CN108855129B - Nickel-silver hydrogenation catalyst and preparation method thereof - Google Patents
Nickel-silver hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN108855129B CN108855129B CN201710339787.8A CN201710339787A CN108855129B CN 108855129 B CN108855129 B CN 108855129B CN 201710339787 A CN201710339787 A CN 201710339787A CN 108855129 B CN108855129 B CN 108855129B
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- Prior art keywords
- nickel
- silver
- solution
- hydrogenation catalyst
- acidic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 65
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000010956 nickel silver Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 337
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 168
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 73
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 72
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 75
- 238000001035 drying Methods 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 230000002378 acidificating effect Effects 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 24
- 150000002815 nickel Chemical class 0.000 claims description 24
- 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 24
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 22
- 230000032683 aging Effects 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000007598 dipping method Methods 0.000 claims description 17
- -1 alkali metal aluminate Chemical class 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 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 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 6
- 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 6
- 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 5
- 238000000465 moulding Methods 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 229910021585 Nickel(II) bromide 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
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 239000000843 powder Substances 0.000 description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 24
- 230000001276 controlling effect Effects 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 238000004898 kneading Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 241000219782 Sesbania Species 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000004033 plastic Substances 0.000 description 13
- 229910001961 silver nitrate Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 229910052746 lanthanum Inorganic materials 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229940078494 nickel acetate Drugs 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 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 6
- 239000000047 product Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000012752 auxiliary agent 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
- 239000006229 carbon black Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 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 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 125000003118 aryl group Chemical group 0.000 description 1
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- 238000010335 hydrothermal treatment Methods 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a nickel-silver catalyst and a preparation method thereof, in particular to a preparation method of a nickel-silver hydrogenation catalyst taking nickel-containing alumina as a carrier. The nickel-containing alumina carrier is a nickel-containing pseudo-boehmite precursor, and the preparation process of the nickel-containing pseudo-boehmite includes acid-base neutralization and gelling. The catalyst of the invention uses a specific carrier, and has the advantages that the nickel and the pseudo-boehmite can be organically combined, so that the active component nickel is effectively dispersed in the pseudo-boehmite, and a nickel-containing alumina carrier with a specific crystal form is formed, and meanwhile, the pore structure and the acidity of the carrier are better regulated. The nickel-silver hydrogenation catalyst has high hydrogenation activity and selectivity, and good chemical stability and thermal stability.
Description
Technical Field
The invention relates to a nickel-silver catalyst and a preparation method thereof, in particular to a preparation method of a nickel-silver hydrogenation catalyst taking nickel-containing alumina as a carrier.
Background
In 2017, the ethylene capacity in China will continuously rise. Pyrolysis gasoline is an important byproduct of ethylene pyrolysis, and accounts for about 50-80% of the ethylene production capacity. How to utilize the part of byproducts has great influence on improving the economic benefit of enterprises. Meanwhile, the pyrolysis gasoline also contains a large amount of various unsaturated hydrocarbons such as diolefin, alkyl alkenyl arene, indene and the like and impurities such as sulfur, nitrogen, oxygen and the like, so that the gasoline property is unstable. Two-stage hydrogenation is generally adopted for refining in industry, and chain conjugated olefin, cyclic conjugated olefin, styrene and the like are saturated through one-stage low-temperature liquid-phase hydrogenation; then two-stage high-temp. gas-phase hydrogenation is carried out to remove organic impurities containing sulfur, nitrogen and oxygen, mono-olefin is saturated by hydrogenation and then used as raw material for extracting aromatic hydrocarbon to prepare benzene, toluene and xylene. Therefore, the hydrogenation technology taking the pyrolysis gasoline hydrogenation catalyst as the core is an important branch in the hydrogenation field, and plays a significant role in the post-treatment of preparing ethylene by steam cracking. The currently adopted first-stage hydrogenation catalysts are roughly divided into two types, wherein one active component is a nickel non-noble metal catalyst; another class of active components are catalysts for noble metals. The non-noble metal catalyst has certain impurity resistance and water resistance due to factors such as structural difference, high metal content and the like, and the price advantage is obvious. Therefore, the industrial products of the non-noble metal catalysts are gradually replacing noble metal catalysts to be applied to cracking product hydrogenation series catalysts.
CN101254465B researches a catalyst for selective hydrogenation of cracked carbon five, which comprises the following components by mass percent: 10 to 35 percent of nickel, 0.5 to 3 percent of lanthanum, 0.3 to 3 percent of silver and 59 to 89.2 percent of alumina carrier by the total mass of the catalyst. Potassium and/or strontium and lead may also be included. The catalyst can be used for selective hydrogenation of cracking C5 and full hydrogenation of cracking C5, and has excellent conversion rate, selectivity and stability.
US3472763 reports a diene selective hydrogenation catalyst, the active component Ni content is 1-20%, and the auxiliary agent MoO31-5% of the catalyst, 1-5% of the auxiliary agent alkali metal and alkaline earth metal, more than 0.4ml/g of the catalyst pore volume and more than 30m of the specific surface2The catalyst is prepared by impregnating Al with aqueous solution of active component and auxiliary agent2O3And (3) preparing the carrier.
CN1218822A reports a Ni/Al2O3The catalyst is prepared by loading nickel on an alumina carrier containing lithium or alkaline earth metal, and is poor in bearing hydrogenation load and hydrogenation stability.
Hydrated aluminas such as pseudo-boehmite, and the like are widely used as raw materials for preparing alumina carriers, and although methods such as PH swing, addition of organic pore-expanding agents, hydrothermal treatment, and the like can be employed in the preparation of alumina carriers to improve the properties of alumina as a carrier, there is a limit to improving the properties of alumina as a carrier material of hydrogenation catalysts by these methods. The nature of the hydrated alumina feedstock used to prepare the alumina support is one of the most critical factors in producing an alumina support with superior performance.
