours at 650 ℃ in an air atmosphere to obtain the composite oxide catalyst D. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 5
228.5g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 120.7g zinc nitrate (Zn (NO) 3 ) 2 ) The starch slurry (34.0 g of starch and 100ml of deionized water are boiled) is added into 800ml of deionized water, then coprecipitation is carried out at room temperature and pH value of 9.0 by using 18% ammonia water, the slurry (solid content of 2.4 weight percent) obtained by precipitation is aged for 3 hours at 32 ℃, and after filtration, the slurry is respectively pulped and washed twice by 800ml of deionized water, and 200ml of deionized water is pulped and dispersed into slurry (solid content of 23 weight percent) for later use.
44g of silica sol (38%, 63 nm) was diluted with 300ml of water, and 86.3g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), 73.5g strontium nitrate (Sr (NO) 3 ) 2 ·4H 2 O) and 12.3g of zirconium nitrate (Zr (NO) 3 ) 4 .5H 2 O), 7.0g of niobium pentachloride (NbCl) 5 ) Mixing with the 200ml slurry, stirring uniformly, heating to 260deg.C at inlet temperature of dryer, 190 deg.C at outlet temperature, rotating at 10000r/min,air 4.2m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 5 hours at 680 ℃ in an air atmosphere to obtain the composite oxide catalyst E. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 6
331.6g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 174.5g zinc nitrate (Zn (NO) 3 ) 2 ) And 22.1g of sodium methylcellulose in 800ml of deionized water, then coprecipitating with 19% ammonia water at room temperature and pH of 8.6, aging the precipitated slurry (solid content of 6.5 wt%) at 35 ℃ for 2 hours, filtering, pulping and washing twice with 800ml of deionized water respectively, pulping and dispersing with 200ml of deionized water to obtain slurry (solid content of 38 wt%) for later use.
33g of silica sol (28%, 156 nm) was diluted with 300ml of water, and 64.0g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), 80.4g of magnesium nitrate (Mg (NO) 3 ) 2 ·6H 2 O) and 16.8g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture at the inlet temperature of 280 ℃ and the outlet temperature of 180 ℃ of a dryer at the rotating speed of 11000r/min and air of 3.2m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 10 hours at 640 ℃ in an air atmosphere to obtain the composite oxide catalyst F. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 7
227.3g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 120.1g zinc nitrate (Zn (NO) 3 ) 2 ) And 10.9g of sodium methylcellulose in 800ml of deionized water, then coprecipitating with 19% ammonia water at room temperature and pH of 9.3, aging the slurry (solid content of 2.7% by weight) obtained by precipitation at 26 ℃ for 3.5h, filtering, pulping and washing twice with 800ml of deionized water respectively, pulping and dispersing with 200ml of deionized water to obtain slurry (solid content of 28% by weight) for later use.
45g of silica sol (28%, 163 nm) was diluted with 300ml of water, and 224.1g of magnesium nitrate (Mg (NO) 3 ) 2 ·6H 2 O) and 5.5g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O), 2.7g of ammonium molybdate ((NH) 4 ) 6 Mo 7 O 4 ·4H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture at the inlet temperature of 270 ℃ and the outlet temperature of 170 ℃ of a dryer at the rotating speed of 12000r/min and air of 3.8m 3 Spray drying and forming under the condition of/h, and roasting the obtained catalyst powder for 5 hours at 670 ℃ in an air atmosphere to obtain the composite oxide catalyst G. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Example 8
186.7g of ferric nitrate (Fe (NO) 3 ) 3 9H 2 O), 98.6g nickel nitrate (Ni (NO) 3 ) 2 ) And 21.8g of sodium methylcellulose in 800ml of deionized water, then coprecipitating with 16% ammonia water at room temperature and pH of 9.5, aging the precipitated slurry (solid content of 2.1 wt%) at 18 ℃ for 4 hours, filtering, pulping and washing twice with 800ml of deionized water respectively, pulping and dispersing with 200ml of deionized water to obtain slurry (solid content of 23 wt%) for later use.
