CN110813288A - Catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne, preparation method and application thereof - Google Patents
Catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne, preparation method and application thereof Download PDFInfo
- Publication number
- CN110813288A CN110813288A CN201911000611.5A CN201911000611A CN110813288A CN 110813288 A CN110813288 A CN 110813288A CN 201911000611 A CN201911000611 A CN 201911000611A CN 110813288 A CN110813288 A CN 110813288A
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- CN
- China
- Prior art keywords
- catalyst
- drying
- hours
- concentration
- tetraalkyne
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 201
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 67
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims description 124
- 239000007864 aqueous solution Substances 0.000 claims description 80
- 239000002131 composite material Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 229910052799 carbon Inorganic materials 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 54
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 53
- 239000002243 precursor Substances 0.000 claims description 52
- 150000003839 salts Chemical class 0.000 claims description 51
- 230000032683 aging Effects 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000002791 soaking Methods 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 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 claims description 36
- 230000008569 process Effects 0.000 claims description 33
- 238000000975 co-precipitation Methods 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 26
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 25
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 238000005336 cracking Methods 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Chemical class 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical class [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000002161 passivation Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical class [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 55
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 55
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 description 30
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 30
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000012299 nitrogen atmosphere Substances 0.000 description 28
- 238000005303 weighing Methods 0.000 description 26
- 239000012065 filter cake Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 230000009467 reduction Effects 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 description 15
- 241000219782 Sesbania Species 0.000 description 15
- 239000004480 active ingredient Substances 0.000 description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 14
- 229960002303 citric acid monohydrate Drugs 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- -1 acetylene hydrocarbon Chemical class 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing butadiene by selective hydrogenation of carbon-tetraalkyne, a preparation method and application thereof. The catalyst comprises ZrO2/CdO/Bi2O3The carrier and active component, the active component composition includes: at least one of Pd or oxide thereof, VIIB metal or oxide thereof, La or oxide thereof. The catalyst can be used in the application of recovering butadiene by selective hydrogenation of carbon-tetrayne, and mainly solves the problems of poor catalyst stability, short service life, poor alkyne selectivity and high butadiene loss in the prior art.
Description
Technical Field
The invention relates to a catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne, belonging to the technical field of petrochemical industry, in particular to a catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne contained in a material after extraction of a butadiene device, a preparation method and application thereof.
Background
The ethylene cracking gas contains a large amount of carbon tetrahydrocarbons and cracked gasoline besides diene. The cracking gas can separate out four carbon components in the separation process of the ethylene device, and then the cracking gas enters a butadiene device to carry out deep separation on the four carbon raw materials. The carbon four raw material contains isobutene, normal butane, isobutene, vinyl acetylene, butyne and other substances besides butadiene and 1-butene, the butadiene can be separated from the raw material after secondary extraction, alkyne substances in the raw material can be gradually enriched in the butadiene material, a butadiene device can generally extract the alkyne-rich material from a lower tower of a second extraction tower through a lateral line, the total content of alkyne-rich materials in the material reaches about 30 percent, and the carbon four alkyne, especially vinyl acetylene, is a very flammable and explosive substance, so the material is very dangerous, the industrial application value is very low, the quality of butadiene products is influenced, and a treatment method generally adopted in industry is to reduce the alkyne concentration of the material by mixing butane or butene and other materials in a stream, and then sending the stream to a torch for incineration treatment. Taking a set of butadiene device with 5.4 ten thousand tons/year as an example, the quantity of alkyne materials (mainly butyne and vinyl acetylene) sent to a torch system is as high as 757 tons/year, and the danger of explosion of alkyne exists while huge material waste is caused. Therefore, how to reduce the risk of alkyne and effectively utilize it is a new direction of current research. The popular research direction is to use a high-selectivity catalyst to selectively convert carbon tetraalkyne into butadiene, 1-butene and a small amount of butane, so that alkyne impurities in butene materials can be removed, waste can be changed into valuable, corresponding alkene is converted, and the economic benefit of the operation of the full-flow zero-emission improving device is further realized.
There are two main processes for hydrogenation of carbon tetraalkyne. One is a pre-hydrogenation scheme, the main process flow of which is to hydrogenate the carbon four feedstock from the ethylene plant to 1-butene and butadiene prior to two-stage extraction, and selectively hydrogenate the butynes and vinyl acetylenes therein while avoiding hydrogenation of olefins in the feedstock. The technical difficulty of the method is that the handling capacity of the catalyst is large, alkyne in the raw material must be reduced to below 20ppm, simultaneously olefin loss cannot exceed 1%, vinyl acetylene and butadiene in the raw material belong to conjugated diene, the chemical stability is poor, and if the selectivity of the catalyst is poor, butadiene and vinyl acetylene are very easy to hydrogenate simultaneously, so unnecessary loss is caused, and therefore the used catalyst must have stability and high selectivity simultaneously.
The other technology is a post-hydrogenation scheme, namely, after the C-C raw material is subjected to secondary extraction, the alkyne-rich butadiene raw material which is extracted from the side line of the second extraction lower tower is hydrogenated. After the alkyne is hydrogenated into olefin, the olefin is sent back to an extraction tower for feeding, and the hydrogenation process is completed. The process has the greatest advantages of reducing the treatment capacity of the hydrogenation catalyst and avoiding economic loss caused by excessive hydrogenation of butadiene due to change of working conditions. However, 20-30% of alkyne is enriched in the butadiene material extracted from the side line, so if the operation is careless, the explosion risk is very high. Meanwhile, the materials are all active alkyne, alkene and alkane substances, and a small amount of water, acetonitrile, dimers and heavy components are mixed in the materials, so that the selectivity requirement on the catalyst is high, the poisoning resistance requirement on the catalyst is strict, and the application of the catalyst in the industry is limited, so that the research on the catalyst in the industry is relatively less at present.
The current academic application of selective hydrogenation catalysts for acetylene hydrocarbon or olefin hydrocarbon is the palladium catalyst and non-noble metal catalyst. As is well known, the performance research of palladium catalysts on selective hydrogenation of diene is very common, and the academic research in recent years finds that the palladium catalysts can obtain better selectivity on alkyne in butadiene materials through proper modification, and can be completely suitable for industrial application of selective hydrogenation of alkyne; as for non-noble metal catalysts, one type is a copper-based catalyst, and the catalyst has good selectivity on carbon four-alkyne, but the alkene and alkyne in the raw materials are easy to generate polymerization reaction due to high reaction temperature required in the catalytic process, so that the active site of the catalyst is blocked, and the service life of the Cu-based catalyst is shortened. The other kind of non-noble metal catalyst is Ni catalyst with low cost and poor alkyne selectivity, and is only suitable for use as assistant to regulate and control the performance of catalyst. In comparison, the Pd-based catalyst has mild operating conditions and better selective activity for alkyne, and on this basis, the Pd-based catalyst can be modified by adding an additive to improve the selectivity and anti-poisoning performance thereof, and is most suitable as an alkyne hydrogenation catalyst.
