CN108855093A - A kind of nickel-copper series hydrocatalyst and preparation method thereof - Google Patents
A kind of nickel-copper series hydrocatalyst and preparation method thereof Download PDFInfo
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- CN108855093A CN108855093A CN201710338496.7A CN201710338496A CN108855093A CN 108855093 A CN108855093 A CN 108855093A CN 201710338496 A CN201710338496 A CN 201710338496A CN 108855093 A CN108855093 A CN 108855093A
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- Prior art keywords
- nickel
- nickeliferous
- preparation
- catalyst
- solution
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- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical class [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000003054 catalyst Substances 0.000 claims abstract description 114
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 69
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000004033 plastic Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 18
- 150000002815 nickel Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- -1 preferably 0.05~3wt% Chemical compound 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 159000000013 aluminium salts Chemical class 0.000 claims description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 claims 1
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000012876 carrier material Substances 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000000843 powder Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- 239000001569 carbon dioxide Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 241000219782 Sesbania Species 0.000 description 16
- 238000007598 dipping method Methods 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000908 ammonium hydroxide Substances 0.000 description 12
- 239000000284 extract Substances 0.000 description 12
- 238000002803 maceration Methods 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052746 lanthanum Inorganic materials 0.000 description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229940116318 copper carbonate Drugs 0.000 description 6
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920000034 Plastomer Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- 229910052791 calcium Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
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- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of nickel-copper series catalysts and preparation method thereof, and in particular to a kind of using nickeliferous aluminium oxide as the preparation method of the nickel-copper series hydrocatalyst of carrier.Containing active component nickel and copper, using nickeliferous aluminium oxide as carrier, the presoma of alumina carrier containing Ni is nickeliferous boehmite, there is acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite.Specific carrier is used in catalyst of the present invention, advantage is organically combine nickel and boehmite, it is effectively dispersed in active component nickel in boehmite, and form the alumina carrier containing Ni of specific crystal formation, there is preferable adjustment effect to the pore structure and acidity of carrier simultaneously, with merely using preparation catalyst compared with, have many advantages, such as that process is simple, while the easy modulation of carrier material performance.Nickel-copper hydrogenation catalyst hydrogenation activity and selectivity of the invention is high.
Description
Technical field
The present invention relates to a kind of nickel-copper series catalysts and preparation method thereof, and in particular to one kind is to carry with nickeliferous aluminium oxide
The preparation method of the nickel-copper series hydrocatalyst of body.
Background technique
2016, go up within the world Ethylene cracker utilization of capacity continuous 4th year.Drippolene is as cracking of ethylene
Important by-products account for about the 50%~80% of ethylene production capacity.How this part byproduct is made good use of, to the warp for improving enterprise
Ji benefit will generate great influence.Meanwhile it is also various containing a large amount of diolefin, alkyl alkenyl arene, indenes etc. in drippolene
The impurity such as unsaturated hydrocarbons and sulphur, nitrogen, oxygen, cause gasoline property unstable.It is industrial generally to be refined using two-stage hydrogenation,
First hydrogen saturation chain conjugated alkene, cyclic conjugated alkene and styrene etc. are added through one section of Low Temperature Liquid；Again through two sections of high temperature gas phases
Add hydrogen removal sulfur-bearing, nitrogen, the organic impurities of oxygen etc. and after being saturated monoolefin hydrogenation as aromatics extraction raw material produce benzene, toluene and
Dimethylbenzene.Therefore, it is an important branch in field of hydrogenation by the hydrogen addition technology of core of pyrolysis gasoline hydrogenation catalyst, is steaming
There is very important status in the post-processing of vapour cracking ethylene preparation.Currently used one-stage hydrogenation catalyst is roughly divided into two
Class, a kind of active component are nickel non-precious metal catalysts；Another kind of active component is catalyst used in noble metal.Your non-gold
Because the factors such as architectural difference and tenor height have, certain anti-impurity and water-resistant capacity, price advantage also compare metal catalyst
Significantly.Therefore non-precious metal catalyst industrialization product is gradually replacing noble metal catalyst to be applied to pyrolysis product and is adding hydrogen system
Column catalyst.
CN1218822A reports a kind of Ni/Al2O3Suitable for the selective hydrocatalyst of pyrolysis gasoline cut fraction, this is urged
Agent is by nickel load in obtained on the alumina support containing lithium or alkaline-earth metal, this catalyst is bearing plus hydrogen load and adding
It is not good enough in terms of stabilized hydrogen.
IT1312334 discloses a kind of selective hydrocatalyst for the alkadienes selective hydrogenation in distillate, packet
Aluminium oxide, nickel oxide content 5~25%, lithium or alkaline earth metal content 0.1~2.0% are included, is that nickel load is being contained into lithium or alkali
On the aluminium oxide of earth metal.
CN101954282A is related to a kind of Hydrobon catalyst and preparation method thereof, with molybdenum, nickel, zinc, copper composite metal
Oxide at least two is active component, and addition Si, Ti, Ca, Ce, Mg, P oxide at least one is auxiliary agent, and surplus is oxidation
Aluminium.On the basis of catalyst quality, wherein active component mass percentage is 5~15%, and auxiliary agent oxide mass percentage contains
Amount is 0.2~25%, and aluminium oxide is surplus.Hydrodesulfurization, but hydrodesulfurization less effective are used under high temperature.
US3472763 reports a kind of diene selective hydrogenation catalyst, active component Ni content 1~20%, auxiliary agent
MoO3Content 1~5%, auxiliary agent alkali metal and alkaline earth metal content 1~5%, catalyst pores, which are held, is greater than 0.4ml/g, and specific surface is big
In 30m2/ g, this catalyst are to impregnate Al by the aqueous solution of active component and auxiliary agent2O3Carrier is made.