CN1123392C describes a nickel-containing alumina carrier and a preparation method thereof, the mixture of nickel-containing compound and carbon black which are treated by alkali is mixed and kneaded with aluminum hydroxide dry glue powder, and the alumina carrier containing 2.0-14.0% of nickel is prepared by extrusion molding, drying and roasting, the pore volume of the carrier is 0.4cm3/g～1.0cm3Per g, specific surface area of 160m2/g～420m2The average pore diameter is 8.0-15.0 nm, the proportion of pores larger than 6.0nm accounts for more than 85 percent of the total pores, the pore volume and the average pore diameter are larger, the proportion of macropores is more, and the porous silicon material is particularly suitable for being used as a porous materialA carrier of a heavy oil hydrofining catalyst.
CN200710179630.X discloses a method for preparing nickel-coated alumina powder, which is characterized in that a mixed solution of nano alumina added with a dispersant is prepared into a suspension, a nickel salt solution is added under stirring, ammonia water is dropped into the mixed solution after uniform stirring, and distilled water is added to obtain a dark blue nickel-ammonia complex ([ Ni (NH)3)6]2+)-Carrying out hydrothermal aging, filtering, washing and drying on the alumina mixed solution C to obtain a green intermediate coating product; and then carrying out reduction roasting to obtain black nickel-coated alumina powder.
CN1102862C discloses a nickel-containing hydrogenation catalyst, which contains: 65-80% nickel, calculated as nickel oxide, 10-25% silicon, calculated as silica, 2-10% zirconium, calculated as zirconia, 0-10% aluminium, calculated as alumina, with the proviso that the sum of the contents of silica and alumina is at least 15% by weight, based on the total weight of the catalyst, which catalyst is obtainable by adding an acidic aqueous solution of a salt of nickel, zirconium and, if desired, aluminium to an alkaline aqueous solution or suspension of silicon and, if desired, a compound of aluminium, reducing the pH of the mixture thus obtained to at least 6.5, then adjusting the pH to 7-8 by further adding an alkaline solution, separating the solid thus deposited, drying, shaping and sintering. Also disclosed are methods of making the catalyst and its use in making medicinal white oils, high purity medicinal paraffins and low boiling, low aromatic content or aromatic-free hydrocarbon mixtures. The preparation method of the catalyst is usually used for preparing the catalyst with high active component content, but the catalyst prepared by the method has poor activity.
The article "changes induced by catalysis in the hydrolysis activity of NiCo-Mo/Al" by Agudo A L et Al2O3Catalysis, Applied Catalysis, 1987,30:185-2O3Influence of the desulfurization activity of the catalyst thiophene. The results show that the desulfurization activity of the catalyst activated at 500 ℃ is significantly higher than that of the catalyst activated at 600 ℃ because of the sulfur reduction activity in the presence of the catalystWhen the catalyst is activated at 600 ℃, the metal in the catalyst and the alumina carrier have strong interaction to generate a spinel structure, so that the activity of the catalyst is obviously reduced. The higher the activation temperature is, the higher the content of the generated nickel aluminate spinel phase is, and the more obvious the activity of the catalyst is reduced. "infection of support-interaction of the support latent developer and hydrolysis activity of Al2O3similar conclusions were also drawn for support W, CoW and NiW model catalysts, J Phys Chem B, 2002, 106: 5897-. Because the nickel and the alumina carrier can generate strong interaction to generate a spinel structure in the high-temperature roasting process, the activity of the catalyst is obviously reduced, and the nickel and the alumina carrier are used as carefully as possible before the high-temperature roasting, so that the spinel structure is avoided. Unlike other metals, nickel-containing pseudo-boehmite has been reported only to a lesser extent because it is often calcined at high temperatures to prepare catalyst supports.
In the preparation process of the catalyst carrier, a compound containing an active metal component is introduced in a kneading mode, so that a certain amount of the compound containing the active metal component is contained in the formed carrier, and the problem of load difficulty in the preparation process of the catalyst with high content of the active metal component is solved. However, the active metal compound and the aluminum hydroxide dry glue powder or the alumina powder are directly mixed and molded by a mixing and kneading method in a mixing and kneading mode, the method has the problems of uneven mixing of crystal grains, poor catalyst strength and the like, and simultaneously, the components are not easy to combine to form a specific framework structure by simple mixing and kneading.
Disclosure of Invention
The invention provides a nickel-silver hydrogenation catalyst and a preparation method thereof.
The nickel-silver hydrogenation catalyst comprises active components of nickel and silver, wherein nickel-containing alumina is used as a carrier, and the catalyst comprises 10-20 wt% (preferably 14.5-18.2 wt%) of nickel oxide, 0.01-3 wt% (preferably 0.05-1.5 wt%) of silver oxide, 0-5 wt% (preferably 0.2-1.2 wt%) of cerium oxide and/or lanthanum oxide, and 0-6 wt% (preferably 0.5-3 wt%) of alkali metal and/or alkaline earth metal oxide, wherein the total weight of the catalyst is 100%; the specific surface area of the catalyst is 50-150 m2A pore volume of 0.25 to 0.55ml/g, bulk density of 0.5-1.1 g/cm3. The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, which can organically combine nickel and the pseudo-boehmite, and simultaneously the nickel-containing pseudo-boehmite and the carrier prepared from the nickel-containing pseudo-boehmite have proper pore size distribution.
The carrier in the nickel-silver hydrogenation catalyst is nickel-containing alumina, nickel-containing pseudo-boehmite needs to be prepared firstly, namely a precursor of the nickel-containing alumina carrier is the nickel-containing pseudo-boehmite, the simple physical mixing or coating of the pseudo-boehmite and a nickel-containing compound or a nickel salt solution is not performed, an acid-base reaction is performed, a gelling process is performed, and finally the carrier with a specific nickel and aluminum mixed crystal form is prepared. Only in this way can nickel and pseudoboehmite be organically combined, preferably the nickel-containing pseudoboehmite and the support prepared therefrom also have a suitable pore size distribution.