Based on the above facts, there is a widely recognized need in the academia to modify Pd-based catalysts to improve the overall catalytic performance of Pd-based catalysts as alkyne hydrogenation catalysts. The modification method is mainly characterized in that a modification auxiliary agent is introduced, the activity of Pd is passivated, and the type and structure of a carrier are improved, so that the interaction of Pd and alkyne is improved, and the selective activity of the Pd on a target product butadiene is improved. CN108927173A reports a catalyst for selective hydrogenation of alkyne, which regulates the acidity of a catalyst carrier by introducing Mg, Li and Ag auxiliaries into a Pd catalyst taking alumina as the carrier, thereby improving the activity and stability of the catalyst. CN102249838A indicates that the selectivity of Pd is related to the exposed active sites on the carrier, and it uses ionizing radiation and adds free radical cleaning agent to control the crystal face state of Pd sites during the preparation of the catalyst, so as to achieve the purpose of increasing its selectivity to alkyne, and its selectivity to alkyne can reach 74.11% at most, but this invention does not give a detailed description of its lifetime. CN108863699A is prepared by adding Li and Ni auxiliary agents in the preparation process of an alumina carrier and adding Mo, K and other auxiliary agents in the process of Pd co-impregnationThe palladium-molybdenum catalyst with the crystal form and the nickel-containing alumina carrier obtains better selective activity, but the selected hydrogenation raw material is simpler, and the anti-poisoning performance of the catalyst under the condition of heavy component/acetonitrile is not considered. CN108863696A on the basis of the catalyst, the auxiliary agent K is replaced by Ag, and the reaction temperature is 25-100 ℃, the pressure is 0.6-2.5 MPa, and the liquid hourly space velocity is 15-25 h-1Under the working condition, the alkyne removal rate can reach 99.97%, but the butadiene is greatly lost, and the butadiene is removed from 10.01% to 0.0094% of the raw material. The catalyst disclosed in CN102886262A uses Ni-Cu bimetallic active elements, wherein the Ni content is 10-20%, the Cu content is 3-10%, and the rest is an alumina carrier. The selectivity of the catalyst to EA (butyne) and VA (vinyl acetylene) can reach 90 percent and 84.1 percent, but the catalyst also has great loss to butadiene, and the butadiene of the catalyst is reduced by 67.5 percent in the whole reaction process. At present, the research on the modifying assistants Ag and Cu is very extensive, for example, as described in patents US4547600, US6717022, CN1090997 and the like, the loss of Pd can be effectively inhibited, the service life of the catalyst is prolonged, but the addition of Ag also reduces the catalytic activity and the processing capacity of the catalyst on raw materials; the copper additive needs higher reaction temperature, so that coking in raw materials is serious, and the stability of the catalyst is reduced. In addition, in the prior art, an impregnation method is generally used for loading active components and auxiliaries, but the active components are distributed unevenly due to the fact that the surface and internal pore channels of the carrier are complex and the impregnation process is improper, and if the added auxiliaries are excessive, the pore channels can be blocked, particularly, the elements in IB families and IVA families, such as Ag, Cu, Si, Sn and the like are added, and the content of the elements is far higher than that of the main active components, so that the catalytic activity is not obviously improved. In addition, experimental research also finds that most of the modification aids in the prior art have strong inhibition effect on the activity of the catalyst, especially elements such as Cu, Ag and Ni, and the addition of the elements can have large inhibition effect on the activity of the catalyst or can be unfavorable for the selectivity of the catalyst, so that the unit consumption of the catalyst is increased.
In summary, the butadiene selective hydrogenation catalysts developed at present still have many technical problems, and the industrial implementation schemes are few. The carrier is mainly alumina, and the modification auxiliary agent is selected from various types and usage, but the reaction activity and stability of Pd can be effectively improved, and particularly, the catalyst with better effect on the hydrogenation selectivity of carbon four is still less. Therefore, the catalyst with high activity, high selectivity and good stability for preparing butadiene by selective hydrogenation of the C-tetraalkyne is found, and the catalyst has extremely important significance for the application of separating and purifying the four extracted C components and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne aiming at the problems of low hydrogenation selectivity of carbon tetraalkyne, large consumption of diolefin and low catalytic activity of the existing catalyst on the carbon tetraalkyne in a butene raw material and a preparation method thereof.
The second technical problem to be solved by the invention is to provide an application method of the catalyst, and particularly, under the condition of the catalyst, tail gas obtained from a lateral line after secondary extraction of a butadiene device in an ethylene cracking process is used as a raw material, and carbon tetraalkyne in the tail gas is converted into butadiene through selective hydrogenation. The catalyst has strong coking resistance, can still keep high hydrogenation activity particularly in raw materials containing dimers and heavy components, and can reduce the loss of dialkene caused by deep hydrogenation.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne, which comprises ZrO2/CdO/Bi2O3The following contents of the composite carrier and the active component are based on the total mass of the catalyst, and ZrO is2/CdO/Bi2O3The content of the composite carrier is 86.5-92.3%, and the content of the active component is 7.7-13.5%;
the active component comprises the following components:
pd or its oxide, the content is 0.05-0.8%, preferably 0.2-0.5% calculated by Pd element;
VIIB metal or at least one of oxides thereof, in terms of metal elements, in an amount of 0.2 to 6.0%, preferably 2.0 to 5.0%;
la or an oxide thereof in an amount of 0.1 to 4.0%, preferably 0.5 to 2.0% in terms of oxide form.
Catalyst of the invention, the ZrO2/CdO/Bi2O3Composite support, ZrO2(zirconia) as a main carrier component, CdO (cadmium oxide) and Bi2O3(bismuth oxide) as a support modifier. Based on the total mass of the catalyst, the content of CdO is 1-10%, preferably 1.0-4.0%; bi2O3The content of (B) is 0.1 to 5.0%, preferably 1.0 to 2.0%.
Preferably, the ZrO2/CdO/Bi2O3The composite carrier has a total pore volume of 0.3-0.9 mL/g and a specific surface area of 90-180 m3/g。
The catalyst of the present invention, said VIIB metal or oxide thereof, is preferably Re (rhenium) or an oxide thereof.
The invention also provides a preparation method of the catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne, which comprises the steps of ZrO2/CdO/Bi2O3Preparing a composite carrier and loading an active component.
In the production method of the present invention, the ZrO2/CdO/Bi2O3The composite carrier is prepared by the following method: firstly, preparing a carrier precursor by using a coprecipitation method, then adding a pore-forming agent, an adhesive and water to perform isostatic pressing molding, and aging, drying and roasting to obtain the catalyst.