Hydrated alumina such as boehmite and boehmite etc. are widely used as the raw material for preparing alumina support,
Although in carrying alumina production procedure can using as the methods of pH value swing method, the organic expanding agent of addition, hydro-thermal process come
Improve the property of the aluminium oxide as carrier, but the aluminium oxide of catalyst carrier for hydrgenating material is improved by these methods
Performance is limited.The property for preparing aqua oxidation aluminum feedstock used in alumina support is to produce excellent properties carrying alumina
One of body most critical factor.
CN1123392C describes a kind of alumina carrier containing Ni and preparation method thereof, by alkali-treated nickeliferous chemical combination
The mixture of object and carbon black and aluminum hydroxide solid elastomer powder kneading, being made a kind of through extruded moulding and drying, roasting nickeliferous is
2.0%~14.0% alumina support, it is 0.4cm which, which holds,3/ g~1.0cm3/ g, specific surface area 160m2/ g~
420m2/ g, average pore size are 8.0nm~15.0nm, account for the 85% more of its total hole greater than the ratio in the hole 6.0nm, Kong Rong, average
Aperture is larger, and macropore proportion is more, is particularly suitable for the carrier as hydrorefining catalyst for heavy oil.
CN200710179630.X discloses a kind of preparation method of nickel-coated alumina powder, it is characterised in that will be added and divide
Suspension is made in the mixed liquor of the nano aluminium oxide of powder, is added with stirring nickel salt solution, after mixing evenly, drips in mixed liquor
Enter ammonium hydroxide, add distilled water, obtains navy blue nickel amine complex ([Ni (NH3)6]2+)-Aluminium oxide mixed solution C, using water
Heat ageing is filtered, washed, dries, and obtains coating product among green；Roasting is restored again, the oxidation of black nickel coated is obtained
Aluminium powder body.
CN1102862C discloses a kind of nickel-containing hydrogenationcatalysts, contains：In terms of nickel oxide, the nickel of 65-80%, with dioxy
SiClx meter, the silicon of 10-25%, in terms of zirconium oxide, the zirconium of 2-10%, in terms of aluminium oxide, the aluminium of 0-10%, precondition is two
The sum of content of silica and aluminium oxide is at least 15% (weight %, based on the total weight of catalyst), this catalyst
It is by the way that by nickel, zirconium, if necessary, there are also the acidic aqueous solutions of the salt of aluminium to be added to silicon, if necessary, there are also the compounds of aluminium
Alkaline aqueous solution or suspension in, so that the pH of the mixture so obtained is reduced at least 6.5, then by further adding
Alkaline solution adjusts pH value to 7-8, separates the solid so deposited, dries, forms and is sintered.Furthermore it also discloses
Prepare catalyst method and its in preparation medicinal white oils, high-purity medical paraffin and low boiling point low arene content or be free of
The method of the hydrocarbon mixture of aromatic hydrocarbons.The preparation method of the catalyst is commonly used to prepare high-activity component content catalyst, still
The catalyst activity prepared using this method is poor.
Article " the changes induced by calcination temperature in of Agudo A L etc.
hydrodesulfurization activity of NiCo-Mo/Al2O3Catalysis, Applied Catalysis,
1987,30:185-188 " has investigated maturing temperature to NiCoMo/A12O3The active influence of catalyst rhohene desulfiirization.As a result table
Bright, the desulphurizing activated of the catalyst activated at 500 DEG C is significantly higher than the catalyst activated under the conditions of 600 DEG C, this is because
In 600 DEG C of activation, strong interaction generation spinel structure occurs for metal and alumina support so as to cause catalysis in catalyst
Agent activity is remarkably decreased.Activation temperature is higher, and the nickel aluminate phase content of generation is higher, and the activity decline of catalyst is brighter
It is aobvious."Influence of support-interaction on the sulfidation behavior and
hydrodesulfurization activity of Al2O3Support W, CoW and NiW model catalysts, J
PhysChem B, 2002,106:5897-5906 " equally obtains similar conclusion.Since nickel and alumina support are in high-temperature roasting
Strong interaction can occur in the process and generate spinel structure, be remarkably decreased so as to cause catalyst activity, therefore roasted in high temperature
It is all as prudent using the two as possible before burning, avoid the generation of spinel structure.It is different from other metals, it is rare nickeliferous to intend thin water
Aluminium stone report generally requires to carry out high-temperature roasting when because preparing catalyst carrier with it.
The catalyst with higher hydrogenation activity is prepared, corresponding active metal component content also wants high.Simple answers
Hydrotreating catalyst is prepared with infusion process, the solution for needing to prepare high activity metal constituent content carries out dipping system to carrier
?.Therefore there are the following problems in dipping process：(1) since the water absorption rate of carrier is certain, using incipient impregnation method
Maceration extract given volume, active metal component additional amount is excessively high to will lead to dissolution not exclusively；(2) it prepares in catalyst process and needs
Repeatedly dipping active component, twice, three times even four times could be by the activity component impregnation to carrier of certain content, this just makes
At preparation section the problems such as cumbersome, long preparation period, loss of active component；(3) it is repeatedly generally required during dipping
Organic or inorganic dispersing agent is added in maceration extract to increase the dispersion degree of active metal component, but these meetings in last handling process
There are problems that removing.
In the preparation process of catalyst carrier, the compound containing active metal component is introduced in the form of kneading,
Make the compound for containing a certain amount of active metal component in shaping carrier, reduces the catalysis of high-content active metal component to reach
The problem of load difficulty encountered in agent preparation process.But by active metallic compound by way of kneading method is using kneading
With aluminum hydroxide solid elastomer powder or the direct mixed-forming of alumina powder, there are crystal grain to mix uneven and catalyst strength for this method
The problems such as variation, while being also not easy to combine between simple kneading each component and forming specific skeleton structure.
Summary of the invention
The purpose of the present invention is to provide a kind of New Nickel-copper system hydrogenation catalysts and preparation method thereof, are suitable for higher
The preparation requirement of active metal component content catalyst.