The nickel-containing alumina carrier is obtained by molding, drying and roasting the nickel-containing pseudo-boehmite. According to different use purposes of the final nickel-containing alumina carrier, the preparation method of the nickel-containing pseudo-boehmite, the nickel source, the nickel content, the preparation method of the nickel-containing alumina carrier, the activation roasting temperature and the like can be different.
The nickel-containing alumina carrier precursor, namely the nickel-containing pseudo-boehmite, is preferably (calculated by taking the total weight of the nickel-containing pseudo-boehmite as 100 wt%), and the nickel content is 0.1-10 wt%, preferably 0.5-5 wt%; the specific surface area is 300-420 m2A pore volume of 0.7-1.2 cm3The pore diameter is 5-10 nm; the nickel-containing pseudo-boehmite has the processes of acid-base neutralization and gel forming in the preparation process.
The nickel-containing alumina carrier used in the catalyst of the present invention is preferably prepared by molding and roasting nickel-containing pseudo-boehmite, and contains delta-Al2O3、δ-NiAl26O40And NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
The nickel-containing alumina carrier used in the catalyst of the invention contains delta-Al2O3、δ-NiAl26O40And NiAl2O4Mixed crystals of crystal forms, preferably delta-Al2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 wt% of the total weight of the nickel-containing alumina carrier. Except for containing delta-Al2O3、δ-NiAl26O40And NiAl2O4Besides the mixed crystal of the crystal form, the carrier can also contain theta-Al2O3、α-Al2O3And/or gamma-Al2O3Preferably alpha-Al2O3The content is less than 30 wt%.
The preparation method of the nickel-containing pseudo-boehmite, the nickel source, the nickel content, the activation roasting temperature of the nickel-containing alumina carrier and the like can be different according to different use purposes of final catalysts. The nickel-containing alumina carrier of the present invention preferably contains nickel in an amount of 0.1 to 10 wt%, preferably 0.5 to 5 wt%. The specific surface area is 25-250 m2A pore volume of 0.15-0.85 cm3The pore diameter is 8-40 nm.
In the invention, the active components of nickel and silver are added in the form of soluble salts, the nickel source is selected from one or more of nickel nitrate, nickel acetate, nickel chloride or nickel sulfate, and the nickel nitrate and the nickel acetate are preferred. The silver is preferably added in the form of silver nitrate. The preparation method of the catalyst is not limited in detail, and if the catalyst can be prepared by an isometric impregnation method, the catalyst is prepared by impregnating an aqueous solution containing nickel and silver soluble salt on a carrier, drying the carrier and roasting the dried carrier at 300-500 ℃ for 3-8 hours. The nickel content in the catalyst is calculated by taking the total weight of the catalyst as 100 wt%, and calculated by oxides: 10 to 20 wt% (preferably 14.5 to 18.2 wt%) of nickel oxide, and 0.01 to 3 wt% (preferably 0.05 to 1.5 wt%) of silver oxide.
The catalyst of the present invention may contain cerium and/or lanthanum (in the form of oxides) as rare earth elements in an amount of 0 to 5 wt%, preferably 0.2 to 1.2 wt%. After cerium and/or lanthanum are added, the growth of catalyst carrier grains during high-temperature roasting can be inhibited, the dispersion degree of active component nickel is improved, and the hydrogenation selectivity and stability of the catalyst are improved. In the present invention, cerium and/or lanthanum are preferably added in the form of soluble nitrates.
The catalyst of the present invention may further contain an alkali metal and/or an alkaline earth metal (in the form of an oxide) in an amount of 0 to 6 wt%, preferably 0.5 to 3 wt%. The alkali metal and/or alkaline earth metal is one or more of Li, Na, K, Ca, Mg, Sr and Be, preferably one or two of Li and Mg. When the catalyst is used for selective hydrogenation of pyrolysis gasoline, olefin and diene in an oil product are easy to polymerize to form colloid and are inactivated, the pH value of the surface of a catalyst carrier can be adjusted by adding alkali metal and/or alkaline earth metal, the hydrogenation activity and the hydrogenation stability can be improved by adjusting the pH value of the surface of the catalyst, the deposition of carbon and colloid in the hydrogenation process can be reduced, and the service life of the catalyst can be prolonged. In the present invention, the alkali metal and/or alkaline earth metal is preferably added in the form of a soluble nitrate, acetate or citrate.
The rare earth elements cerium and/or lanthanum and alkali metal and/or alkaline earth metal can be added in the carrier forming process; or the active components can be added into the carrier before being impregnated after the carrier is formed; it can also be added simultaneously with the active ingredient impregnation solution when the active ingredient is impregnated.
The invention also provides a preparation method of the more specific nickel-silver hydrogenation catalyst, which comprises the steps of dipping the nickel-containing alumina carrier by one step or multiple steps by using the solution containing nickel and silver, drying and roasting to obtain the catalyst; the nickel-containing alumina carrier is obtained by molding, drying and roasting nickel-containing pseudo-boehmite; the nickel-containing pseudo-boehmite is preferably obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the mixed solution to be 50-90 ℃, wherein the concentration of the acidic aluminum salt aqueous solution is preferably 10-80 g of Al2O3The concentration of the acidic nickel salt aqueous solution is preferably 3-50 gNiO/L;
(3) preparing alkali metal aluminate solution,the alkali metal aluminate solution preferably has a concentration of 50 to 300gAl2O3/L；
(4) Adding the (2) and the (3) into the (1) in a concurrent flow manner, and continuously ventilating and stirring;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
In the preparation method, air can be introduced into the tank bottom in the step (1); and (5) the pH value of the gel is preferably 7-9.