Further, the above-mentioned ZrO2/CdO/Bi2O3Preparing a composite carrier, wherein a carrier precursor is prepared by the coprecipitation method, and the preferable method comprises the following steps: and uniformly mixing soluble salts of zirconium, cadmium and bismuth with water, then coprecipitating with ammonia water, keeping the pH value of a reaction system at 3-6 (preferably 4-5) for reaction until the raw materials are exhausted, taking precipitates after the reaction is finished, washing with water, and drying (the drying environment is at 60-80 ℃) to obtain the carrier precursor.
In the coprecipitation method, the soluble salts of zirconium, cadmium and bismuth are one or more of nitrate, acetate and the like; the soluble salt of zirconium is preferably zirconium nitrate, the concentration is preferably 3.0-4.0 mol/L, the soluble salt of cadmium is preferably cadmium acetate, the concentration is preferably 0.04-0.30 mol/L, the soluble salt of bismuth is preferably bismuth nitrate, and the concentration is preferably 0.02-0.25 mol/L.
The concentration of ammonia water used for coprecipitation is 1.0-4.5 moL/L, preferably 2.0-4.0 moL/L. And (3) preferably dropwise adding soluble salt water solution of zirconium, cadmium and bismuth and ammonia water in the precipitation reaction process, and controlling the dropwise adding speed through the pH value of a reaction system to keep the pH value at 3-6.
Preferably, after the drying is completed, the carrier precursor is crushed into particles with the particle size range of 80-120 meshes, and preferably 100-120 meshes.
Further, the above-mentioned ZrO2/CdO/Bi2O3Preparing a composite carrier, wherein the drying process needs temperature programming and drying, and the preferable scheme is as follows: heating to 50-80 ℃ at a heating rate of 1-3 ℃/min (preferably 1 ℃/min), and drying for 10-24 h; and then heating to 80-120 ℃ at a heating rate of 1-3 ℃/min (preferably 1 ℃/min), and drying for 6-10 h. It should be noted that direct drying (e.g. 120 ℃, 12h) may cause collapse of the pore structure of the zirconia carrier due to the surface tension effect of water, so that the specific surface area is small, and therefore, the drying process of the carrier according to the present embodiment needs to be performed at 50-80 ℃ for a long time to increase the specific surface area.
Further, the above-mentioned ZrO2/CdO/Bi2O3Preparing a composite carrier, and roasting, wherein the preferable scheme is as follows: after drying, raising the temperature to 800-1200 ℃ at a heating rate of 5 ℃/min, and roasting for 4-8 h.
ZrO of the above2/CdO/Bi2O3In the preparation method of the composite carrier, the adhesive is not particularly limited, and includes but is not limited to sesbania powder and/or polyvinyl alcohol; the pore former is also not particularly limited, including but not limited to citric acid.
The mass ratio of the carrier precursor to the adhesive, the pore-forming agent and the water is 1.00: 0.01-0.10: 0.10-0.40: 0.50-1.00. In more detail, the mass ratio of the carrier precursor to the adhesive, the pore-forming agent and the water can be 1.00:0.03:0.50:0.67, for example.
In the preparation method of the present invention, the active ingredient may be supported by an optional impregnation method, such as an equal-volume impregnation or an excess impregnation, but the present invention is not limited thereto, and an equal-volume impregnation method is preferred. In the active components of the catalyst, Pd is a main active component, VIIB metal and La are auxiliary agents, and according to the characteristics of different types of active components, the preferable loading scheme is as follows: firstly, ZrO is firstly2/CdO/Bi2O3VIIB metal is impregnated and loaded on the composite carrier, and Pd and La are impregnated and loaded after the treatment of drying, roasting and the like, wherein the specific loading method comprises the following steps:
1) ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier in a VIIB metal soluble salt aqueous solution for 8-10 h (preferably equal-volume soaking), then aging for 4-6 h, drying at 50-80 ℃ for 5-8 h after aging is completed, drying at 80-120 ℃ for 6-10 h, and finally roasting at 330-550 ℃ for 4-8 h to obtain a VIIB metal-loaded catalyst;
2) mixing a palladium soluble salt aqueous solution and a lanthanum soluble salt aqueous solution, adjusting the pH to 2-4 by using a nitric acid aqueous solution with the concentration of 15-25 g/L, then adding the catalyst loaded with the VIIB metal prepared in the step 1) to impregnate for 5-10 h (preferably equal-volume impregnation), and repeating the aging, drying and roasting processes in the step 1) to obtain the catalyst for preparing butadiene through selective hydrogenation of C-C alkyne.
In the step 1), the VIIB metal soluble salt is selected from soluble salts of rhenium elements, preferably ammonium perrhenate, ammonium perrhenate and the like; the concentration of the aqueous solution of the VIIB metal soluble salt is 0.04-2.20 mol/L, preferably 0.75-1.50 mol/L.
In the step 2), the soluble salt of palladium is selected from palladium chloride, palladium nitrate and the like, preferably palladium nitrate; the concentration of the soluble salt water solution of palladium is 0.01-0.13 mol/L, preferably 0.05-0.10 mol/L.
The soluble salt of lanthanum is selected from lanthanum nitrate and lanthanum acetate, preferably lanthanum nitrate; the concentration of the lanthanum soluble salt aqueous solution is 0.20-8.00 mol/L, preferably 0.70-4.00 mol/L.
The mass ratio of the soluble salt water solution of palladium to the soluble salt water solution of lanthanum is 0.7-7.0: 1, preferably 2.0 to 4.0: 1.
in the step 1) and 2), the impregnation is carried out, wherein the mass ratio of the carrier to the impregnation liquid is 1: 1-3, preferably 1: 1-1.5, and most preferably 1: 1.3.
Preferably, in the preparation method of the present invention, the catalyst for preparing butadiene by selective hydrogenation of carbon-tetrayne obtained in step 2) further comprises a passivation treatment process. The catalyst of the present invention, which needs to be passivated for storage, is generally passivated by the following methods in the embodiments of the present invention: firstly, nitrogen (the volume content of hydrogen is 1-5%) containing a certain proportion of hydrogen is used for reducing the hydrogen, and the specific working conditions of the reduction process are as follows: the temperature is 200-500 ℃, the time is 4-8 h, and the gas hourly space velocity is 40-100 h-1. Then passivating for 4-8 h by using nitrogen (the volume content of oxygen is 5-10%) containing a certain proportion of oxygen, wherein the passivating temperature is 10-90 ℃, and the gas hourly space velocity is 70-160h-1And the reduction and passivation processes both comprise a temperature programming step.