Nickel-copper hydrogenation catalyst of the invention contains active component nickel and copper, using nickeliferous aluminium oxide as carrier, with catalyst
Total weight is 100% meter, contains 10~20wt% of nickel oxide (preferably 14.5~18.5wt%), 0.01~5wt% of copper oxide
(preferably 0.05~3wt%), 0~5wt% of cerium oxide and/or lanthana (preferably 0.2~1.8wt%), alkali metal and/or
0~6wt% of alkaline earth oxide (preferably 0.5~3wt%)；50~180m of specific surface area of catalyst2/ g, hole appearance 0.30~
0.60ml/g, 0.5~1.1g/cm of heap density3.The presoma of alumina carrier containing Ni is nickeliferous boehmite, can be by nickel
Organically combine with boehmite, while the nickeliferous boehmite and carrier prepared therefrom have suitable aperture
Distribution.
Carrier in nickel-copper series hydrocatalyst of the invention is nickeliferous aluminium oxide, needs to prepare first and nickeliferous intends thin water
Aluminium stone, the i.e. presoma of alumina carrier containing Ni are nickeliferous boehmites, be not boehmite and nickel compound containing or
The simple physical of nickel salt solution blends or cladding, but acid-base reaction occurs, and has plastic process, and final be made has specific nickel
With the carrier of aluminium mixing crystalline form.Only in this way nickel and boehmite can organically be combined, preferably this is nickeliferous quasi-
Boehmite and carrier prepared therefrom also have suitable pore-size distribution.
Nickeliferous boehmite is through alumina carrier containing Ni obtained from molding, drying, roasting.Depending on finally containing in the present invention
Nickel alumina support is different using purpose, the preparation method of nickeliferous boehmite, nickel source, nickel content, alumina carrier containing Ni
Preparation method, calcination for activation temperature etc. can be different.
The presoma of alumina carrier containing Ni of the present invention, that is, nickeliferous boehmite preferably (intends thin water with nickeliferous
Aluminium stone total weight is 100wt% meter), 0.1~10wt% of nickel content, preferably 0.5~5wt%；300~420m of specific surface area2/ g,
Hole holds 0.7~1.2cm3/ g, 5~10nm of aperture；The nickeliferous boehmite has acid-base neutralization and plastic mistake during the preparation process
Journey.
Alumina carrier containing Ni used in catalyst in the present invention, is preferably formed by nickeliferous boehmite, is roasted
And obtain, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45≤B1/B2≤0.85 in XRD spectra, B1 refer to
The integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to the product at the peak that 2 θ are 43.3~48.5 ° in XRD spectra
Divide intensity.
In the present invention in alumina carrier containing Ni used in catalyst, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4It is brilliant
The mixed crystal of type, best δ-Al2O3、δ-NiAl26O40And NiAl2O4Account for 30~100wt% of alumina carrier containing Ni total weight.It removes
Contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Outside the mixed crystal of crystal form, θ-Al can be also contained in carrier2O3、α-Al2O3And/or
γ-Al2O3, best α-Al2O3Content is lower than 30wt%.
It is different using purpose that final catalyst is regarded in the present invention, the preparation method of nickeliferous boehmite, nickel source, nickel contain
Amount, alumina carrier containing Ni calcination for activation temperature etc. can be different.Best nickel content is in alumina carrier containing Ni of the invention
0.1~10wt%, preferably 0.5~5wt%.25~250m of specific surface area20.15~0.85cm of/g, Kong Rongwei3/ g, aperture be 8~
40nm。
Active component nickel and copper in the present invention, nickel source are selected from one kind or several of nickel nitrate, nickel acetate, nickel chloride or nickel sulfate
Kind, preferably nickel nitrate, nickel acetate.Copper is preferably added in the form of copper nitrate or basic copper carbonate.The present invention is to catalyst
Preparation method does not limit in detail, and equi-volume impregnating preparation such as can be used, and nickeliferous and copper soluble-salt aqueous solution is impregnated
In on carrier, 3~8h is roasted at 300~500 DEG C after dry.By total catalyst weight for 100wt% in terms of, nickel contains in catalyst
Amount is calculated as with oxide：10~20wt% of nickel oxide (preferably 14.5~18.5wt%), 0.01~5wt% of copper oxide are (best
It is 0.05~3wt%).
Rare-earth element cerium and/or lanthanum (existing in the form of an oxide), content 0 can be contained in catalyst of the present invention
~5wt%, preferably 0.2~1.8wt%.After cerium and/or lanthanum is added, catalyst carrier crystal grain is long when being able to suppress high-temperature roasting
Greatly, the dispersion degree for improving active component nickel improves the hydrogenation selectivity and stability of catalyst.Cerium and/or lanthanum be most in the present invention
It is to be added in the form of soluble nitrate well.
Alkali metal and/or alkaline-earth metal (existing in the form of an oxide) can also be contained in catalyst of the present invention, contained
Amount is 0~6wt%, preferably 0.5~3wt%.Alkali metal and/or alkaline-earth metal are one in Li, Na, K, Ca, Mg, Sr, Be
In or a variety of, preferably one or both of Li, Mg.It, can be to catalyst carrier table by addition alkali metal and/or alkaline-earth metal
The acid-base property in face plays adjustment effect, can improve hydrogenation activity and stabilized hydrogenation by adjusting catalyst surface acid-base property, have
Conducive to carbonaceous, the deposition of colloid in hydrogenation process is reduced, to extend the service life of catalyst.In the present invention alkali metal and/
Or alkaline-earth metal is preferably to be added in the form of soluble nitrate, acetate or citrate.
Rare-earth element cerium and/or lanthanum and alkali metal and/or alkaline-earth metal can be added in carrier forming process；?
It can be added in advance into carrier before dipping active constituent after carrier molding；It can also be when impregnating active constituent, with
Active constituent dipping solution is added simultaneously.
