CN108855129B - 一种镍-银系加氢催化剂及其制备方法 - Google Patents
一种镍-银系加氢催化剂及其制备方法 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
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- 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
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- 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
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- 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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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
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- 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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- 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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- 239000011591 potassium Substances 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
-
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Abstract
本发明涉及一种镍‑银系催化剂及其制备方法,具体涉及一种以含镍氧化铝为载体的镍‑银系加氢催化剂的制备方法。含活性组分镍和银,以含镍氧化铝为载体,含镍氧化铝载体的前驱体是含镍拟薄水铝石,该含镍拟薄水铝石的制备过程中有酸碱中和和成胶过程。本发明催化剂中使用特定的载体,优点在于能够将镍和拟薄水铝石有机的结合起来,使活性组分镍有效分散在拟薄水铝石中,并形成特定晶型的含镍氧化铝载体,同时对载体的孔结构以及酸性有较好的调节作用,与单纯采用浸渍法制备催化剂相比,具有过程简单,同时载体材料性能易调变等优点。本发明的镍‑银加氢催化剂加氢活性和选择性高,化学稳定性和热稳定性好。
Description
技术领域
本发明涉及一种镍-银催化剂及其制备方法,具体涉及一种以含镍氧化铝为载体的镍-银加氢催化剂的制备方法。
背景技术
2017年,中国乙烯产能将持续呈上升趋势。裂解汽油作为乙烯裂解的重要副产物,约占乙烯生产能力的50%~80%。如何利用好这部分副产品,对提高企业的经济效益将产生重大的影响。同时,裂解汽油中还含有大量的双烯烃、烷烯基芳烃、茚等各种不饱和烃以及硫、氮、氧等杂质,导致汽油性质不稳定。工业上一般采用两段加氢进行精制,先经一段低温液相加氢饱和链状共轭烯烃、环状共轭烯烃及苯乙烯等;再经二段高温气相加氢去除含硫、氮、氧等的有机杂质并使单烯烃加氢饱和后作芳烃抽提原料制取苯、甲苯和二甲苯。因此,以裂解汽油加氢催化剂为核心的加氢技术是加氢领域中一个重要分支,在蒸汽裂解制乙烯的后处理中有着举足轻重的地位。目前采用的一段加氢催化剂大致分为两类,一类活性组分是镍非贵金属催化剂;另一类的活性组分是贵金属所用的催化剂。非贵金属催化剂因结构差异和金属含量高等因素具有一定抗杂质和耐水能力,其价格优势也比较显著。因此非贵金属催化剂工业化产品正在逐步取代贵金属催化剂应用于裂解产物加氢系列催化剂。