The temperature in the step (1) in the preparation method is preferably 60-80 ℃; the temperature in the step (2) is preferably 50-70 ℃, and the stability is 3-5 min. The temperature difference between the acid aluminum salt and nickel salt mixed solution and the alkali metal aluminate solution and the solution in the gel forming tank is not more than 3 ℃, and the temperature of the acid aluminum salt and nickel salt mixed solution and the temperature of the alkali metal aluminate solution are preferably the same.
In the preparation method, the pH value of the alkali metal aluminate solution in the step (3) is 9-14, and the preferable pH value is 12-14.
In the preparation method, in the step (5), the gelling temperature is preferably 50-70 ℃; the pH value of the gelling is preferably 7.5-9.5.
The aluminum salt and the nickel salt in the preparation method of the nickel-containing pseudo-boehmite can adopt industrial raw materials. The acidic aluminum salt aqueous solution can be one or a mixed solution of more of aluminum chloride, aluminum sulfate and aluminum nitrate, and is preferably an aluminum sulfate solution. The acidic nickel salt aqueous solution can be one or a mixture of nickel chloride, nickel sulfate, nickel bromide and nickel nitrate, and the nickel nitrate solution is preferred. And mixing the acidic aluminum salt solution and the acidic nickel salt solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, wherein the pH value is 2-5, and preferably 2-4. The alkali metal aluminate solution is sodium metaaluminate or potassium metaaluminate solution.
And (4) aging the material in the step (6) refers to keeping the gelatinized solution at a certain temperature and pH value for a certain time under the condition of continuous ventilation stirring or static state. Wherein the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
The washing mode of the material in the step (6) is common knowledge of technicians in the field, and can adopt modes such as water adding washing during filtration, pulping washing, washing by using lower alcohols and the like, wherein the temperature is controlled to be 40-80 ℃, the pH value is 4-8, the washing time is 20-40 min, and the washing times are 2-5.
The drying mode in the step (6) can adopt oven drying, spray drying, mesh belt kiln drying, fluidized bed drying, natural drying, microwave drying and the like, the drying temperature is 70-150 ℃, the drying time is 2-24 hours, and preferably, segmented drying at different temperatures is adopted. Before the nickel-containing pseudo-boehmite is formed, one or more of peptizing agent, extrusion assistant and alumina dry glue powder can be added according to the requirement, and the specific adopted substances and the adding amount can be determined according to the knowledge in the field. For example, the peptizing agent can be one or more of nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, and the addition amount of the peptizing agent is 3-10 wt% of the total weight of the sample to be molded; the extrusion aid can be sesbania powder and the like, and the dosage of the extrusion aid is 2-6 wt% of the total weight of a sample to be molded; the alumina dry glue powder is prepared by a conventional method, but the adding amount is preferably less than 10 wt% of the total mass of the nickel-containing pseudo-boehmite.
The roasting method and conditions are common methods and conditions for roasting the catalyst carrier, and can adopt a vertical furnace, a converter and a mesh belt kiln for roasting, and the roasting conditions of the carrier are as follows: roasting for 4-10 h at 800-1200 ℃, wherein the roasting temperature is preferably 850-1100 ℃. The roasting temperature of the carrier is the roasting temperature of the carrier before active components Ni and Ag are impregnated so as to ensure the specific surface and pore volume required by the catalyst and finally prepare the carrier with a specific nickel and aluminum mixed crystal form. Before the calcination at this temperature, the carrier may be prepared by low-temperature calcination, but all the intermediate calcination steps are used.
The preparation method comprises the steps of dipping a nickel-containing alumina carrier by using a solution containing nickel and silver through one step or multiple steps, and then drying and roasting to prepare the catalyst; the roasting conditions are as follows: roasting for 3-8 h at 300-500 ℃.
Before the catalyst is used, hydrogen is preferably used for reduction for 6-16 h at 380-450 ℃, and the hydrogenation catalyst is particularly suitable for the reaction of selective hydrogenation of diolefin into monoolefin.
The catalyst of the invention uses a specific carrier, and has the advantages that the nickel and the pseudo-boehmite can be organically combined, so that the active component nickel is effectively dispersed in the pseudo-boehmite, a nickel-containing alumina carrier with a specific crystal form is formed, the pore structure and the acidity of the carrier are well adjusted, and the finally prepared catalyst has higher hydrogenation activity. Compared with the catalyst prepared by adopting the impregnation method, the method has the advantages of simple process, easy modulation of the performance of the carrier material and the like.
In the preparation process of the carrier precursor used by the catalyst, the compound containing the active component is introduced firstly, so that the prepared carrier contains a certain amount of the compound containing the active metal component, and the preparation difficulty of the catalyst with higher active metal component content can be greatly reduced. On the basis of ensuring the performance of the catalyst, the purposes of simplifying the preparation process of the catalyst and optimizing the preparation process are achieved. The nickel-silver hydrogenation catalyst has high hydrogenation activity and selectivity, and good chemical stability and thermal stability.
Detailed Description
The content of active metal in the nickel-silver hydrogenation catalyst is measured by adopting an atomic absorption method; the crystal form of the carrier is determined by an X-ray powder diffractometer (XRD) of D8Advance model produced by Bruker company in Germany, and the specific conditions are as follows: CuKalpha radiation, 40 kilovolts, 40 milliamperes, a scanning speed of 0.02 DEG/step and 0.5 seconds/step, wherein B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 DEG in an XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 DEG in the XRD spectrogram.