The present invention also provides a kind of preparation method of more specific nickel-copper series hydrocatalyst, with nickeliferous and copper molten
Liquid impregnates alumina carrier containing Ni by one or more steps, obtains catalyst by drying, roasting；Alumina carrier containing Ni is by containing
Nickel boehmite through molding, drying, roasting and obtain；Wherein nickeliferous boehmite is preferably obtained by following methods, specifically
Process includes the following steps：
(1) it neutralizes in kettle and bottom water is added, bottom water is deionized water, is heated to 50~90 DEG C；
(2) acid aluminum saline solution, acid nickel salt aqueous solution are prepared respectively, by acid aluminium salt aqueous solution and acid nickel salt water
Solution is uniformly mixed, and obtains the acidic aqueous solution of aluminium containing salt and nickel salt, and adjusting mixed solution temperature is 50~90 DEG C, wherein acid
Aluminum saline solution concentration is preferably 10~80g Al2O3/ L, acid nickel salt aqueous solution concentration is preferably 3~50gNiO/L；
(3) alkali metal aluminate solution is prepared, alkali metal aluminate solution concentration is preferably 50~300gAl2O3/L；
(4) (2) and (3) cocurrent are added in (1), constant ventilation stirring；
(5) 50~90 DEG C of gelling temperature of rate-determining steps (4), plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
Tank bottom can be passed through air in the preparation method step (1)；Step (5) plastic pH value preferably 7~9.
Preferably 50~70 DEG C of temperature described in step (1) in preparation method of the present invention；Step (2) described temperature preferably 50~
70 DEG C, stablize 3~5min.Solution temperature is being just in acid aluminium salt and nickel salt mixed solution, alkali metal aluminate solution and plastic cans
For subzero temperature difference preferably no more than 3 DEG C, three's temperature is preferably identical.
The pH value of alkali metal aluminate solution is 9~14 in step (3) in preparation method of the present invention, preferable ph 12~
14。
In preparation method of the present invention in step (5), preferably 50~70 DEG C of gelling temperature；Plastic pH value preferably 7.5~9.5.
The raw material of industry can be used in aluminium salt described in the preparation method of nickeliferous boehmite and nickel salt.The acidity
Aluminum saline solution can be the mixed solution of one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, preferably sulfuric acid aluminum solutions.
The mixing that the acid nickel salt aqueous solution can be one or more of nickel chloride, nickel sulfate, nickelous bromide and nickel nitrate is molten
Liquid, preferably nickel nitrate solution.Acid aluminium salt and acid nickel salt solution mixing, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, PH
Value is 2~5, preferable ph 2~4.The alkali metal aluminate solution refers to sodium metaaluminate or potassium metaaluminate solution.
The aging of step (6) described material refers to the solution after making plastic under continuing ventilation stirring or stationary state one
Kept for certain time at fixed temperature and pH value.Wherein aging temperature is 50~80 DEG C, and ageing time is 10~60min.
The mode of washing of step (6) described material is common sense well known to those skilled in the art, can add water using when filtering
Washing, mashing washing the modes such as wash using lower alcohols, control 40~80 DEG C of temperature when washing, pH value 4~8, wash time
For 20~40min, washing times are 2~5 times.
Drying mode described in step (6) can using oven drying, spray drying, mesh-belt kiln drying, fluidized bed drying,
Natural drying, microwave drying etc., drying temperature are 70~150 DEG C, drying time 2~for 24 hours, and it is segmented preferably with different temperatures dry
It is dry.The nickeliferous boehmite of the present invention before shaping, can according to need and peptizing agent, extrusion aid and aluminum oxide dry glue powder is added
One or more of, the substance and additional amount specifically used can have knowledge by this field and be determined.For example, the glue
Solvent can one or more of for nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, additional amount be need molded samples total weight 3~
10wt%；The extrusion aid can be sesbania powder etc., and dosage is generally the 2~6wt% for needing molded samples total weight；The oxygen
Change aluminium dry glue powder to be made using conventional method, but additional amount is preferably lower than the 10wt% of nickeliferous boehmite gross mass.
The method of roasting and condition are that catalyst carrier roasts common method and condition, can be used vertical heater, converter and
Mesh-belt kiln is roasted, and the roasting condition of the carrier is：800~1200 DEG C of 4~10h of roasting, maturing temperature preferably 850~
1100℃.This maturing temperature refers to the carrier the final shaping maturing temperature before catalyst dipping active component.In this temperature
Before roasting, carrier may be prepared by low-temperature bake, but be middle transition calcination steps.
Preparation method of the present invention is to impregnate alumina carrier containing Ni by one or more steps with nickeliferous and copper solution, by
Catalyst is made in dry, roasting；Its roasting condition is：3~8h is roasted at 300~500 DEG C.
Catalyst of the invention before the use, preferably at 380~450 DEG C with 6~16h of hydrogen reducing, it is of the invention plus
Hydrogen catalyst is the reaction of monoolefine especially suitable for diolefin hydrogenate.
Specific carrier is used in catalyst of the present invention, advantage is organically combine nickel and boehmite
Come, is effectively dispersed in active component nickel in boehmite, and form the alumina carrier containing Ni of specific crystal formation, while to load
The pore structure and acidity of body have preferable adjustment effect, and final catalyst obtained hydrogenation activity with higher.With
It is compared using preparation catalyst merely, has many advantages, such as that process is simple, while the easy modulation of carrier material performance.
In the preparation process of catalyst used carrier precursor, the compound containing active component is first introduced, is made obtained
The compound for containing a certain amount of active metal component in carrier, will be greatly reduced greater activity metal component content catalyst
Prepare difficulty.On the basis of guaranteeing catalyst performance, achieve the purpose that simplified catalyst preparation process, optimization preparation process.
Nickel-copper hydrogenation catalyst hydrogenation activity and selectivity of the invention is high.
Specific embodiment
Nickel and copper content are measured using atom absorption method in nickel-copper hydrogenation catalyst in the present invention；Using Germany
The crystal form of D8Advance type x-ray powder diffraction instrument (XRD) the measurement carrier of Bruker company production, actual conditions：CuK α spoke
It penetrates, 40 kilovolts, 40 milliamperes, 0.02 ° of scanning speed/step, 0.5 second/step, B1 refers to the peak that 2 θ are 34.2~39.8 ° in XRD spectra
Integrated intensity, B2 refers to that 2 θ in XRD spectra are the integrated intensity at 43.3~48.5 ° of peak.