51g of silica sol (39%, 127 nm) were diluted with 300ml of water and 121.2g of barium nitrate (Ba (NO) 3 ) 2 ) And 4.9g sodium tungstate (Na 2 WO 4 ·2H 2 O) and mixing with the 200ml slurry, stirring uniformly, and placing the mixture at the inlet temperature of 280 ℃ and the outlet temperature of 180 ℃ of a dryer at the rotating speed of 11000r/min and air of 3.2m 3 Spray drying and forming under the condition of/H, and roasting the obtained catalyst powder for 8 hours at 650 ℃ in an air atmosphere to obtain the composite oxide catalyst H. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Comparative example 1
A catalyst was prepared as in example 4, except that ammonium molybdate and zirconium nitrate were not added. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Comparative example 2
A catalyst was prepared as in example 4, except that no silica sol or barium nitrate was added. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
Comparative example 3
A catalyst was prepared as in example 4, except that no silica sol, barium nitrate, and ammonium molybdate and zirconium nitrate were added. The weight percentage composition of the obtained catalyst is shown in Table 1, and the physical properties of the catalyst are shown in Table 2.
TABLE 1 catalyst composition
TABLE 2 physical Properties of catalyst
The catalyst of the invention has obviously raised spinel activity compared with available catalyst.
Example 9
Catalyst A-comparative example 3 butene volume space velocity at 380 ℃,0.2MPa, 400 hours -1 ，O 2 /C 4 H 8 The performance evaluation was carried out under the conditions that the volume ratio was 0.75 and the water-olefin volume ratio was 11, and the butene dehydrogenation reaction was carried out on a continuous flow stainless steel reactor micro catalytic reaction device. The product analysis adopts an HP-6820 gas chromatograph (TCD, FID dual detector) to analyze the contents of organic matters such as olefin, diene and the like and gases such as oxygen, carbon monoxide, carbon dioxide and the like in the dehydrogenation product on line, and calculates the conversion rate, selectivity and yield of the reaction. The results are shown in Table 3.
TABLE 3 catalyst Performance
Example 11
Catalyst D (example 4), catalyst G (example 7) and comparative example 3 were evaluated under the conditions of example 9 to compare the stability of the three catalysts and the performance of the catalysts after 1000 hours is shown in Table 4.
TABLE 4 Table 4
The catalyst is used for co-producing butenol and butadiene with the total conversion rate higher than 73 percent and the total selectivity higher than 89 percent, wherein the butenol selectivity is higher than 38 percent and the butadiene selectivity is higher than 38 percent; the stability test is inactive and reduced for more than 1000 hours, the stability is good, and a better technical effect is obtained.
The technical scheme disclosed by the invention can keep higher selectivity of the butenol under the condition of higher selectivity of the butadiene, and can be used for obtaining stable butenol byproducts in industrial production of preparing butadiene by oxidative dehydrogenation of the butene.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A solid catalyst for preparing butadiene and 3-butene-1-ol from butene raw material is characterized by that said catalyst contains spinel phase and silicate crystal phase of IIA metal and metal auxiliary agent, and the metal auxiliary agent is one or several of IVB, VB, VIB and lanthanide series metal elements.
2. The catalyst according to claim 1, wherein the catalyst is used in the preparation of a catalyst for the catalytic reaction of,
the spinel phase is present in an amount of 29.0 to 59.0 wt.%, preferably 35.0 to 55.0 wt.%;
the content of group IIA metal silicate crystalline phase is 40.0-70.0 wt%, preferably 50.0-60.0 wt%;
the metal auxiliary is contained in an amount of 1.0 to 5.0wt% in terms of oxide, preferably 2.0 to 4.0wt%.