The analysis method comprises the following steps:
oil product distillation range: the petroleum product test method SYB-2110-60 is adopted for determination;
bromine number: measuring by using SH/T0236-92 standard;
diene: measuring by adopting SH/T0714-;
specific surface area: measured by GB/T19587 standard;
pore volume, pore size and pore size distribution: GB/T21650.2-2008 standard determination;
water content: measuring by using GB/T11133-89 standard;
sulfur content: measuring by adopting a WK-2B micro coulometer;
nitrogen content: measuring by using a KY-3000N chemiluminescence azotometer;
arsenic content: measured by DV-4300 atomic emission spectrometer.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
(1) Nickel-containing pseudo-boehmite
3L of Al with a concentration of 65g2O3The method comprises the following steps of uniformly mixing an aluminum nitrate solution and a nickel nitrate solution with the concentration of 11.8g NiO/L, putting the mixture into a container at a high position, preparing an ammonia water solution with the concentration of 8 wt% into the container at the high position, controlling the flow rate of the ammonia water solution under the two containers by a peristaltic pump, flowing the ammonia water solution into a stainless steel container which is provided with a stirrer and 3L of bottom water and can be filled with gas at the bottom of the container, controlling the reaction temperature to be 50 ℃, controlling the flow to adjust the pH value of a reaction system to be 7.5, adding ammonia water to adjust the pH value of slurry to be 8.5 after the reaction is finished, aging for 60 minutes, filtering and separating mother liquor. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 620 ℃ for 4h to obtain the nickel-containing carrier precursor. Preparing lanthanum nitrate aqueous solution, dipping the lanthanum nitrate aqueous solution on a nickel-containing carrier by adopting an isometric dipping method, drying the carrier for 4h at 120 ℃, and roasting the carrier for 4h at 880 ℃ to obtain the carrier containing nickel and lanthanum.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and silver nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid onto 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 380 ℃ for 4 hours to obtain the catalyst C1.
Example 2
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3The aluminum nitrate solution/L and the nickel nitrate solution 0.5L with the concentration of 14.5g NiO/L are mixed evenly and put into a container at a high position to prepare ammonia with the concentration of 8 weight percentAnd (2) putting the aqueous solution into a high-position container, connecting peristaltic pumps below the two containers to control the flow rate to flow into a stainless steel container which is filled with 2L of bottom water, is provided with a stirrer and can be filled with gas at the bottom of the tank, controlling the reaction temperature to be 55 ℃, controlling the flow to adjust the pH value of the reaction system to be 7.7, adding ammonia water to adjust the pH value of the slurry to be 8.6 after the reaction is finished, aging for 30 minutes, filtering and separating mother liquor, and washing. Drying at 120 ℃ for 5h to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 940 ℃ for 4h to obtain the nickel-and-lithium-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid on 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 420 ℃ for 4 hours to obtain the catalyst C2.
Comparative example 1
(1) Pseudo-boehmite
4L of Al with a concentration of 50g is prepared2O3Respectively filling aluminum nitrate solution and ammonia water solution with the concentration of 8 wt% into a high-position container, connecting a peristaltic pump below the two containers to control the flow rate to flow into a stainless steel container which is filled with 2L of bottom water, is provided with a stirrer, can be filled with gas at the bottom of the container, controlling the reaction temperature to be 45 ℃, controlling the flow to adjust the pH value of a reaction system to be 8.0, after the reaction is finished, adding ammonia water to adjust the pH value of slurry to be 8.5, aging for 40 minutes, filtering and separating mother liquor, and washing. Drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with nitric acid, citric acid, phosphoric acid, sesbania powder, lithium carbonate and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 6h, and roasting at 920 ℃ for 4h to obtain the lithium-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate and silver nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid on 80g of the carrier prepared in the step (2), drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 3 hours at 450 ℃ to obtain the catalyst D1.
Example 3
(1) Nickel-containing pseudo-boehmite
1L of Al with a concentration of 50g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 0.5L with the concentration of 6g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 50g2O3And putting 3L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the sodium metaaluminate solution under the two containers by connecting peristaltic pumps, flowing into a stainless steel container which is provided with 2L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 60 ℃, controlling the pH value of a flow regulation reaction system to be 9, regulating the pH value of slurry to be 9.6 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 4h to obtain the nickel-containing carrier precursor. Preparing magnesium nitrate, lithium carbonate and citric acid aqueous solution, dipping the precursor of the nickel-containing carrier by adopting an equal-volume dipping method, drying the precursor of the nickel-containing carrier at 120 ℃ for 4h, and roasting the precursor of the nickel-containing carrier at 960 ℃ for 4h to obtain the carrier containing nickel, magnesium and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate in water to prepare an impregnation solution, impregnating the impregnation solution onto 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 360 ℃ for 4 hours to obtain the catalyst C3.
Comparative example 2
(1) Pseudo-boehmite
1L of Al with a concentration of 50g2O3Aluminum sulfate solution/L and 3L of Al with a concentration of 50g2O3Respectively loading the sodium metaaluminate solution/L into high-position containers, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with a stirrer and 2L of bottom water and can be filled with gas at the bottom of the container, controlling the reaction temperature to be 50 ℃, controlling the flow to adjust the pH value of a reaction system to be 9, adjusting the pH value of slurry to be 9.5 by dripping ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquorAnd (6) washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudo-thin water aluminum, mixing and kneading the pseudo-thin water aluminum with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water to form a plastic body, extruding the plastic body into strips for forming, drying the strips at 120 ℃ for 4 hours, and roasting the strips at 940 ℃ for 4 hours to obtain the carrier.
(3) Catalyst and process for preparing same
The catalyst is prepared by a two-step impregnation method. And step one, dissolving nickel nitrate and magnesium nitrate in water to prepare a dipping solution, and dipping the dipping solution onto 80g of the carrier prepared in the step (2) by an equal-volume dipping method to obtain 60% of the total amount of the nickel nitrate. Drying at 120 ℃, roasting at 350 ℃ for 4h, impregnating silver nitrate and residual nickel nitrate 40% in the second step by an isometric impregnation method, drying at 120 ℃, and roasting at 380 ℃ for 4h to obtain the catalyst D2.