Analysis method：
Oil distillation：It is measured using oil product test method SYB-2110-60；
Bromine valency：Using SH/T0236-92 standard test；
Diene：Using SH/T0714-2002 standard test；
Specific surface：Using 19587 standard test of GB/T；
Kong Rong, aperture and pore-size distribution：GB/T 21650.2-2008 standard test；
Water content：Using GB/T 11133-89 standard test；
Sulfur content：It is measured using WK-2B microcoulomb instrument；
Nitrogen content：It is measured using KY-3000N chemiluminescence azotometer；
Arsenic content：It is measured using DV-4300 Atomic Emission Spectrometer AES.
The present invention is further illustrated below by embodiment, but is not regarded as that present invention is limited only by this.
Embodiment 1
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, the nickel nitrate solution that 1L concentration is 8.95g NiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity
Control.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution is added dropwise, titanium dioxide in mixed gas
Concentration of carbon is 65v%, flow 4Nm3/h.40 DEG C of reaction temperature, reaction end pH value 9.8, stopping is passed through carbon dioxide, aging 30
Minute, it is separated by filtration mother liquor, is washed.In 110 DEG C of dry 5h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader at plastic, extrusion
Molding, then obtains nickeliferous carrier in 120 DEG C of dry 4h, 960 DEG C of roasting 4h.
(3) catalyst
Maceration extract is made in nickel acetate, copper nitrate, cerous nitrate co-dissolve in water, is impregnated into the 100g prepared in (2)
On carrier, 120 DEG C of drying, 480 DEG C of roasting 3h obtain catalyst C1.
Comparative example 1
(1) boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 60v%, flow 4Nm3/
h.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide, aging 35 minutes, is separated by filtration mother liquor, washs.
120 DEG C of dry 4h, obtain boehmite.
(2) carrier
The boehmite for weighing preparation, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader at plastic, extruded moulding,
Then in 120 DEG C of dry 4h, 970 DEG C of roasting 4h, carrier is made.
(3) catalyst
Maceration extract is made in nickel nitrate, copper nitrate, cerous nitrate co-dissolve in water, is impregnated into the 100g prepared in (2)
On carrier, 120 DEG C of drying, 410 DEG C of roasting 3h obtain catalyst D1.
Embodiment 2
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, the nickel nitrate solution that 1L concentration is 10g NiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity control
System.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution, carbon dioxide in gas mixture is added dropwise
Concentration is 70v%, flow 3Nm3/h.35 DEG C of reaction temperature, reaction end pH value 9.5, stopping is passed through carbon dioxide, and aging 45 divides
Clock is separated by filtration mother liquor, washing.110 DEG C of dry 3h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic
Then body, extruded moulding obtain nickeliferous precursor carrier in 120 DEG C of dry 4h, 620 DEG C of roasting 4h.Prepare lithium carbonate and citric acid
Aqueous solution is impregnated into nickeliferous precursor carrier using equi-volume impregnating, is contained in 120 DEG C of dry 4h, 1000 DEG C of roasting 4h
The carrier of nickel and lithium.
(3) catalyst
Using two step preparation catalysts.The first step, nickel nitrate, basic copper carbonate and ammonium hydroxide is soluble in water that leaching is made
Stain liquid is impregnated on the 100g carrier prepared in (2) using equi-volume impregnating, and the 60% of dipping nickel nitrate total amount.120 DEG C of bakings
Dry, 350 DEG C of roasting 4h, second step is using the 35% of equi-volume impregnating dipping nickel nitrate total amount, and 120 DEG C of drying, 380 DEG C roast
4h obtains catalyst C2.
Embodiment 3
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, the nickel nitrate solution that 1L concentration is 3g NiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity control
System.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution, carbon dioxide in gas mixture is added dropwise
Concentration is 60v%, flow 5Nm3/h.30 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide, and aging 40 divides
Clock is separated by filtration mother liquor, and nickeliferous boehmite is made in 100 DEG C of dry 2h, 120 DEG C of dry 2h in washing.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, mixes with magnesium nitrate, lithium carbonate, nitric acid, citric acid, sesbania powder and water and pinches
Plastic is synthesized, then extruded moulding obtains the carrier of nickeliferous, magnesium and lithium in 120 DEG C of dry 4h, 910 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, nickel nitrate is soluble in water that maceration extract is made, and is impregnated into preparation in (2) using two step equi-volume impregnatings
100g carrier on, a step using equi-volume impregnating dipping nickel nitrate total amount 65%, 120 DEG C drying, 350 DEG C of roasting 4h,
For second step using the 35% of equi-volume impregnating dipping nickel nitrate total amount, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst
C3。
Embodiment 4
(1) nickeliferous boehmite
It is 30g Al by 2L concentration2O3The nickel nitrate solution mixing that the aluminum sulfate solution and 1L concentration of/L is 12gNiO/L is equal
In the even container for being packed into high level, compound concentration is 50g Al2O3/ L sodium aluminate solution 3L is packed into the container of high level, and two
Connect the stainless steel that peristaltic pump progress flow control inflow is equipped with the belt stirrer of 2L bottom water and tank bottom can be passed through gas under container to hold
In device, 56 DEG C of reaction temperature, it is 9.3 that control flow, which adjusts reacting system PH value, is by the way that ammonium hydroxide adjusting slurry pH value is added dropwise
9.5, aging 30 minutes, are separated by filtration mother liquor after reaction, and nickeliferous boehmite is made in washing, 120 DEG C of dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation is squeezed with nitric acid, citric acid, sesbania powder and water mixer kneader at plastic
Item molding, then obtains alumina carrier containing Ni precursor in 120 DEG C of dry 4h, 600 DEG C of roasting 4h.Prepare lanthanum nitrate, lithium carbonate
And aqueous citric acid solution, it is impregnated into nickeliferous precursor carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 980 DEG C of roastings
4h obtains the carrier of nickeliferous, lanthanum and lithium.