Before the catalyst is put into use, some active elements in the catalyst are generally reduced to a metal form. The alkyne selective hydrogenation butadiene catalyst of the invention also needs to be activated before use, and one of the adopted activation methods is as follows: activating with nitrogen containing hydrogen in a certain proportion (the volume concentration of hydrogen is preferably 1-5%), wherein the activation temperature is 80-150 ℃, and the activation time is 2-5 h.
The invention also provides the application of the catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne, which is suitable for the selective hydrogenation reaction of carbon tetraalkyne in raw materials containing carbon tetraalkyne, in particular in raw materials with high content of carbon tetraalkyne, and the carbon tetraalkyne is converted into butadiene through the hydrogenation reaction.
In the application, the raw material containing the carbon tetraalkyne comprises one or more of butyne, vinyl acetylene, carbon tetraalkene and alkane; the carbotetraalkynes include butyne, vinylacetylene, and the like.
Further, the raw material containing the carbon tetraalkyne is selected from a material containing the carbon tetraalkyne, which is a byproduct of an ethylene cracking process, preferably a material extracted from a side line after secondary extraction of a butadiene device in the ethylene cracking process, wherein the content of the carbon tetraalkyne is preferably 20-40% in terms of mass percentage, and the rest components are mainly C4 alkene and C4 alkane, such as butane, propadiene, butadiene, isobutene, 1-butene, 2-butene and the like, and in addition, the raw material also contains a small amount of impurity water, acetonitrile and the like.
The catalyst is suitable for single-stage bed, double-stage bed or other types of isothermal fixed bed reactors.
Further, the hydrogenation reaction is carried out under the conditions of: the temperature is 20-60 ℃, the inlet temperature of the reactor is 35-50 ℃, and the preferred temperature is 40-45 ℃; the liquid hourly space velocity is 7-20 h-1Preferably 9h-1(ii) a The reaction pressure is 0.5-2.5 MPa (G), preferably 1.1MPa (G); the hydrogen/alkyne molar ratio is 1 to 4, preferably 1.6 to 2.5, and most preferably 1.8 to 2.0.
After the hydrogenation reaction is finished, the removal rate of carbon tetraalkyne in the system can reach more than 90 wt%, the selectivity to butadiene can reach more than 56 wt%, the content of carbon tetraalkyne after the reaction can be reduced to less than 2 wt%, and the total consumption rate of olefin is not higher than 0.4 wt%, so that the aim of basically not consuming mono/diolefin is achieved, and the hydrogenation catalyst has high application value.
The invention relates to a catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne, which adopts ZrO2/CdO/Bi2O3Composite support, ZrO2As main component of carrier, CdO and Bi2O3Is a carrier modifier. Main component ZrO of carrier2The carrier has acid-base dual active centers, can well play a synergistic effect with loaded active component elements through reasonable regulation and control, and increases the uniform dispersion effect of the active elements on the surface of the carrier. With ZrO in the support2And the catalyst can effectively dissociate and adsorb hydrogen to generate ZrOH and ZrH, so that the chemical adsorption and utilization of the catalyst on the hydrogen are further improved, and the hydrogenation reaction efficiency is improved. In addition, CdO and Bi are introduced into the carrier2O3As a carrier modifier, some kinds of cadmium soluble salts (such as cadmium acetate) are easy to form spinel oxides under the high-temperature roasting, a coated composite cadmium oxide carrier with a remarkable limited domain structure can be constructed, and the carrier not only can promote the main active element Pd to be in the high-temperature roasting stateThe dispersion on the surface of the catalyst can also effectively inhibit ZrO2Reduction of specific surface area and abrasion during the reaction due to high-temperature calcination and during long-term reaction. And the assistant Bi2O3The addition of the catalyst not only has the functions of controlling the removal of the butylene α -H and inhibiting the excessive hydrogenation of the butadiene, but also can effectively adjust the acidity and alkalinity of the catalyst so as to inhibit ZrO2The activity of the acid center of the catalyst can prevent olefin and alkyne from polymerizing at the surface acid center to generate green oil, colloid and the like to block the pore channel of the catalyst, and influence the activity, stability and service life of the catalyst.
In the active component loaded by the catalyst, Pd is a main active component, and VIIB element and La are promoters.
Because the main active component Pd is easy to generate a complex with the raw material under the long-term reaction state, the complex is lost in the catalytic process, and the VIIB element (such as Re) of the cocatalyst component is introduced, so that the electronic action between the Pd and the carrier is changed, the interaction between the Pd and the carrier is enhanced, the loss of the Pd element is reduced, and the stability and the service life of the catalyst are further improved. In addition, because Pd has strong hydrogenation catalytic activity and poor selectivity for hydrogenation of carbon tetraalkyne, and is very easy to catalyze olefin to deeply hydrogenate to generate alkane and consume butadiene, the catalyst provided by the invention forms an alloy similar to a solid solution type by adding the catalyst promoter component La and Pd, La can preferentially occupy the side, edge or step position on the Pd crystal phase, and modifies the defect position on the active site of the Pd which is easy to generate side reaction, so that the lattice structure of Pd or an oxide thereof is effectively improved, the poisoning resistance of the catalyst on a dimer and a heavy component can be improved, the catalytic activity of the catalyst on the reaction of producing alkane by hydrogenation of monoolefin, the deep hydrogenation capability of Pd on monoolefin is inhibited, and the hydrogenation selectivity of carbon tetraalkyne is improved.
The technical scheme of the invention has the beneficial effects that: the catalyst of the invention can effectively improve the selectivity of hydrogenation of carbon tetraalkyne to butadiene, and the conversion rate of the carbon tetraalkyne reaches more than 90%, and can also effectively reduce the loss of olefin and improve the anti-poisoning performance of the catalyst on components. Even under the condition of improving the flux of raw materials, the loss of Pd element in the catalyst can be reduced, and good catalytic activity and hydrogenation selectivity to carbon tetraalkyne can be maintained for a long time. In addition, the catalyst has strong coking resistance and good long-period running stability, and 500h online evaluation results show that the selectivity and activity of the catalyst are basically unchanged, the online running is stable, and the operation requirement of recovering butadiene by selective hydrogenation of carbon tetraalkyne in tail gas of an alkyne distillation tower unit of a butadiene device can be met.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
The feed used in the following examples was taken from the side of the lower column of the carbon four-unit two-stage extraction column of the ethylene cracking process (S & W process flow) and the composition is detailed in table 1.
TABLE 1
Composition of raw materials | In specific wt/%) |
Water (W) | 1.20 |
1-butene | 0.04 |
2-butene | 15.40 |
1, 3-butadiene | 15.02 |
1, 2-butadiene | 0.14 |
Butyne | 4.16 |
Vinyl acetylene | 26.72 |
1-pentene | 4.16 |
N-butane | 22.93 |
Acetonitrile | 4.62 |
Heavy fraction | 5.30 |
For the catalyst for preparing butadiene by selective hydrogenation of carbon-tetraalkyne, the performance of the catalyst is evaluated by acetylene hydrocarbon removal rate and butadiene selectivity after hydrogenation reaction.