Example 4
(1) Nickel-containing pseudo-boehmite
2L of Al with a concentration of 22.5g2O3The aluminum sulfate solution of/L and the nickel nitrate solution of 1L with the concentration of 15.8g NiO/L are mixed evenly and put into a container at a high position to prepare Al with the concentration of 50g2O3Putting 3L of sodium metaaluminate solution into a high-position container, controlling the flow rate of the solution by connecting peristaltic pumps below the two containers to flow into a stainless steel container which is provided with 2L of bottom water and is provided with a stirrer, and the bottom of the stainless steel container can be filled with gas, controlling the reaction temperature to be 65 ℃, controlling the pH value of a flow regulation reaction system to be 9.0, regulating the pH value of slurry to be 9.5 by dripping ammonia water, aging for 40 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 120 deg.c for 4 hr to obtain nickel containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with cerous nitrate, nitric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1050 ℃ for 4h to obtain the nickel-and-cerium-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate in water to prepare an impregnation solution, impregnating the impregnation solution onto 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 400 ℃ for 4 hours to obtain the catalyst C4.
Comparative example 3
This comparative example a nickel-containing support was prepared according to the method described in the example in CN1123392C, with the following specific steps:
weighing 200g of aluminum hydroxide dry glue powder and 8.5g of sesbania powder, uniformly mixing, weighing 38g of carbon black and 11.65g of basic nickel carbonate, uniformly mixing, and adding tetrabutyl ammonium hydroxide (wherein C is the tetrabutyl ammonium hydroxide measured in a cylinder previously16H37NO content about 10 w%) 67ml, stirring with a glass rod to make the tetrabutylammonium hydroxide solution fully contact with the mixture, standing for 35 minutes, adding the tetrabutylammonium hydroxide solution into aluminum hydroxide dry glue powder mixed with sesbania powder, and uniformly mixing again;
adding a mixed solution of acetic acid, citric acid and deionized water into aluminum hydroxide dry glue powder mixed with basic nickel carbonate, carbon black and sesbania powder, kneading into uniform pasty plastic, extruding into clover-shaped strips on a strip extruder, drying at 120 ℃ for 3.5 hours, and roasting at 550 ℃ for 4 hours to obtain the nickel-containing carrier precursor. Preparing a cerous nitrate aqueous solution, dipping the cerous nitrate aqueous solution on a nickel-containing carrier precursor by adopting an isometric dipping method, drying the precursor for 6h at 110 ℃, and roasting the precursor for 4h at 1020 ℃ to obtain the nickel-containing and cerium-containing carrier.
And dissolving nickel nitrate and silver nitrate in water together to prepare impregnation liquid, impregnating the impregnation liquid on 80g of the prepared nickel-containing carrier, drying the impregnation liquid at 120 ℃, and roasting the impregnation liquid for 4 hours at 460 ℃ to obtain the catalyst D4.
The physical properties and compositions of the catalysts C1-C8 of examples 1-8 and the catalysts D1-D4 of comparative examples 1-4 are shown in Table 1.
Example 5
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 1L nickel nitrate solution with the concentration of 8.95g NiO/L into a container at a high position, and controlling the flow rate by connecting a peristaltic pump. Introducing mixed gas of carbon dioxide and air, and simultaneously dropwise adding the prepared nickel nitrate solution, wherein the concentration of carbon dioxide in the mixed gas is 60 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.7,stopping introducing carbon dioxide, aging for 35 min, filtering to separate mother liquor, and washing. Drying at 110 deg.c for 6 hr to obtain nickel containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, sesbania powder, lanthanum nitrate and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 580 ℃ for 4h to obtain the nickel-and-lanthanum-containing carrier precursor. Preparing lithium carbonate and citric acid aqueous solution, dipping the lithium carbonate and citric acid aqueous solution on a carrier precursor containing nickel and lanthanum by adopting an equal-volume dipping method, drying the carrier precursor at 120 ℃ for 4h, and roasting the carrier precursor at 1020 ℃ for 4h to obtain the carrier containing nickel, lanthanum and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate into water to prepare an impregnation solution, impregnating the impregnation solution on 80g of the carrier prepared in the step (2), drying the impregnation solution at 120 ℃, and roasting the impregnation solution at 450 ℃ for 3 hours to obtain the catalyst C5.
Comparative example 4
(1) Pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 30 minutes, and mother liquor is filtered and separated and washed. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain pseudo-boehmite.
(2) Carrier
Weighing the prepared pseudoboehmite, mixing with nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 650 ℃ for 4h to obtain a carrier precursor. Preparing lanthanum nitrate, lithium carbonate and citric acid aqueous solution, impregnating the carrier by adopting an isometric impregnation method, drying the carrier at 110 ℃ for 6 hours, and roasting the carrier at 990 ℃ for 4 hours to obtain the carrier containing lanthanum and lithium.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate in water to prepare an impregnation solution, impregnating the impregnation solution on 80g of the carrier prepared in the step (2), drying the impregnation solution at 120 ℃, and roasting the impregnation solution at 410 ℃ for 5 hours to obtain the catalyst D3.