(3) catalyst
By nickel nitrate, copper nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2)
On 100g carrier, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C4.
Embodiment 5
(1) nickeliferous boehmite
It is 30g Al by 2L concentration2O3The nickel nitrate solution mixing that the aluminum sulfate solution and 1L concentration of/L is 6g NiO/L is equal
In the even container for being packed into high level, compound concentration is 50g Al2O3//L sodium aluminate solution 3L is packed into the container of high level, and two
Connect the stainless steel that peristaltic pump progress flow control inflow is equipped with the belt stirrer of 2L bottom water and tank bottom can be passed through gas under container to hold
In device, 60 DEG C of reaction temperature, it is 9 that control flow, which adjusts reacting system PH value, is 9.8 by the way that ammonium hydroxide is added dropwise to adjust plasm PH value,
Aging 25 minutes after reaction are separated by filtration mother liquor, washing.120 DEG C of dry 4h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic
Then body, extruded moulding obtain nickeliferous carrier in 120 DEG C of dry 4h, 1020 DEG C of roasting 4h.
(3) catalyst
It is impregnated on the 100g carrier prepared in (2) using two step equi-volume impregnatings, a step is made into total nickel content 50%
Nickel nitrate solution impregnated carrier, 120 DEG C of drying, 350 DEG C of roasting 4h, second step is molten by nickel acetate, basic copper carbonate and ammonium hydroxide
Maceration extract is made in Yu Shuizhong, and the nickel content of residue 50%, 120 DEG C of drying is added, and 380 DEG C of roasting 4h obtain catalyst C5.
Embodiment 6
(1) nickeliferous boehmite
It is 25g Al by 2L concentration2O3The nickel nitrate solution mixing that the aluminum sulfate solution and 1L concentration of/L is 25gNiO/L is equal
In the even container for being packed into high level, compound concentration is 50g Al2O3/ L sodium aluminate solution 3L is packed into the container of high level, and two
Connect the stainless steel that peristaltic pump progress flow control inflow is equipped with the belt stirrer of 2L bottom water and tank bottom can be passed through gas under container to hold
In device, 65 DEG C of reaction temperature, it is 9.0 that control flow, which adjusts reacting system PH value, is by the way that ammonium hydroxide adjusting slurry pH value is added dropwise
9.5, aging 20 minutes, are separated by filtration mother liquor after reaction, washing.In 120 DEG C of dry 4h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with magnesium nitrate, nitric acid, citric acid, sesbania powder and water mixer kneader at can
Then plastomer, extruded moulding obtain nickeliferous precursor carrier in 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Prepare lanthanum nitrate, carbonic acid
Lithium and aqueous citric acid solution are impregnated into nickeliferous precursor carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 950 DEG C of roastings
4h obtains the carrier of nickeliferous, magnesium, lanthanum and lithium.
(3) catalyst
Using two step preparation catalysts.The first step, nickel acetate, basic copper carbonate and ammonium hydroxide is soluble in water that leaching is made
Stain liquid is impregnated on the 100g carrier prepared in (2) using equi-volume impregnating, and the 40% of dipping nickel nitrate total amount.120 DEG C of bakings
Dry, 360 DEG C of roasting 4h, second step is using the 60% of equi-volume impregnating dipping nickel nitrate total amount, and 120 DEG C of drying, 400 DEG C roast
4h obtains catalyst C6.
Comparative example 2
(1) boehmite
It is 30g Al by 2L concentration2O3The aluminum sulfate solution and 3L concentration of/L is 60g Al2O3/ L sodium aluminate solution difference
It is packed into the container of high level, peristaltic pump is connected under two containers and carries out belt stirrer and tank bottom that flow control inflow is equipped with 2L bottom water
It can be passed through in the rustless steel container of gas, 50 DEG C of reaction temperature, it is 9 that control flow, which adjusts pH value of reaction system, by the way that ammonia is added dropwise
It is 9.5 that water, which adjusts slurry pH value, and aging 30 minutes, are separated by filtration mother liquor after reaction, washing.120 DEG C of dry 5h, must intend thin
Diaspore.
(2) carrier
The boehmite for weighing preparation, with magnesium nitrate, nitric acid, citric acid, sesbania powder and water mixer kneader at plastic,
Precursor carrier is made then in 120 DEG C of dry 4h, 550 DEG C of roasting 4h in extruded moulding.Prepare lanthanum nitrate, lithium carbonate and citric acid
Aqueous solution is impregnated into precursor carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 920 DEG C of roasting 4h, is obtained containing magnesium, lanthanum
With the carrier of lithium.
(3) catalyst
Using two step preparation catalysts.The first step, nickel acetate, basic copper carbonate and ammonium hydroxide is soluble in water that leaching is made
Stain liquid is impregnated on the 100g carrier prepared in (2) using equi-volume impregnating, and the 40% of dipping nickel nitrate total amount.120 DEG C of bakings
Dry, 350 DEG C of roasting 4h, two steps are using the 60% of equi-volume impregnating dipping nickel nitrate total amount, and 120 DEG C of drying, 420 DEG C roast
4h obtains catalyst D2.
Embodiment 7
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 60v%, flow 4Nm3/
h.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, 0.5L concentration is added
It is 9.5 by the way that ammonium hydroxide is added dropwise to adjust plasm PH value, after reaction after stablizing 30 minutes for the nickel nitrate solution of 24gNiO/L
Aging 30 minutes, it is separated by filtration mother liquor, is washed.Nickeliferous boehmite is made in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic
Then body, extruded moulding obtain nickeliferous precursor carrier in 120 DEG C of dry 4h, 600 DEG C of roasting 4h.Prepare lithium carbonate and citric acid
Aqueous solution is impregnated into nickeliferous precursor carrier using equi-volume impregnating, is contained in 120 DEG C of dry 4h, 990 DEG C of roasting 4h
The carrier of nickel and lithium.