CN101254465B研究了一种用于裂解碳五选择加氢的催化剂,包含下列质量百分比的组分:镍10%~35%、镧0.5%~3%、银0.3%~3%、氧化铝载体59%~89.2%,以催化剂的总质量计。还可以包含钾和/或锶以及铅。该催化剂可用于裂解碳五选择加氢,还可用于裂解碳五全加氢,它具有优异的转化率、选择性和良好的稳定性。
US3472763报道了一种双烯选择性加氢催化剂,活性组分Ni含量1~20%,助剂MoO3含量1~5%,助剂碱金属和碱土金属含量1~5%,催化剂孔容大于0.4ml/g,比表面大于30m2/g,此催化剂是由活性组分及助剂的水溶液浸渍Al2O3载体制得。
CN1218822A报道了一种Ni/Al2O3适用于裂解汽油馏分的选择性加氢催化剂,该催化剂是将镍负载于含锂或碱土金属的氧化铝载体上制得的,此催化剂在承受加氢负荷及加氢稳定性方面欠佳。
水合氧化铝如拟薄水铝石和薄水铝石等作为制备氧化铝载体的原料被广泛使用,虽然氧化铝载体制备过程中可以采用如PH值摆动法、添加有机扩孔剂、水热处理等方法来改善作为载体的氧化铝的性质,但是通过这些方法来提高加氢催化剂载体材料的氧化铝的性能是有限的。制备氧化铝载体所用的水合氧化铝原料的性质是生产出优异性能氧化铝载体最关键因素之一。
CN1123392C描述了一种含镍氧化铝载体及其制备方法,将经碱处理过的含镍化合物和炭黑的混合物与氢氧化铝干胶粉混捏,经挤条成型和干燥、焙烧而制得一种含镍为2.0%~14.0%的氧化铝载体,该载体孔容为0.4cm3/g~1.0cm3/g、比表面积为160m2/g~420m2/g、平均孔径为8.0nm~15.0nm,大于6.0nm孔的比例占其总孔的85%还多,孔容、平均孔径较大,大孔所占比例多,尤其适用于做为重质油加氢精制催化剂的载体。
CN200710179630.X公开了一种镍包氧化铝粉末的制备方法,其特征在于将加入分散剂的纳米氧化铝的混合液制成悬浮液,搅拌下加入镍盐溶液,搅拌均匀后,在混合液中滴入氨水,再加入蒸馏水,得到深蓝色镍氨配合物([Ni(NH3)6]2+)-氧化铝混合溶液C,再经过水热老化,过滤、洗涤、烘干,得到绿色中间包覆产物;再进行还原焙烧,得到黑色镍包覆氧化铝粉体。
CN1102862C公开了一种含镍加氢催化剂,含有:以氧化镍计,65-80%的镍,以二氧化硅计,10-25%的硅,以氧化锆计,2-10%的锆,以氧化铝计,0-10%的铝,其前提条件是二氧化硅和氧化铝的含量之和至少为15%(重量%,以催化剂的总重量为基础),这种催化剂是通过将镍、锆,必要的话,还有铝的盐的酸性水溶液添加到硅,必要的话,还有铝的化合物的碱性水溶液或悬浮液中,使如此获得的混合物的pH降低到至少6.5,然后通过进一步添加碱性溶液将pH值调节到7-8,分离如此沉积的固体,干燥、成型并烧结得到的。此外还公开了制备催化剂的方法,以及其在制备医用白油、高纯度医用石蜡和低沸点低芳烃含量或不含芳烃的烃类混合物的方法。该催化剂的制备方法常用来制备高活性组分含量催化剂,但是采用该方法制备的催化剂活性较差。
Agudo A L等的文章“changes induced by calcination temperature inhydrodesulfurization activity of NiCo-Mo/Al2O3catalysis,Applied Catalysis,1987,30:185-188”,考察了焙烧温度对NiCoMo/A12O3催化剂噻吩脱硫活性的影响。结果表明,在500℃下活化的催化剂的脱硫活性显著高于在600℃条件下活化的催化剂,这是由于在600℃活化时催化剂中金属与氧化铝载体发生强相互作用生成尖晶石结构从而导致催化剂活性显著下降。活化温度越高,生成的镍铝尖晶石相含量越高,催化剂的活性下降越明显。“Influence of support-interaction on the sulfidation behavior andhydrodesulfurization activity of Al2O3support W,CoW and NiW model catalysts,JPhys Chem B,2002,106:5897-5906”同样得出类似的结论。由于镍与氧化铝载体在高温焙烧过程中会发生强相互作用生成尖晶石结构,从而导致催化剂活性显著下降,因此在高温焙烧之前都尽可能慎重使用两者,避免尖晶石结构的产生。与其它金属不同,少有含镍拟薄水铝石报导,因为要用其制备催化剂载体时往往需要进行高温焙烧。