Example 6
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 46.25g2O3Putting the/L sodium metaaluminate solution into a stainless steel container with a stirrer and a gas-permeable tank bottom, putting 1L nickel nitrate solution with the concentration of 12.45g NiO/L into a container at a high position, and controlling the flow rate by connecting a peristaltic pump. Introducing mixed gas of carbon dioxide and air, and simultaneously dropwise adding the prepared nickel nitrate solution, wherein the concentration of the carbon dioxide in the mixed gas is 70 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value at the end of the reaction is 9.5, the introduction of carbon dioxide is stopped, the aging is carried out for 45 minutes, and mother liquor is filtered and separated and washed. Drying at 120 ℃ for 4h to prepare the nickel-containing pseudo-boehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel nitrate, silver nitrate and lanthanum nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid onto 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 350 ℃ for 4 hours to obtain the catalyst C6.
Example 7
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 3Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value is 10 at the end of the reaction, and the introduction of carbon dioxide is stopped. Adding 1L of nickel nitrate solution with the concentration of 5.13g NiO/L under the condition of air stirring, stabilizing for 25 minutes, then adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 30 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 90 deg.C for 3h, and drying at 120 deg.C for 2h to obtain nickel-containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with nitric acid, phosphoric acid, citric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 1100 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) dissolving nickel acetate and silver nitrate in water to prepare impregnation liquid, impregnating the impregnation liquid onto 80g of the carrier prepared in the step (2) by an isometric impregnation method, drying the carrier at 120 ℃, and roasting the carrier at 370 ℃ for 4 hours to obtain the catalyst C7.
Example 8
(1) Nickel-containing pseudo-boehmite
4L of Al with a concentration of 50g2O3Putting the/L sodium metaaluminate solution into a stainless steel container which is provided with a stirrer and can be filled with gas at the bottom of the tank, filling mixed gas of carbon dioxide and air, wherein the concentration of the carbon dioxide in the mixed gas is 60 v%, and the flow rate is 4Nm3H is used as the reference value. The reaction temperature is 35 ℃, the pH value is 10 at the end of the reaction, and the introduction of carbon dioxide is stopped. Adding 1L of nickel nitrate solution with the concentration of 18.6g NiO/L under the condition of air stirring, stabilizing for 25 minutes, then adjusting the pH value of the slurry to 9.5 by dropwise adding ammonia water, aging for 40 minutes after the reaction is finished, filtering and separating mother liquor, and washing. Drying at 120 deg.c for 4 hr to obtain nickel containing pseudoboehmite.
(2) Nickel-containing support
Weighing the prepared nickel-containing pseudo-boehmite, mixing with lanthanum nitrate, nitric acid, citric acid, phosphoric acid, sesbania powder and water, kneading into a plastic body, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 980 ℃ for 4h to obtain the nickel-containing carrier.
(3) Catalyst and process for preparing same
And (3) soaking the carrier prepared in the step (2) on 80g by adopting a two-step isometric soaking method, preparing a nickel acetate solution soaked carrier with the total nickel content of 40% in the first step, drying at 120 ℃, roasting at 350 ℃ for 4h, dissolving nickel nitrate and silver nitrate in water to prepare a soaking solution in the second step, adding the rest 60% of nickel content, drying at 120 ℃, and roasting at 380 ℃ for 4h to obtain the catalyst C8.
TABLE 1 physical Properties and compositions of catalysts of examples and comparative examples
Evaluation of catalyst:
the pyrolysis gasoline is used as a raw material, the properties of the raw material are shown in table 2, and the catalysts of C1-C8 and D1-D4 are evaluated. The evaluation was carried out for 300h, and samples were taken every 12h for analysis of bromine number and diene, and the average data are shown in Table 3 below.
The catalyst evaluation is carried out on a 100ml adiabatic bed hydrogenation reaction device, the catalyst is firstly reduced for 10 hours under hydrogen at 380-450 ℃, then the temperature is reduced to 35 ℃, and the raw oil is passivated by cyclohexane containing 1000ppm of dimethyl disulfide for 4 hours. Evaluating process conditions: reaction pressure: 2.8MPa, inlet temperature: 50 ℃, space velocity of fresh raw oil: 3.0h-1Hydrogen to oil volume ratio: 200: 1 (volume ratio based on fresh oil).
TABLE 2 Hydrofeed oil Properties
Table 3 catalyst evaluation average data
It can be seen from the above examples and comparative examples that the hydrogenation catalyst of nickel-silver series prepared by using the nickel-containing alumina of the present invention has relatively low diene and bromine number of the hydrogenation product under the same evaluation process conditions, which fully indicates that the catalyst prepared in the examples has higher hydrogenation activity and selectivity.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (25)
1. A nickel-silver hydrogenation catalyst contains active components of nickel and silver, and takes alumina containing nickel as a carrier, and is characterized in that: the catalyst comprises, by weight, 100 wt% of nickel oxide, 0.01-3 wt% of silver oxide, 0-5 wt% of cerium oxide and/or lanthanum oxide, and 0-6 wt% of alkali metal and/or alkaline earth metal oxide; the specific surface area of the catalyst is 50-150 m2A pore volume of 0.25-0.55 cm/g3(ii) a bulk density of 0.5 to 1.1g/cm3(ii) a The precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite; dipping the nickel-containing alumina carrier in the solution containing the active components, drying and roasting to prepare the nickel-silver hydrogenation catalyst;
wherein, the preparation process of the nickel-containing pseudo-boehmite comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic aqueous solution to 50-90 ℃;
(3) preparing alkali metal aluminate solution;
(4) adding the (2) and the (3) into the (1) in a concurrent flow manner, and continuously ventilating and stirring;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
2. The nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: the specific surface area of the nickel-containing pseudo-boehmite is 300-420 m2A pore volume of 0.7 to 1.2 cm/g3(ii)/g, the pore diameter is 5-10 nm; the nickel content is 0.1-10 wt% based on the total weight of the nickel-containing pseudo-boehmite as 100 wt%.
3. The nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: the nickel content of the nickel-containing alumina carrier is 0.1-10 wt% based on the total weight of the nickel-containing alumina carrier being 100%The surface area is 25 to 250m2A pore volume of 0.15-0.85 cm3The pore diameter is 8-40 nm.