(3) catalyst
Nickel nitrate, basic copper carbonate are dissolved in ammonium hydroxide and water, maceration extract is made, (2) are impregnated into using equi-volume impregnating
On the 50g carrier of middle preparation, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C7.
Comparative example 3
This comparative example prepares nickeliferous carrier according to the method that embodiment in CN1123392C describes, and specific step is as follows：
It weighs 200g aluminum hydroxide solid elastomer powder and 7.5g sesbania powder after mixing, then weighs 35g carbon black and 16g alkali formula carbon
After mixing, tetrabutylammonium hydroxide (the wherein C previously measured with graduated cylinder is wherein being added in sour nickel16H37The content of NO is about
10w%) 68ml is stirred with glass bar, comes into full contact with tetrabutylammonium hydroxide solution with mixture, will after placing 30 minutes
It is added in the aluminum hydroxide solid elastomer powder for being mixed with sesbania powder, mixes again；
By the mixed solution of acetic acid and citric acid, deionized water, it is added to and is mixed with basic nickel carbonate, carbon black and sesbania powder
In aluminum hydroxide solid elastomer powder, after kneading is at uniform paste plastic, cloverleaf pattern item is extruded on banded extruder, at 120 DEG C
It after 4 hours dry, is roasted 4 hours at 920 DEG C, alumina carrier containing Ni is made.
Maceration extract is made in nickel nitrate, copper nitrate, lithium carbonate co-dissolve in water, the 100g for being impregnated into above-mentioned preparation contains
On nickel carrier, 120 DEG C of drying, 420 DEG C of roasting 4h obtain catalyst D4.
Embodiment 8
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas
In steel container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 70v%, flow 3Nm3/
h.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, 1L concentration, which is added, is
The nickel nitrate solution of 5g NiO/L is stablized after twenty minutes, is 9.5 by the way that ammonium hydroxide is added dropwise to adjust plasm PH value, after reaction always
Change 40 minutes, be separated by filtration mother liquor, washs.In 120 DEG C of dry 4h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation is squeezed with nitric acid, citric acid, sesbania powder and water mixer kneader at plastic
Item molding, then obtains nickeliferous carrier in 120 DEG C of dry 4h, 1050 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, copper nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2)
On 50g carrier, 120 DEG C of drying, 400 DEG C of roasting 4h obtain catalyst C8.
Embodiment 9
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The nickel nitrate solution that the aluminum nitrate solution and 1L concentration of/L is 8gNiO/L is uniformly mixed
It is packed into the container of high level, the ammonia spirit that compound concentration is 8wt% is packed into the container of high level, and wriggling is connected under two containers
Pump carries out belt stirrer of the flow control inflow equipped with 5L bottom water and tank bottom can be passed through in the rustless steel container of gas, reaction temperature
50 DEG C, it is 7.5 that control flow, which adjusts reacting system PH value, after reaction, ammonium hydroxide is added and adjusts plasm PH value 8.5, aging 60
Minute, it is separated by filtration mother liquor, is washed.Nickeliferous boehmite is made in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with lanthanum nitrate, nitric acid, citric acid, sesbania powder and water mixer kneader at can
Plastomer, extruded moulding, then in 120 DEG C of dry 4h.350 DEG C of roasting 4h, obtain the precursor carrier containing lanthanum and nickel.Prepare magnesium nitrate
Aqueous solution is impregnated on nickeliferous carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 850 DEG C of roasting 4h, is obtained containing lanthanum, magnesium
With the carrier of nickel.
(3) catalyst
By nickel nitrate, copper nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2)
On 50g carrier, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C9.
Comparative example 4
(1) boehmite
Preparation 4L concentration is 50g Al2O3The aluminum nitrate solution and concentration of/L is that the ammonia spirit of 8wt% is respectively charged into a high position
In the container at place, peristaltic pump progress belt stirrer of the flow control inflow equipped with 3L bottom water is connected under two containers and tank bottom can be passed through gas
In the rustless steel container of body, 45 DEG C of reaction temperature, it is 8.0 that control flow, which adjusts reacting system PH value, after reaction, ammonia is added
Water adjusts plasm PH value 8.5, aging 30 minutes, is separated by filtration mother liquor, washs.In 120 DEG C of dry 6h, boehmite is obtained.
(2) carrier
The boehmite for weighing preparation, with lanthanum nitrate, nitric acid, citric acid, sesbania powder and water mixer kneader at plastic,
Extruded moulding, then in 120 DEG C of dry 4h.Obtain the precursor carrier containing lanthanum.Magnesium nitrate aqueous solution is prepared, using incipient impregnation
Method is impregnated on nickeliferous carrier, obtains the carrier containing lanthanum and magnesium in 120 DEG C of dry 4h, 880 DEG C of roasting 4h.
(3) catalyst
Nickel nitrate is dissolved in the water, maceration extract is made, is impregnated on 100g carrier, 120 DEG C of drying, 450 DEG C of roasting 4h,
Obtain catalyst D3.
1 embodiment catalyst of table and comparative example catalyst physical property and composition
Evaluating catalyst：
Use drippolene for raw material, feedstock property is shown in Table 2, evaluates C1~C9 and D1~D4 catalyst.Respectively
300h is evaluated, every 12h sampling analysis bromine valency and diene, average data see the table below 3.
Evaluating catalyst is carried out on 100ml adiabatic reactor hydrogenation reaction device, and catalyst is first at 380~450 DEG C
It is restored 10 hours under hydrogen, then cools to 50 DEG C, be passivated the laggard raw material of 5h with the hexamethylene of the 1000ppm containing dimethyl disulfide
Oil.Evaluate process conditions：Reaction pressure：2.8MPa, inlet temperature：55 DEG C, fresh feed oil air speed：3.0h-1, hydrogen and oil volume
Than：200: 1 (volume ratio is in terms of green oils).