在催化剂载体的制备过程中,将含有活性金属组分的化合物以混捏的形式引入,使成型载体中含有一定量的活性金属组分的化合物,来达到降低高含量活性金属组分催化剂制备过程中遇到的负载难度的问题。但是通过混捏法采用混捏的形式将活性金属化合物与氢氧化铝干胶粉或氧化铝粉直接混合成型,该方法存在晶粒子混合不均匀和催化剂强度变差等问题,同时单纯混捏各组分之间也不易结合形成特定骨架结构。
发明内容
本发明提供一种镍-银系加氢催化剂及其制备方法。
本发明的镍-银系加氢催化剂,含活性组分镍和银,以含镍氧化铝为载体,以催化剂总重量为100%计,含有氧化镍10~20wt%(最好是14.5~18.2wt%),氧化银0.01~3wt%(最好是0.05~1.5wt%),氧化铈和/或氧化镧0~5wt%(最好是0.2~1.2wt%),碱金属和/或碱土金属氧化物0~6wt%(最好是0.5~3wt%);催化剂比表面积50~150m2/g,孔容0.25~0.55ml/g,堆密度0.5~1.1g/cm3。含镍氧化铝载体的前驱体是含镍拟薄水铝石,能够将镍和拟薄水铝石有机的结合起来,同时该含镍拟薄水铝石及由其制备的载体具有适宜的孔径分布。
本发明的镍-银系加氢催化剂中的载体是含镍氧化铝,需要首先制备含镍拟薄水铝石,即含镍氧化铝载体的前驱体是含镍拟薄水铝石,并非是拟薄水铝石与含镍化合物或镍盐溶液的简单物理掺混或包覆,而是发生酸碱反应,具有成胶过程,最终制得具有特定镍和铝混合晶形的载体。只有这样才能够将镍和拟薄水铝石有机地结合起来,最好该含镍拟薄水铝石及由其制备的载体还具有适宜的孔径分布。
含镍拟薄水铝石经成型、干燥、焙烧而得到的含镍氧化铝载体。本发明中视最终含镍氧化铝载体使用目的不同,含镍拟薄水铝石的制备方法、镍源、镍含量、含镍氧化铝载体制备方法、活化焙烧温度等可以不同。
本发明所述的含镍氧化铝载体的前驱体即含镍拟薄水铝石最好为(以含镍拟薄水铝石总重量为100wt%计),镍含量0.1~10wt%,优选0.5~5wt%;比表面积300~420m2/g,孔容0.7~1.2cm3/g,孔径5~10nm;该含镍拟薄水铝石在制备过程中有酸碱中和和成胶过程。
本发明中催化剂所用的含镍氧化铝载体,最好是由含镍拟薄水铝石经成型、焙烧而得到,含有δ-Al2O3、δ-NiAl26O40和NiAl2O4晶型,且XRD谱图中0.45≤B1/B2≤0.85,B1是指XRD谱图中2θ为34.2~39.8°的峰的积分强度,B2是指XRD谱图中2θ为43.3~48.5°的峰的积分强度。
本发明中催化剂所用的含镍氧化铝载体中,含有δ-Al2O3、δ-NiAl26O40和NiAl2O4晶型的混晶,最好δ-Al2O3、δ-NiAl26O40和NiAl2O4占含镍氧化铝载体总重量的30~100wt%。除含有δ-Al2O3、δ-NiAl26O40和NiAl2O4晶型的混晶外,载体中还可含有θ-Al2O3、α-Al2O3和/或γ-Al2O3,最好α-Al2O3含量低于30wt%。
本发明中视最终催化剂使用目的不同,含镍拟薄水铝石的制备方法、镍源、镍含量、含镍氧化铝载体活化焙烧温度等可以不同。本发明的含镍氧化铝载体中最好镍含量为0.1~10wt%,优选0.5~5wt%。比表面积25~250m2/g,孔容为0.15~0.85cm3/g,孔径为8~40nm。
本发明中活性组分镍、银是以可溶性盐的形式加入的,镍源选自硝酸镍、醋酸镍、氯化镍或硫酸镍的一种或几种,优选硝酸镍、醋酸镍。银最好是以硝酸银的形式加入。本发明对催化剂的制备方法不作详细限定,如可采用等体积浸渍法制备,将含镍和银可溶性盐的水溶液浸渍于载体上,干燥后在300~500℃下焙烧3~8h。以催化剂总重量为100wt%计,催化剂中镍含量以氧化物计为:氧化镍10~20wt%(最好是14.5~18.2wt%),氧化银0.01~3wt%(最好是0.05~1.5wt%)。
本发明所述的催化剂中可含有稀土元素铈和/或镧(以氧化物形式存在),含量为0~5wt%,最好为0.2~1.2wt%。加入铈和/或镧后,能够抑制高温焙烧时催化剂载体晶粒长大,提高活性组分镍的分散度,提高催化剂的加氢选择性和稳定性。本发明中铈和/或镧最好是以可溶性硝酸盐的形式加入的。