3. The catalyst according to claim 1 or 2, wherein,
the metal auxiliary agent is selected from one or more of Mo, nb, W, zr and Ce elements, preferably one or more of Nb, mo and Ce elements; and/or
The spinel phase structure satisfies the chemical formula: AB (AB) 2 O 4 Wherein A is 2+ Selected from Ca 2+ 、Mn 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2 + 、Hg 2+ And Sn (Sn) 2+ One or more of the following; b (B) 3+ Selected from Al 3+ 、Co 3+ 、Bi 3+ 、Fe 3+ 、Ti 3+ 、V 3+ And In 3+ One or more of the following; and/or
The IIA metal is selected from one or more of Be, mg, ca, sr and Ba; and/or
The pore volume of the catalyst is 0.2-6.0 ml/g, preferably 1.0-5.0 ml/g; and/or
The average pore diameter of the catalyst is 200-600 nm, preferably 300-500 nm; and/or
The specific surface area of the catalyst is 5-60 m 2 Preferably 10 to 30m 2 /g。
4. A method of synthesizing a catalyst according to any one of claims 1 to 3, comprising:
(1) Coprecipitating a solution containing inorganic salts and high molecular organics required for constituting the spinel phase with an inorganic base to form a first slurry;
(2) Aging, filtering and washing the first slurry, and dispersing the first slurry in water to form a second slurry;
(3) Mixing silica sol, a IIA metal source and a metal auxiliary agent source, and then mixing with the second slurry obtained in the step (2) to form a third slurry;
(4) Forming granular powder by a spray forming method of the third slurry obtained in the step (3);
(5) And (3) roasting the granular powder obtained in the step (4) to obtain the catalyst.
5. The synthesis method according to claim 4, wherein,
the inorganic salt required for forming the spinel phase comprises a salt containing A 2+ Inorganic salts of (C) and B-containing 3+ Inorganic salt of A) 2+ Selected from Ca 2+ 、Mn 2 + 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Hg 2+ And Sn (Sn) 2+ One or more of the following; b (B) 3+ Selected from Al 3+ 、Co 3+ 、Bi 3+ 、Fe 3+ 、Ti 3+ 、V 3+ And In 3+ One or more of the following; and/or
The polymer organic matter is at least one of polyethylene glycol, starch, sodium carboxymethyl cellulose and sucrose, and the addition amount of the polymer organic matter is 0.1-5 wt% of the total addition amount of all substances for synthesizing the catalyst, preferably 0.6-3.0 wt%; and/or
The inorganic base is selected from one or more of sodium carbonate, sodium hydroxide, urea, ammonia water, diamine and potassium hydroxide.
6. The synthesis method according to claim 4 or 5, wherein,
the most probable distribution of the particle diameter of the silica sol in the step (3) is 20-200 nm, preferably 80-160 nm; and/or
The side pressure strength of the catalyst obtained after the roasting in the step (5) is higher than 160N/cm, and the particle size is 20-160 mu m, preferably 30-120 mu m.
7. The synthesis method according to any one of claims 4 to 6, wherein,
the conditions for the coprecipitation in step (1) include: the temperature is 10-50 ℃, the pH value is 8.0-11.0, preferably 8.2-9.8, and the stirring is carried out; and/or
The aging conditions in step (2) include: the aging temperature is 10-50 ℃ and the aging time is 0.5-4 hours; and/or
The conditions of spray drying in step (3) include: the inlet temperature is 260-300 ℃, the outlet temperature is 150-200 ℃, the rotating speed is 6000-15000 r/min, and the air flow is 2.8-5.0 m 3 /h; and/or
The conditions of the calcination in step (5) include: the baking is carried out in air atmosphere at 550-750 deg.c, preferably 620-690 deg.c for 4-12 hr.
8. The synthesis method according to any one of claims 4 to 7, wherein,
the solids content of the first slurry is 1.5 to 8.0 wt.%; and/or
The solids content of the second slurry is 20-40 wt.%.
9. A process for co-producing butenol and butadiene, the process comprising: contacting butene with a catalyst comprising the catalyst of any of claims 1-3 and a diluent and an oxidant to produce butadiene and butenol.
10. The method of claim 9, wherein the diluent is water and the oxidant is an oxygen-containing gas, and the reaction conditions include: the reaction temperature is 320-600 ℃, the reaction pressure is 0-0.4MPa, and the butene volume space velocity is 200-500 hours -1 ，H 2 The volume ratio of O/butene is 6-20, O 2 The volume ratio of the butene is 0.4-1.0.
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