Wherein, the content of the residual alkyne is directly tested by using an Agilent 7890B gas chromatography, and the test method adopts the composition determination SH-T1141092 analysis of industrial cracking carbon four.
Butadiene selectivity was calculated using the following formula:
note: in the following examples, all chemical reagents used were analytical reagents unless otherwise specified; all references to gas concentrations are molar.
Example 1
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate are respectively weighed and added into 200mL of deionized water to be uniformly dissolved, and the preparation concentrations are respectively 3.66mol/L of zirconium nitrate, 0.10mol/L of cadmium acetate and 0.04mol/L of bismuth nitrate. The method comprises the steps of coprecipitating zirconium nitrate, cadmium acetate, bismuth nitrate and ammonia water (1.5mol/L) to prepare a carrier precursor, dropwise adding a metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 5.0 in the coprecipitation process, reacting until the raw materials are used up, filtering precipitates after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing to be 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 100 ℃ at the heating rate of 2 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 5 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
Subjecting the above-mentioned ZrO to heat treatment2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (the concentration is 0.04mol/L) for 10 hours in the same volume, aging for 6 hours at normal temperature, drying for 6 hours at 60 ℃, drying for 7 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining the Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in the same volume, aging for 6h at normal temperature, drying for 6h at 60 ℃, drying for 7 h at 90 ℃, and roasting for 4h at 330 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The single-stage fixed bed reactor is operated, and the prepared catalyst for preparing the 1-butene by the selective hydrogenation of the butadiene is filled in the reactor. Activation is carried out before feeding: reducing for 4 hours by using nitrogen with 3 percent of hydrogen volume fraction, wherein the reduction temperature is 140 ℃, and the hydrogen space-time rate is 90 hours-1. After the reduction is complete, the feed is operated in a continuous manner.
The prepared catalyst for preparing butadiene by selective hydrogenation of the carbon-four alkyne is used for a raw material containing the carbon-four alkyne, and the carbon-four alkyne is converted into butadiene through a hydrogenation reaction. The operating conditions are as follows: single-stage fixed bed isothermal reactor, liquid hourly space velocity of 9h-1The reaction inlet temperature is 40 ℃, the reaction pressure is 1.1MPa (G), and the molar ratio of hydrogen to butadiene is 1.8; the specific evaluation results are shown in Table 3.
Example 2
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate are respectively weighed and added into 200mL of deionized water to be uniformly dissolved, and the preparation concentrations are respectively 3.79mol/L of zirconium nitrate, 0.04mol/L of cadmium acetate and 0.03mol/L of bismuth nitrate. And (2) coprecipitating zirconium nitrate, cadmium acetate, bismuth nitrate and ammonia water (2.0mol/L) to prepare a carrier precursor, dropwise adding a metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 6.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering precipitates after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 50 ℃ at the rate of 2 ℃/min, and drying for 10 hours; then the temperature is raised to 110 ℃ at the heating rate of 1 ℃/min, and the drying is carried out for 10 hours. After the drying is finished, the temperature is raised to 1200 ℃ in a muffle furnace at the temperature rise rate of 5 ℃/min, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (0.91mol/L) for 9 hours in the same volume, aging for 4 hours at normal temperature, drying for 8 hours at 50 ℃, drying for 8 hours at 80 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.13mol/L and lanthanum nitrate hexahydrate concentration of 3.85mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, soaking the catalyst loaded with Re in an isovolumetric manner for 10h, aging at normal temperature for 4h, drying at 50 ℃ for 8h, drying at 80 ℃ for 8h, and roasting at 550 ℃ for 8h to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Example 3
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of the zirconium nitrate, the cadmium acetate and the bismuth nitrate with the concentration of 3.63mol/L, the concentration of 0.17mol/L and the concentration of 0.04mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 3.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing the filter cake with deionized water to be neutral, drying at 60-80 ℃, and crushing to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 80 ℃ at the rate of 3 ℃/min, and drying for 24 hours; then the temperature is raised to 100 ℃ at the heating rate of 3 ℃/min, and the drying is carried out for 6 hours. After the drying is finished, the temperature is raised to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min, and the ZrO is roasted for 7 hours to obtain the ZrO2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.27mol/L) for 8 hours in the same volume, aging for 5 hours at normal temperature, drying for 6 hours at 80 ℃, drying for 9 hours at 120 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.05mol/L and lanthanum nitrate hexahydrate concentration of 0.23mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in equal volume, aging for 5h at normal temperature, drying for 6h at 80 ℃, drying for 9h at 120 ℃, and roasting for 7 h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
Prepared by the above stepsThe catalyst for preparing butadiene by selective hydrogenation of carbon tetraalkyne is reduced for 4 hours in nitrogen atmosphere with the volume concentration of hydrogen being 3 percent, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Example 4
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.79mol/L, 0.05mol/L and 0.03mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 4.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 50 ℃ at the rate of 2 ℃/min, and drying for 15 hours; then the temperature is raised to 120 ℃ at the heating rate of 3 ℃/min, and the drying is carried out for 8 hours. After the drying is finished, the temperature is raised to 1000 ℃ in a muffle furnace at the heating rate of 5 ℃/min, and the ZrO is roasted for 6 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (0.75mol/L) for 9 hours in the same volume, after the soaking is finished,aging at normal temperature for 4 hours, drying at 70 ℃ for 7 hours, drying at 100 ℃ for 7 hours, and roasting at 400 ℃ for 4 hours to obtain a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.10mol/L and lanthanum nitrate hexahydrate concentration of 4.08mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in the same volume, aging for 4h at normal temperature, drying for 7 h at 70 ℃, drying for 7 h at 100 ℃, and roasting for 5h at 450 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Example 5
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.25mol/L, cadmium acetate with the concentration of 0.28mol/L and bismuth nitrate with the concentration of 0.21mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 5.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (with the mass concentration of 5 percent), adding 130mL of water,after extrusion forming, aging for 6 hours at normal temperature, then placing the mixture in an oven, raising the temperature to 70 ℃ at the heating rate of 3 ℃/min, and drying for 20 hours; then the temperature is raised to 80 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 7 hours. After the drying is finished, the temperature is raised to 880 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.83mol/L) for 10 hours in the same volume, aging for 5 hours at normal temperature, drying for 5 hours at 80 ℃, drying for 10 hours at 110 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.02mol/L and lanthanum nitrate hexahydrate concentration of 7.71mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in the same volume, aging for 5h at normal temperature, drying for 5h at 80 ℃, drying for 10h at 110 ℃, and roasting for 6h at 500 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Example 6
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.51mol/L, cadmium acetate with the concentration of 0.11mol/L and bismuth nitrate with the concentration of 0.03mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 4.5 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 70 ℃ at the rate of 1 ℃/min, and drying for 16 hours; then the temperature is raised to 90 ℃ at the heating rate of 2 ℃/min, and the drying is carried out for 10 hours. After the drying is finished, the temperature is raised to 1100 ℃ in a muffle furnace at the heating rate of 5 ℃/min, and the ZrO is roasted for 8 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (2.20mol/L) for 8 hours in the same volume, aging for 6 hours at normal temperature, drying for 8 hours at 60 ℃, drying for 6 hours at 105 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.01mol/L and lanthanum nitrate hexahydrate concentration of 7.93mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in equal volume, aging for 6h at normal temperature, drying for 8h at 60 ℃, drying for 6h at 105 ℃, and roasting for 5h at 350 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 1