本发明所述的催化剂中还可含有碱金属和/或碱土金属(以氧化物形式存在),含量为0~6wt%,最好为0.5~3wt%。碱金属和/或碱土金属为Li、Na、K、Ca、Mg、Sr、Be中的一中或多种,优选Li、Mg中的一种或两种。催化剂用于裂解汽油选择加氢时,油品中的烯烃、二烯烃容易聚合形成胶质而失活,通过添加碱金属和/或碱土金属,可对催化剂载体表面的酸碱性起到调节作用,通过调整催化剂表面酸碱性可改善加氢活性和加氢稳定性,有利于降低加氢过程中炭质、胶质的沉积,从而延长催化剂的使用寿命。本发明中碱金属和/或碱土金属最好是以可溶性硝酸盐、醋酸盐或柠檬酸盐的形式加入的。
稀土元素铈和/或镧以及碱金属和/或碱土金属均可以在载体成型过程中加入;也可以在载体成型后,浸渍活性组份之前先行加入至载体中;还可以是在浸渍活性组份时,与活性组份浸渍溶液同时加入。
本发明还提供了一种更具体的镍-银系加氢催化剂的制备方法,用含镍和银的溶液通过一步或多步浸渍含镍氧化铝载体,后经干燥、焙烧而得催化剂;含镍氧化铝载体由含镍拟薄水铝石经成型、干燥、焙烧而得到;其中含镍拟薄水铝石最好由下述方法得到,具体过程包括如下步骤:
(1)中和釜中加入底水,底水为去离子水,加热到50~90℃;
(2)分别配制酸性铝盐水溶液、酸性镍盐水溶液,将酸性铝盐水溶液和酸性镍盐水溶液混合均匀,得到含铝盐和镍盐的酸性水溶液,调节混合溶液温度为50~90℃,其中酸性铝盐水溶液浓度最好为10~80g Al2O3/L,酸性镍盐水溶液浓度最好为3~50gNiO/L;
(3)配制碱金属铝酸盐溶液,碱金属铝酸盐溶液浓度最好为50~300gAl2O3/L;
(4)将(2)和(3)并流加入(1)中,持续通风搅拌;
(5)控制步骤(4)成胶温度50~90℃,成胶pH值7~10;
(6)成胶结束后,经老化、过滤、洗涤、干燥制得含镍拟薄水铝石。
所述制备方法步骤(1)中罐底可通入空气;步骤(5)成胶pH值优选7~9。
本发明制备方法中步骤(1)所述的温度优选60~80℃;步骤(2)所述温度优选50~70℃,稳定3~5min。酸性铝盐和镍盐混合溶液、碱金属铝酸盐溶液与成胶罐中溶液温度正负温差不超过3℃,三者温度最好相同。
本发明制备方法中步骤(3)中碱金属铝酸盐溶液的pH值为9~14,优选pH值12~14。
本发明制备方法中步骤(5)中,成胶温度优选50~70℃;成胶pH值优选7.5~9.5。
含镍拟薄水铝石的制备方法中所述的铝盐和镍盐均可采用工业原料。所述的酸性铝盐水溶液可以是氯化铝、硫酸铝及硝酸铝中的一种或几种的混合溶液,优选硫酸铝溶液。所述的酸性镍盐水溶液可以是氯化镍、硫酸镍、溴化镍及硝酸镍中的一种或几种的混合溶液,优选硝酸镍溶液。酸性铝盐和酸性镍盐溶液混合,得到含铝盐和镍盐的酸性水溶液,PH值为2~5,优选pH值2~4。所述的碱金属铝酸盐溶液是指偏铝酸钠或偏铝酸钾溶液。
步骤(6)所述物料的老化是指在继续通风搅拌或静止状态下使成胶后的溶液在一定的温度和pH值下保持一定时间。其中老化温度为50~80℃,老化时间为10~60min。
步骤(6)所述物料的洗涤方式是本领域技术人员公知常识,可以采用过滤时加水洗涤、打浆洗涤、使用低级醇类洗涤等方式,洗涤时控制温度40~80℃,pH值4~8,洗涤时间为20~40min,洗涤次数为2~5次。
步骤(6)所述的干燥方式可以采用烘箱干燥、喷雾干燥、网带窑干燥、流化床干燥、自然干燥、微波干燥等,干燥温度为70~150℃,干燥时间2~24h,最好采用不同温度分段干燥。本发明含镍拟薄水铝石在成型之前,可以根据需要加入胶溶剂、助挤剂和氧化铝干胶粉中的一种或几种,具体采用的物质和加入量可以按本领域已有知识进行确定。比如,所述胶溶剂可以为硝酸、磷酸、盐酸和硫酸中的一种或几种,加入量为需成型样品总重量的3~10wt%;所述助挤剂可以为田菁粉等,其用量一般为需成型样品总重量的2~6wt%;所述氧化铝干胶粉采用常规方法制得,但加入量最好低于含镍拟薄水铝石总质量的10wt%。
所述焙烧方法和条件为催化剂载体焙烧常用方法和条件,可采用立式炉、转炉和网带窑进行焙烧,所述载体的焙烧条件为:800~1200℃焙烧4~10h,焙烧温度优选850~1100℃。该载体的焙烧温度为浸渍活性组分Ni、Ag之前载体的焙烧温度,以保证催化剂所需的比表面、孔容,并使最终制得具有特定镍和铝混合晶形的载体。在此温度焙烧前,可能经过低温焙烧制备载体,但均为中间过渡焙烧步骤。