2 hydrogenating materials oil nature of table
3 evaluating catalyst average data of table
As can be seen from the above Examples and Comparative Examples, hydrogen is added to urge using the nickel-copper system of the nickeliferous aluminium oxide preparation of the present invention
Agent, under identical evaluation process conditions, the diene of hydrogenated products, bromine valency are relatively low, this has been absolutely proved in embodiment
The catalyst of preparation Hydrogenation with higher.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (16)
1. a kind of nickel-copper series hydrocatalyst, active component nickel and copper are contained in catalyst, using nickeliferous aluminium oxide as carrier,
It is characterized in that：By catalyst weight for 100wt% in terms of, contain 10~20wt% of nickel oxide, preferably 14.5~18.5wt%, oxygen
Change 0.01~5wt% of copper, preferably 0.05~3wt%, cerium oxide and/or lanthana 0~5wt%, preferably 0.2~
1.8wt%, alkali metal and/or alkaline earth oxide 0~6wt%, preferably 0.5~3wt%；Specific surface area of catalyst 50~
180m2/ g, hole hold 0.30~0.60cm3/ g, 0.5~1.1g/cm of heap density3；The presoma of alumina carrier containing Ni is nickeliferous quasi-
Boehmite has acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite；It is impregnated containing active component solution
Nickel-copper series hydrocatalyst is made through drying, roasting in alumina carrier containing Ni.
2. nickel-copper series hydrocatalyst according to claim 1, it is characterised in that：The specific surface of nickeliferous boehmite
300~420m of product20.7~1.2cm of/g, Kong Rongwei3/ g, aperture are 5~10nm；It is with nickeliferous boehmite total weight
100wt% meter, nickel content are 0.1~10wt%, preferably 0.5~5wt%.
3. nickel-copper series hydrocatalyst according to claim 1, it is characterised in that：With alumina carrier containing Ni total weight
For 100% meter, the nickel content of alumina carrier containing Ni is 0.1~10wt%, preferably 0.5~5wt%, specific surface area 25~
250m20.15~0.85cm of/g, Kong Rongwei3/ g, aperture are 8~40nm.
4. nickel-copper series hydrocatalyst according to claim 1, it is characterised in that：Alumina carrier containing Ni is by nickeliferous quasi-
Boehmite is obtained through molding, roasting, contains δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45 in XRD spectra≤
B1/B2≤0.85, B1 refer to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to that 2 θ are in XRD spectra
The integrated intensity at 43.3~48.5 ° of peak.
5. nickel-copper series hydrocatalyst according to claim 1, it is characterised in that：δ-Al in alumina carrier containing Ni2O3、
δ-NiAl26O40And NiAl2O4Account for 30~100wt% of alumina carrier containing Ni total weight.
6. nickel-copper series hydrocatalyst according to claim 1, it is characterised in that：Also contain in alumina carrier containing Ni
θ-Al2O3、α-Al2O3And/or γ-Al2O3；Best α-Al2O3Content is lower than 30wt%.
7. nickel-copper series hydrocatalyst according to claim 4, it is characterised in that：Alumina carrier containing Ni roasting condition
For：800~1200 DEG C of 4~10h of roasting, preferably 850~1100 DEG C of maturing temperature.
8. a kind of preparation method of nickel-copper series hydrocatalyst described in claim 1, it is characterised in that：With nickeliferous and copper
Solution impregnates alumina carrier containing Ni by one or more steps, obtains catalyst by drying, roasting；Alumina carrier containing Ni by
Nickeliferous boehmite is obtained through molding, roasting；Wherein nickeliferous boehmite is obtained by following methods, and detailed process includes
Following steps：
(1) it neutralizes in kettle and bottom water is added, bottom water is deionized water, is heated to 50~90 DEG C；
(2) acid aluminum saline solution, acid nickel salt aqueous solution are prepared respectively, by acid aluminium salt aqueous solution and acid nickel salt aqueous solution
It is uniformly mixed, obtains the acidic aqueous solution of aluminium containing salt and nickel salt, adjusting its solution temperature is 50~90 DEG C, wherein acidic aluminum salt water
Solution concentration is preferably 10~80gAl2O3/ L, acid nickel salt aqueous solution concentration is preferably 3~50gNiO/L；
(3) alkali metal aluminate solution is prepared, alkali metal aluminate solution concentration is preferably 50~300gAl2O3/L；
(4) step is added in the acidic aqueous solution that step (2) obtains and the alkali metal aluminate solution cocurrent that step (3) obtains
(1) in the neutralization kettle in, constant ventilation stirring, until plastic；
(5) 50~90 DEG C of gelling temperature of rate-determining steps (4), plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
9. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：In in step (1)
Air is passed through with the bottom of kettle.
10. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：It is adjusted in step (2)
The temperature for saving the acidic aqueous solution is 50~70 DEG C.
11. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：In step (5), at
50~70 DEG C of glue temperature；Plastic pH value 7.5~9.5.
12. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：Alkali in step (3)
The pH value of metal aluminate solution is 9~14, preferable ph 12~14.
13. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：Acid aluminium salt is water-soluble
Liquid is the mixed solution of one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, preferably sulfuric acid aluminum solutions；Acid nickel salt is water-soluble
Liquid is the mixed solution of one or more of nickel chloride, nickel sulfate, nickelous bromide and nickel nitrate, preferably nickel nitrate solution；Alkali gold
Belong to aluminate solution and refers to sodium metaaluminate or potassium metaaluminate solution.
14. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：In step (2), acid
Property aluminium salt and acid nickel salt aqueous solution mixing, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, pH value is 2~5, preferable ph 2
~4.
15. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：In step (6), always
Changing temperature is 50~80 DEG C, and ageing time is 10~60min.
16. the preparation method of nickel-copper series hydrocatalyst according to claim 8, it is characterised in that：With nickeliferous and copper
Solution impregnates alumina carrier containing Ni by one or more steps, by drying, roasts obtained catalyst；Its roasting condition is：300
3~8h is roasted at~500 DEG C.
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