1. Catalyst preparation
1)ZrO2Preparation of/CdO composite carrier
Respectively weighing zirconium nitrate pentahydrate and cadmium acetate dihydrate, adding the zirconium nitrate pentahydrate and the cadmium acetate dihydrate into 200mL of deionized water, uniformly dissolving, preparing carrier precursors with the concentrations of 3.36mol/L and 0.48mol/L respectively, coprecipitating zirconium nitrate, cadmium acetate, bismuth nitrate and ammonia water (5.0mol/L), dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 7.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering precipitates after the reaction is finished, washing filter cakes to be neutral by using the deionized water, drying at 60-80 ℃, and crushing to 100 meshes to obtain the carrier precursors.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2a/CdO composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2Soaking the/CdO composite carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in equal volume, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after soaking is completed to obtain a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h with equal volume, aging for 6h at normal temperature, drying for 10h at 60 ℃, drying for 6h at 90 ℃, and roasting for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 2
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.76mol/L, cadmium acetate with the concentration of 0.10mol/L and bismuth nitrate with the concentration of 0.04mol/L, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 3.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (with the mass concentration of 5%), adding 130mL of water, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in the same volume, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing an aqueous solution of lanthanum nitrate hexahydrate with the concentration of 3.63mol/L, adjusting the pH to 2-4 by using a nitric acid aqueous solution with the concentration of 20g/L, adding a Re-loaded catalyst to perform isovolumetric impregnation for 10 hours, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ to obtain the C-C alkyne selective hydrogenation butadiene catalyst.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 3
1. Catalyst preparation
1)ZrO2/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate and bismuth nitrate pentahydrate, adding 200mL of deionized water, dissolving uniformly, preparing zirconium nitrate, cadmium acetate, bismuth nitrate and ammonia water (7.0mol/L) with the concentration of 3.76mol/L and 0.04mol/L respectively, coprecipitating to prepare a carrier precursor, dropwise adding a metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 3.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering precipitates after the reaction is finished, washing filter cakes to be neutral by using the deionized water, drying at 60-80 ℃, and crushing to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extrudingAfter the pressure forming, aging for 6 hours at normal temperature, then placing the mixture in an oven, raising the temperature to 60 ℃ at the heating rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in the same volume, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h with equal volume, aging for 6h at normal temperature, drying for 10h at 60 ℃, drying for 6h at 90 ℃, and roasting for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 4
1. Catalyst preparation
1)ZrO2Preparation of the support
Weighing zirconium nitrate pentahydrate, adding 200mL of deionized water, dissolving uniformly, preparing a carrier precursor with the concentration of 3.83mol/L zirconium nitrate, coprecipitating with ammonia water (7.0mol/L) to prepare the carrier precursor, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 3.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using the deionized water, drying at 60-80 ℃, and crushing to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2And (3) a carrier.
2) Active ingredient loading
ZrO 2 is mixed with2Soaking a carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in the same volume, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after finishing soaking to obtain a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h with equal volume, aging for 6h at normal temperature, drying for 10h at 60 ℃, drying for 6h at 90 ℃, and roasting for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 5
1. Catalyst preparation
1)Al2O3/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, uniformly dissolving, preparing carrier precursors with the concentration of 0.10mol/L of cadmium acetate and 0.04mol/L of bismuth nitrate, co-precipitating zirconium nitrate, cadmium acetate, bismuth nitrate and ammonia water (7.0mol/L), dropwise adding a metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 3.0 in the co-precipitation process, reacting until the raw materials are exhausted, filtering precipitates after the reaction is finished, washing filter cakes to be neutral by using the deionized water, drying at 60-80 ℃, and crushing into 100 meshes to obtain the carrier precursors.
Weighing 70.00g of gamma-alumina, pseudo-boehmite with the mass equivalent to 20.00g of alumina, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (with the mass concentration of 5 percent), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After drying, raising the temperature to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and roasting for 4 hours to obtain Al2O3/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
Mixing Al2O3/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in the same volume, aging for 6 hours at normal temperature, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ after the soaking is finished, thus obtaining a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h with equal volume, aging for 6h at normal temperature, drying for 10h at 60 ℃, drying for 6h at 90 ℃, and roasting for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The carbon tetraalkyne prepared in the previous stepThe catalyst for preparing butadiene by hydrocarbon selective hydrogenation is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 6
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.66mol/L, cadmium acetate with the concentration of 0.10mol/L and bismuth nitrate with the concentration of 0.04mol/L, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 7.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and ammonium perrhenate aqueous solution (1.37mol/L) for 8 hours in equal volume, and then, soaking at normal temperatureAging for 6 hours, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ to obtain a Re-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and cerous nitrate hexahydrate concentration of 4.44mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding catalyst loaded with Re, soaking for 10h in equal volume, aging for 6h at normal temperature, drying for 10h at 60 ℃, drying for 6h at 90 ℃, and roasting for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 7
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.66mol/L, cadmium acetate with the concentration of 0.10mol/L and bismuth nitrate with the concentration of 0.04mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 6.0 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, and extrudingAfter molding, aging for 6 hours at normal temperature, then placing the molded product in an oven, raising the temperature to 60 ℃ at the heating rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier and manganese nitrate (1.37mol/L) for 8 hours in equal volume, aging for 6 hours at normal temperature after soaking, drying for 10 hours at 60 ℃, drying for 6 hours at 90 ℃, and roasting for 4 hours at 400 ℃ to obtain a Mn-loaded catalyst;
preparing aqueous solution with palladium nitrate dihydrate concentration of 0.06mol/L and lanthanum nitrate hexahydrate concentration of 3.63mol/L, then adjusting pH to 2-4 with nitric acid aqueous solution with concentration of 20g/L, adding Mn-loaded catalyst for isovolumetric impregnation for 10h, aging at normal temperature for 6h, drying at 60 ℃ for 10h, drying at 90 ℃ for 6h, and roasting at 400 ℃ for 4h to obtain the catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
Comparative example 8
1. Catalyst preparation
1)ZrO2/CdO/Bi2O3Preparation of composite Carrier
Respectively weighing zirconium nitrate pentahydrate, cadmium acetate dihydrate and bismuth nitrate pentahydrate, adding the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate into 200mL of deionized water, dissolving the zirconium nitrate pentahydrate, the cadmium acetate dihydrate and the bismuth nitrate pentahydrate uniformly, preparing the carrier precursor by coprecipitation of zirconium nitrate, cadmium acetate and bismuth nitrate with the concentration of 3.66mol/L, cadmium acetate with the concentration of 0.10mol/L and bismuth nitrate with the concentration of 0.04mol/L respectively, dropwise adding the metal salt aqueous solution and the ammonia water, keeping the pH value of the solution at about 6.2 in the coprecipitation process, reacting until the raw materials are exhausted, filtering the precipitate after the reaction is finished, washing a filter cake to be neutral by using deionized water, drying at 60-80 ℃, and crushing the filter cake to 100 meshes to obtain the carrier precursor.