本发明制备方法为用含镍和银的溶液通过一步或多步浸渍含镍氧化铝载体,后经干燥、焙烧制得催化剂;其焙烧条件为:300~500℃下焙烧3~8h。
本发明的催化剂在使用之前,最好在380~450℃用氢气还原6~16h,本发明的加氢催化剂特别适用于二烯烃选择加氢为单烯烃的反应。
本发明催化剂中使用特定的载体,优点在于能够将镍和拟薄水铝石有机的结合起来,使活性组分镍有效分散在拟薄水铝石中,并形成特定晶型的含镍氧化铝载体,同时对载体的孔结构以及酸性有较好的调节作用,而且最终制得的催化剂具有较高的加氢活性。与单纯采用浸渍法制备催化剂相比,具有过程简单,同时载体材料性能易调变等优点。
在催化剂所用载体前体的制备过程中,先引入含有活性组分的化合物,使制得的载体中含有一定量的活性金属组分的化合物,会大大降低较高活性金属组分含量催化剂的制备难度。在保证催化剂性能的基础上,达到简化催化剂制备过程、优化制备工艺的目的。本发明的镍-银加氢催化剂加氢活性和选择性高,化学稳定性和热稳定性好。
具体实施方式
本发明中镍-银系加氢催化剂中活性金属含量采用原子吸收方法测得;采用德国Bruker公司生产的D8Advance型X射线粉末衍射仪(XRD)测定载体的晶型,具体条件:CuKα辐射,40千伏,40毫安,扫描速度0.02°/步,0.5秒/步,B1是指XRD谱图中2θ为34.2~39.8°的峰的积分强度,B2是指XRD谱图中2θ为43.3~48.5°的峰的积分强度。
分析方法:
油品馏程:采用石油产品试验方法SYB-2110-60测定;
溴价:采用SH/T 0236-92标准测定;
双烯:采用SH/T 0714-2002标准测定;
比表面:采用GB/T 19587标准测定;
孔容、孔径和孔径分布:GB/T 21650.2-2008标准测定;
水含量:采用GB/T 11133-89标准测定;
硫含量:采用WK-2B微库伦仪测定;
氮含量:采用KY-3000N化学发光定氮仪测定;
砷含量:采用DV-4300原子发射光谱仪测定。
下面通过实施例进一步说明本发明,但并不认为本发明仅局限于此。
实施例1
(1)含镍拟薄水铝石
将3L浓度为65g Al2O3/L的硝酸铝溶液和1L浓度为11.8g NiO/L的硝酸镍溶液混合均匀装入高位处的容器内,配制浓度为8wt%的氨水溶液装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有3L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度50℃,控制流量调节反应体系PH值为7.5,反应结束后,加入氨水调节调节浆液PH值8.5,老化60分钟,过滤分离母液,洗涤。在90℃干燥3h,120℃干燥2h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸、磷酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,620℃焙烧4h,得到含镍载体前体。配制硝酸镧水溶液,采用等体积浸渍法浸渍到含镍载体上,在120℃干燥4h,880℃焙烧4h,得到含镍、镧的载体。
(3)催化剂
将硝酸镍、硝酸银溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,380℃焙烧4h,得到催化剂C1。
实施例2
(1)含镍拟薄水铝石
将4L浓度为50g Al2O3/L的硝酸铝溶液和0.5L浓度为14.5g NiO/L的硝酸镍溶液混合均匀装入高位处的容器内,配制浓度为8wt%的氨水溶液装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有2L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度55℃,控制流量调节反应体系PH值为7.7,反应结束后,加入氨水调节调节浆液PH值8.6,老化30分钟,过滤分离母液,洗涤。120℃干燥5h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与碳酸锂、硝酸、磷酸、柠檬酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,940℃焙烧4h,得到含镍和锂的载体。
(3)催化剂