4. The nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: the nickel-containing alumina carrier is obtained by molding and roasting nickel-containing pseudo-boehmite and contains delta-Al2O3、δ-NiAl26O40And NiAl2O4The crystal form is a crystal form, wherein B1/B2 is more than or equal to 0.45 and less than or equal to 0.85 in an XRD spectrogram, B1 refers to the integral intensity of a peak with the 2 theta of 34.2-39.8 degrees in the XRD spectrogram, and B2 refers to the integral intensity of a peak with the 2 theta of 43.3-48.5 degrees in the XRD spectrogram.
5. The nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: Delta-Al in nickel-containing alumina carrier2O3、δ-NiAl26O40And NiAl2O4Accounting for 30-100 wt% of the total weight of the nickel-containing alumina carrier.
6. The nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: the nickel-containing alumina carrier also contains theta-Al2O3、α-Al2O3And/or gamma-Al2O3。
7. The nickel-silver-based hydrogenation catalyst according to claim 4, characterized in that: the roasting conditions of the nickel-containing alumina carrier are as follows: roasting at 800-1200 ℃ for 4-10 h.
8. The nickel-silver-based hydrogenation catalyst according to claim 1, wherein the catalyst comprises 14.5 to 18.2 wt% of nickel oxide, 0.05 to 1.5 wt% of silver oxide, 0.2 to 1.2 wt% of cerium oxide and/or lanthanum oxide, and 0.5 to 3 wt% of an alkali metal oxide and/or an alkaline earth metal oxide, based on 100 wt% of the catalyst.
9. The nickel-silver-based hydrogenation catalyst according to claim 2, wherein the nickel content is 0.5 to 5 wt% based on 100 wt% of the total weight of the nickel-containing pseudo-boehmite.
10. The nickel-silver-based hydrogenation catalyst according to claim 3, wherein the nickel content of the nickel-containing alumina support is 0.5 to 5 wt% based on 100 wt% of the total weight of the nickel-containing alumina support.
11. The nickel-silver-based hydrogenation catalyst according to claim 6, wherein the alpha-Al in the nickel-containing alumina support2O3The content is less than 30 wt%.
12. The nickel-silver-based hydrogenation catalyst according to claim 7, wherein the calcination temperature of the nickel-containing alumina support is 850 to 1100 ℃.
13. A method for preparing the nickel-silver-based hydrogenation catalyst according to claim 1, characterized in that: dipping a nickel-containing alumina carrier by using a solution containing nickel and silver through one step or multiple steps, and then drying and roasting to obtain a catalyst; the nickel-containing alumina carrier is obtained by molding and roasting nickel-containing pseudo-boehmite; the nickel-containing pseudo-boehmite is obtained by the following method, and the specific process comprises the following steps:
(1) adding bottom water into the neutralization kettle, wherein the bottom water is deionized water, and heating to 50-90 ℃;
(2) respectively preparing an acidic aluminum salt aqueous solution and an acidic nickel salt aqueous solution, uniformly mixing the acidic aluminum salt aqueous solution and the acidic nickel salt aqueous solution to obtain an acidic aqueous solution containing aluminum salt and nickel salt, and adjusting the temperature of the acidic aqueous solution to 50-90 ℃;
(3) preparing alkali metal aluminate solution;
(4) adding the (2) and the (3) into the (1) in a concurrent flow manner, and continuously ventilating and stirring;
(5) controlling the gelling temperature of the step (4) to be 50-90 ℃, and controlling the gelling pH value to be 7-10;
(6) after the cementing, the nickel-containing pseudo-boehmite is prepared by aging, filtering, washing and drying.
14. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: and (2) introducing air into the kettle bottom of the neutralization kettle in the step (1).
15. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: and (3) adjusting the temperature of the acidic aqueous solution to 50-70 ℃ in the step (2).
16. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: in the step (5), the gelling temperature is 50-70 ℃; the pH value of the gelling is 7.5-9.5.
17. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: and (4) the pH value of the alkali metal aluminate solution in the step (3) is 9-14.
18. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: the acidic aluminum salt aqueous solution is a mixed solution of one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; the acidic nickel salt aqueous solution is a mixed solution of one or more of nickel chloride, nickel sulfate, nickel bromide and nickel nitrate; the alkali metal aluminate solution is sodium metaaluminate or potassium metaaluminate solution.
19. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: in the step (2), the acidic aluminum salt and the acidic nickel salt aqueous solution are mixed to obtain an acidic aqueous solution containing aluminum salt and nickel salt, wherein the pH value is 2-5.
20. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: in the step (6), the aging temperature is 50-80 ℃, and the aging time is 10-60 min.
21. The method for producing a nickel-silver-based hydrogenation catalyst according to claim 13, characterized in that: dipping a nickel-containing alumina carrier by using a solution containing nickel and silver through one step or multiple steps, and then drying and roasting to prepare a catalyst; the roasting conditions are as follows: roasting for 3-8 h at 300-500 ℃.
22. The method of claim 13, wherein the concentration of the aqueous acidic aluminum salt solution is 10 to 80g Al2O3The concentration of the acidic nickel salt aqueous solution is 3-50 g NiO/L; the concentration of the alkali metal aluminate solution is 50-300 g Al2O3/L。
23. The method for preparing a nickel-silver-based hydrogenation catalyst according to claim 17, wherein the pH of the alkali metal aluminate solution in the step (3) is 12 to 14.
24. The method of claim 18, wherein the aqueous acidic aluminum salt solution is an aluminum sulfate solution; the aqueous acidic nickel salt solution is a nickel nitrate solution.
25. The method of claim 19, wherein the acidic aqueous solution containing an aluminum salt and a nickel salt has a pH of 2 to 4.
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