Weighing 240g of carrier precursor, 6.00g of sesbania powder and 50.00g of citric acid monohydrate, mixing, adding 18.00g of polyvinyl alcohol aqueous solution (mass concentration is 5%), adding 130mL of water, extruding and forming, aging at normal temperature for 6 hours, then placing in an oven, raising the temperature to 60 ℃ at the rate of 1 ℃/min, and drying for 18 hours; then the temperature is raised to 90 ℃ at the heating rate of 1 ℃/min, and the mixture is dried for 9 hours. After the drying is finished, the temperature is raised to 980 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and the ZrO is roasted for 4 hours to obtain the final product2/CdO/Bi2O3And (3) a composite carrier.
2) Active ingredient loading
Preparing an aqueous solution of palladium nitrate dihydrate with the concentration of 0.06mol/L and silver nitrate with the concentration of 10mol/L, adjusting the pH to 2-4 by using an aqueous solution of nitric acid with the concentration of 20g/L, and adding ZrO2/CdO/Bi2O3The composite carrier is soaked for 10h in the same volume, aged for 6h at normal temperature, dried for 10h at 60 ℃, dried for 6h at 90 ℃ and roasted for 4h at 400 ℃ to obtain the catalyst for preparing butadiene by selective hydrogenation of C-C alkyne.
The catalyst for preparing butadiene by selectively hydrogenating the carbon tetraalkyne prepared in the previous step is reduced for 4 hours in a nitrogen atmosphere with the volume concentration of 3 percent of hydrogen, the reduction temperature is 400 ℃, and the gas hourly space velocity is 60 hours-1Then passivating for 5 hours in a nitrogen atmosphere with the volume concentration of oxygen of 7 percent, wherein the passivating temperature is 50 ℃, and the gas hourly space velocity is 80h-1And taking out for later use. The detailed composition is shown in Table 2.
2. Catalyst evaluation
The operation was the same as in example 1. The specific evaluation results are shown in Table 3.
TABLE 2
TABLE 3
Claims (10)
1. A catalyst for preparing butadiene by selective hydrogenation of C-C alkyne is characterized by comprising ZrO2/CdO/Bi2O3The following contents of the composite carrier and the active component are based on the total mass of the catalyst, and ZrO is2/CdO/Bi2O3The content of the composite carrier is 83.5-92.3%, and the content of the active component is 7.7-16.5%;
the active component comprises the following components:
pd or its oxide, the content is 0.05-0.8%, preferably 0.2-0.5% calculated by Pd element;
VIIB metal or at least one of oxides thereof, in terms of metal elements, in an amount of 0.2 to 6.0%, preferably 2.0 to 5.0%;
la or an oxide thereof in an amount of 0.1 to 4.0%, preferably 0.5 to 2.0% in terms of oxide form.
2. The catalyst according to claim 1, wherein the ZrO2/CdO/Bi2O3The composite carrier takes the total mass of the catalyst as a reference, wherein the content of CdO is 1-10%, and preferably 1.0-4.0%; bi2O3The content of (A) is 0.1-5.0%, preferably 1.0-2.0%;
the ZrO2/CdO/Bi2O3The total pore volume of the composite carrier is 0.3-0.9 mL/g, and the specific surface area is 90-180 m3(ii)/g; and/or
Said VIIB metal or oxide thereof, preferably Re or oxide thereof.
3. A process for preparing butadiene catalyst by selective hydrogenation of C-tetraalkyne according to claim 1 or 2, which comprises ZrO2/CdO/Bi2O3CompoundingPreparing a carrier and loading an active component;
the ZrO2/CdO/Bi2O3Preparing a composite carrier, namely preparing a carrier precursor by using a coprecipitation method, adding a pore-forming agent, an adhesive and water pressure strip forming, and aging, drying and roasting to obtain the composite carrier;
the active component is loaded by adopting an impregnation method, including equal-volume impregnation or excessive impregnation.
4. The production method according to claim 3, wherein the coprecipitation method produces a support precursor by: uniformly mixing soluble salts of zirconium, cadmium and bismuth with water, then coprecipitating the mixture with ammonia water, keeping the pH value of a reaction system at 3-6, reacting until the raw materials are exhausted, taking precipitates after the reaction is finished, and washing and drying the precipitates to obtain a carrier precursor;
preferably, the soluble salts of zirconium, cadmium and bismuth are one or more of nitrate and acetate; the soluble salt of zirconium is preferably zirconium nitrate, the concentration is preferably 3.0-4.0 mol/L, the soluble salt of cadmium is preferably cadmium acetate, the concentration is preferably 0.04-0.30 mol/L, the soluble salt of bismuth is preferably bismuth nitrate, and the concentration is preferably 0.02-0.25 mol/L;
preferably, the concentration of the used ammonia water is 1.0-4.5 mol/L, preferably 2.0-4.0 mol/L;
preferably, in the coprecipitation reaction process, soluble salt water solution of zirconium, cadmium and bismuth and ammonia water are dropwise added, and the dropping speed is controlled by the pH value of a reaction system, so that the pH value is kept at 3-6;
preferably, after the drying is completed, the carrier precursor is crushed into particles with the particle size of 80-120 meshes, preferably 100-120 meshes.
5. The method according to claim 4, wherein the drying process is temperature-programmed drying by: heating to 50-80 ℃ at a heating rate of 1-3 ℃/min, drying for 10-24 h, heating to 80-120 ℃ at a heating rate of 1-3 ℃/min, and drying for 6-10 h; and/or
The roasting method comprises the following steps: after drying, raising the temperature to 800-1200 ℃ at a heating rate of 5 ℃/min, and roasting for 4-8 h.