将醋酸镍、硝酸银溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,420℃焙烧4h,得到催化剂C2。
对比例1
(1)拟薄水铝石
配制4L浓度为50g Al2O3/L的硝酸铝溶液和浓度为8wt%的氨水溶液分别装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有2L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度45℃,控制流量调节反应体系PH值为8.0,反应结束后,加入氨水调节调节浆液PH值8.5,老化40分钟,过滤分离母液,洗涤。在120℃干燥2h,得拟薄水铝石。
(2)载体
称取制备的拟薄水铝石,与硝酸、柠檬酸、磷酸、田菁粉、碳酸锂和水混合捏合成可塑体,挤条成型,然后在120℃干燥6h,920℃焙烧4h,得到含锂的载体。
(3)催化剂
将硝酸镍和硝酸银溶解于水中制成浸渍液,浸渍到(2)中制备的80g载体上,120℃烘干,450℃焙烧3h,得到催化剂D1。
实施例3
(1)含镍拟薄水铝石
将1L浓度为50g Al2O3/L的硫酸铝溶液和0.5L浓度为6g NiO/L的硝酸镍溶液混合均匀装入高位处的容器内,配制浓度为50g Al2O3//L偏铝酸钠溶液3L装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有2L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度60℃,控制流量调节反应体系PH值为9,通过滴加氨水调节浆液PH值为9.6,反应结束后老化30分钟,过滤分离母液,洗涤。在90℃干燥3h,120℃干燥2h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸、磷酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,600℃焙烧4h,得到含镍载体前体。配制硝酸镁、碳酸锂和柠檬酸水溶液,采用等体积浸渍法浸渍到含镍载体前体上,在120℃干燥4h,960℃焙烧4h,得到含镍、镁和锂的载体。
(3)催化剂
将醋酸镍、硝酸银溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,360℃焙烧4h,得到催化剂C3。
对比例2
(1)拟薄水铝石
将1L浓度为50g Al2O3/L的硫酸铝溶液和3L浓度为50g Al2O3/L偏铝酸钠溶液分别装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有2L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度50℃,控制流量调节反应体系pH值为9,通过滴加氨水调节浆液pH值为9.5,反应结束后老化30分钟,过滤分离母液,洗涤。在90℃干燥3h,120℃干燥2h,得拟薄水铝石。
(2)载体
称取制备的拟薄水铝,与碳酸锂、硝酸、磷酸、柠檬酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,940℃焙烧4h,制得载体。
(3)催化剂
采用两步浸渍法制备催化剂。第一步,硝酸镍和硝酸镁溶于水配制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,浸渍硝酸镍总量的60%。120℃烘干,350℃焙烧4h,第二步采用等体积浸渍法浸渍硝酸银和剩余硝酸镍总量的40%,120℃烘干,380℃焙烧4h,得到催化剂D2。
实施例4
(1)含镍拟薄水铝石
将2L浓度为22.5g Al2O3/L的硫酸铝溶液和1L浓度为15.8g NiO/L的硝酸镍溶液混合均匀装入高位处的容器内,配制浓度为50g Al2O3/L偏铝酸钠溶液3L装入高位处的容器内,两容器下连蠕动泵进行流速控制流入装有2L底水的带搅拌器且罐底可通入气体的不锈钢容器内,反应温度65℃,控制流量调节反应体系PH值为9.0,通过滴加氨水调节浆液pH值为9.5,反应结束后老化40分钟,过滤分离母液,洗涤。在120℃干燥4h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸铈、硝酸、磷酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,1050℃焙烧4h,得到含镍和铈的载体。
(3)催化剂
将醋酸镍、硝酸银溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,400℃焙烧4h,得到催化剂C4。
对比例3
本对比例按照CN1123392C中实施例描述的方法制备含镍载体,具体步骤如下:
称取200g氢氧化铝干胶粉和8.5g田菁粉混合均匀后,再称取38g炭黑和11.65g碱式碳酸镍混合均匀后,在其中加入先前已用量筒量取的的四丁基氢氧化铵(其中C16H37NO的含量约10w%)67ml,用玻璃棒搅拌,使四丁基氢氧化铵溶液与混合物充分接触,放置35分钟后,将其加入到混有田菁粉的氢氧化铝干胶粉中,再次混匀;
将乙酸和柠檬酸、去离子水的混合溶液,加入到混有碱式碳酸镍、炭黑和田菁粉的氢氧化铝干胶粉中,混捏成均匀的膏状可塑物后,在挤条机上挤成三叶草形条,于120℃下干燥3.5小时,550℃焙烧4h,制得含镍载体前体。配制硝酸铈水溶液,采用等体积浸渍法浸渍到含镍载体前体上,110℃干燥6h,1020℃焙烧4h,得到含镍和铈载体。
将硝酸镍和硝酸银共同溶解于水中制成浸渍液,浸渍到上述制备的80g含镍载体上,120℃烘干,460℃焙烧4h,得到催化剂D4。
实施例1-8中催化剂C1~C8和对比例1-4中催化剂D1~D4催化剂物性和组成见表1。
实施例5
(1)含镍拟薄水铝石
将4L浓度为50g Al2O3/L的偏铝酸钠溶液置于带搅拌器且罐底可通入气体的不锈钢容器内,1L浓度为8.95g NiO/L的硝酸镍溶液装入高位处的容器内,下连蠕动泵进行流速控制。通入二氧化碳和空气的混合气体,同时滴加配制好的硝酸镍溶液,混合气体中二氧化碳浓度为60v%,流量4Nm3/h。反应温度35℃,反应终点PH值9.7,停止通入二氧化碳,老化35分钟,过滤分离母液,洗涤。在110℃干燥6h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸、磷酸、田菁粉、硝酸镧和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,580℃焙烧4h,得到含镍和镧的载体前体。配制碳酸锂和柠檬酸水溶液,采用等体积浸渍法浸渍到含镍和镧载体前体上,在120℃干燥4h,1020℃焙烧4h,得到含镍、镧和锂的载体。
(3)催化剂
将醋酸镍、硝酸银共同溶解于水中制成浸渍液,浸渍到(2)中制备的80g载体上,120℃烘干,450℃焙烧3h,得到催化剂C5。
对比例4
(1)拟薄水铝石
将4L浓度为50g Al2O3/L的偏铝酸钠溶液置于带搅拌器且罐底可通入气体的不锈钢容器内,通入二氧化碳和空气的混合气体,混合气体中二氧化碳浓度为70v%,流量3Nm3/h。反应温度35℃,反应终点PH值9.5,停止通入二氧化碳,老化30分钟,过滤分离母液,洗涤。在90℃干燥3h,120℃干燥2h,得拟薄水铝石。
(2)载体
称取制备的拟薄水铝石,与硝酸、磷酸、柠檬酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,650℃焙烧4h,得到载体前体。配制硝酸镧、碳酸锂和柠檬酸水溶液,采用等体积浸渍法浸渍到载体上,在110℃干燥6h,990℃焙烧4h,得到含镧和锂的载体。
(3)催化剂
将醋酸镍、硝酸银溶解于水中制成浸渍液,浸渍到(2)中制备的80g载体上,120℃烘干,410℃焙烧5h,得到催化剂D3。
实施例6
(1)含镍拟薄水铝石
将4L浓度为46.25g Al2O3/L的偏铝酸钠溶液置于带搅拌器且罐底可通入气体的不锈钢容器内,1L浓度为12.45g NiO/L的硝酸镍溶液装入高位处的容器内,下连蠕动泵进行流速控制。通入二氧化碳和空气的混合气体,同时滴加配制好的硝酸镍溶液,混合气体中二氧化碳浓度为70v%,流量3Nm3/h。反应温度35℃,反应终点PH值9.5,停止通入二氧化碳,老化45分钟,过滤分离母液,洗涤。120℃干燥4h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与碳酸锂、硝酸、磷酸、柠檬酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,1000℃焙烧4h,得到含镍载体。