6. The preparation method according to claim 3, wherein the active component is loaded by: firstly, ZrO is firstly2/CdO/Bi2O3VIIB metal is impregnated and loaded on the composite carrier, and Pd and La are impregnated and loaded after drying and roasting treatment; the specific loading method comprises the following steps:
1) ZrO 2 is mixed with2/CdO/Bi2O3Soaking the composite carrier in a VIIB metal soluble salt aqueous solution for 8-10 h, then aging for 4-6 h, drying at 50-80 ℃ for 5-8 h after aging is completed, drying at 80-120 ℃ for 6-10 h, and finally roasting at 330-550 ℃ for 4-8 h to obtain a VIIB metal-loaded catalyst;
2) mixing a palladium soluble salt aqueous solution and a lanthanum soluble salt aqueous solution, adjusting the pH to 2-4 by using a nitric acid aqueous solution, then adding the VIIB metal-loaded catalyst prepared in the step 1) to impregnate for 5-10 h, and repeating the aging, drying and roasting processes in the step 1) to obtain the butadiene catalyst prepared by selective hydrogenation of C-C alkyne.
7. The preparation method as claimed in claim 6, wherein in step 1), the VIIB metal soluble salt is selected from soluble salts of rhenium element, preferably ammonium perrhenate and ammonium perrhenate; the concentration of the aqueous solution of the VIIB metal soluble salt is 0.04-2.20 mol/L, preferably 0.75-1.50 mol/L; and/or
In the step 2), the soluble salt of palladium is selected from palladium chloride and palladium nitrate, preferably palladium nitrate; the concentration of the soluble salt water solution of palladium is 0.01-0.13 mol/L, preferably 0.05-0.10 mol/L;
the soluble salt of lanthanum is selected from lanthanum nitrate and lanthanum acetate, preferably lanthanum nitrate; the concentration of the lanthanum soluble salt aqueous solution is 0.20-8.00 mol/L, preferably 0.70-4.00 mol/L;
the mass ratio of the soluble salt water solution of palladium to the soluble salt water solution of lanthanum is 0.7-7.0: 1, preferably 2.0 to 4.0: 1; and/or
In the step 1) and the step 2), the impregnation is carried out, wherein the mass ratio of the carrier to the impregnation liquid is 1: 1-3, and preferably 1: 1-1.5.
8. The preparation method according to any one of claims 3 to 7, wherein the catalyst for preparing butadiene by selective hydrogenation of carbon-tetrayne obtained in step 2) comprises a passivation treatment process, and the passivation method comprises the following steps: firstly, nitrogen containing hydrogen is used for reducing the carbon dioxide, the temperature of the reduction process is 200-500 ℃, the time is 4-8 h, and the gas hourly space velocity is 40-100 h-1(ii) a Passivating for 4-8 h by using nitrogen containing oxygen, wherein the passivation temperature is 10-90 ℃, and the gas hourly space velocity is 70-160h-1(ii) a And/or
The catalyst for preparing butadiene by selective hydrogenation of carbon-tetraalkyne comprises an activation process, and the activation method comprises the following steps: activating with nitrogen containing hydrogen at 80-150 deg.c for 2-5 hr.
9. The use of the catalyst for preparing butadiene by selective hydrogenation of C-tetraalkyne according to claim 1 or 2 or the catalyst for preparing butadiene by selective hydrogenation of C-tetraalkyne according to any one of claims 3 to 8, which is suitable for the selective hydrogenation of C-tetraalkyne in a feedstock containing C-tetraalkyne, in particular in a feedstock with a high content of C-tetraalkyne, for converting C-tetraalkyne into butadiene by hydrogenation;
the raw material composition containing the carbon tetraalkyne comprises one or more of butyne, vinyl acetylene, carbon tetraalkene and alkane; and/or
The raw material containing the carbon tetraalkyne is selected from a material containing the carbon tetraalkyne, which is a byproduct of an ethylene cracking process, preferably a material extracted from a lateral line after secondary extraction of a butadiene device in the ethylene cracking process, and the content of the carbon tetraalkyne is preferably 20-40% in percentage by mass.
10. The use according to claim 9, characterized in that the hydrogenation reaction is carried out under the conditions: the temperature is 20-60 ℃, the inlet temperature of the reactor is 35-50 ℃, and the preferred temperature is 40-45 ℃; the liquid hourly space velocity is 7-20 h-1Preferably 9h-1(ii) a The reaction pressure is 0.5 to 2.5MPa (G), preferably1.1MPa (G); the hydrogen/alkyne molar ratio is 1 to 4, preferably 1.6 to 2.5, and most preferably 1.8 to 2.0.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112538000A (en) * | 2020-12-15 | 2021-03-23 | 万华化学集团股份有限公司 | Method for efficiently preparing enol by selective hydrogenation of alkynol |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102039130A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of oxygen-containing olefin material, and preparation method and use thereof |
CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparing olefin by dehydrogenating low-carbon alkane |
WO2014003209A1 (en) * | 2012-06-29 | 2014-01-03 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
CN105428666A (en) * | 2015-11-26 | 2016-03-23 | 福州大学 | Fuel cell catalyst with sulfur dioxide poisoning resistance |
CN107537462A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Butane dehydrogenation butylene/butadiene catalyst and purposes |
-
2019
- 2019-10-21 CN CN201911000611.5A patent/CN110813288B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102039130A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of oxygen-containing olefin material, and preparation method and use thereof |
CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparing olefin by dehydrogenating low-carbon alkane |
WO2014003209A1 (en) * | 2012-06-29 | 2014-01-03 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
CN105428666A (en) * | 2015-11-26 | 2016-03-23 | 福州大学 | Fuel cell catalyst with sulfur dioxide poisoning resistance |
CN107537462A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Butane dehydrogenation butylene/butadiene catalyst and purposes |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112538000A (en) * | 2020-12-15 | 2021-03-23 | 万华化学集团股份有限公司 | Method for efficiently preparing enol by selective hydrogenation of alkynol |
CN115178264A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
CN115178263A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | Catalyst for converting alkyne into olefin and preparation method and application thereof |
CN115178251A (en) * | 2021-04-07 | 2022-10-14 | 中国石油化工股份有限公司 | Alumina catalyst carrier, preparation method and application thereof, and C2 hydrogenation catalyst |
CN115178264B (en) * | 2021-04-07 | 2023-04-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
CN115178263B (en) * | 2021-04-07 | 2023-04-25 | 中国石油化工股份有限公司 | Catalyst for converting alkyne into alkene, preparation method and application thereof |
CN115178251B (en) * | 2021-04-07 | 2023-09-22 | 中国石油化工股份有限公司 | Alumina catalyst carrier, preparation method and application thereof, and C2 hydrogenation catalyst |
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