(3)催化剂
将硝酸镍、硝酸银和硝酸镧溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,350℃焙烧4h,得到催化剂C6。
实施例7
(1)含镍拟薄水铝石
将4L浓度为50g Al2O3/L的偏铝酸钠溶液置于带搅拌器且罐底可通入气体的不锈钢容器内,通入二氧化碳和空气的混合气体,混合气体中二氧化碳浓度为60v%,流量3Nm3/h。反应温度35℃,反应终点PH值10,停止通入二氧化碳。通空气搅拌条件下,加入1L浓度为5.13g NiO/L的硝酸镍溶液,稳定25分钟后,通过滴加氨水调节浆液PH值为9.5,反应结束后老化30分钟,过滤分离母液,洗涤。在90℃干燥3h,120℃干燥2h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸、磷酸、柠檬酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,1100℃焙烧4h,得到含镍载体。
(3)催化剂
将醋酸镍、硝酸银溶于水中制成浸渍液,采用等体积浸渍法浸渍到(2)中制备的80g载体上,120℃烘干,370℃焙烧4h,得到催化剂C7。
实施例8
(1)含镍拟薄水铝石
将4L浓度为50g Al2O3/L的偏铝酸钠溶液置于带搅拌器且罐底可通入气体的不锈钢容器内,通入二氧化碳和空气的混合气体,混合气体中二氧化碳浓度为60v%,流量4Nm3/h。反应温度35℃,反应终点PH值10,停止通入二氧化碳。通空气搅拌条件下,加入1L浓度为18.6g NiO/L的硝酸镍溶液,稳定25分钟后,通过滴加氨水调节浆液PH值为9.5,反应结束后老化40分钟,过滤分离母液,洗涤。在120℃干燥4h,制得含镍拟薄水铝石。
(2)含镍载体
称取制备的含镍拟薄水铝石,与硝酸镧、硝酸、柠檬酸、磷酸、田菁粉和水混合捏合成可塑体,挤条成型,然后在120℃干燥4h,980℃焙烧4h,得到含镍载体。
(3)催化剂
采用两步等体积浸渍法浸渍到(2)中制备的80g载体上,第一步配成总镍含量40%的醋酸镍溶液浸渍载体,120℃烘干,350℃焙烧4h,第二步将硝酸镍和硝酸银溶于水中制成浸渍液,加入剩余60%的镍含量,120℃烘干,380℃焙烧4h,得到催化剂C8。
表1实施例催化剂及对比例催化剂物性和组成
催化剂评价:
采用裂解汽油为原料,原料性质见表2,对C1~C8和D1~D4催化剂进行评价。分别评价300h,每12h取样分析溴价和双烯,平均数据见下表3。
催化剂评价是在100ml绝热床加氢反应装置上进行的,催化剂首先在380~450℃氢气下还原10小时,然后降温到35℃,用含二甲基二硫1000ppm的环己烷钝化4h后进原料油。评价工艺条件:反应压力:2.8MPa,入口温度:50℃,新鲜原料油空速:3.0h-1,氢与油体积比:200∶1(体积比以新鲜油计)。
表2加氢原料油性质
表3催化剂评价平均数据
从以上实施例和对比例可以看出,采用本发明含镍氧化铝制备的镍-银系加氢催化剂,在相同的评价工艺条件下,加氢产品的双烯、溴价相对较低,这充分说明了实施例中制备的催化剂具有较高的加氢活性和选择性。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (25)
1.一种镍-银系加氢催化剂,催化剂中含有活性组分镍和银,以含镍氧化铝为载体,其特征在于:以催化剂重量为100wt%计,含有氧化镍10~20wt%,氧化银0.01~3wt%,氧化铈和/或氧化镧0~5wt%,碱金属和/或碱土金属氧化物0~6wt%;催化剂比表面积50~150m2/g,孔容0.25~0.55cm3/g,堆密度0.5~1.1g/cm3;含镍氧化铝载体的前驱体是含镍拟薄水铝石;含活性组分溶液浸渍含镍氧化铝载体,经干燥、焙烧,制得镍-银系加氢催化剂;
其中,该含镍拟薄水铝石的制备过程包括以下步骤:
(1)中和釜中加入底水,底水为去离子水,加热到50~90℃;
(2)分别配制酸性铝盐水溶液、酸性镍盐水溶液,将酸性铝盐水溶液和酸性镍盐水溶液混合均匀,得到含铝盐和镍盐的酸性水溶液,调节其溶液温度为50~90℃;
(3)配制碱金属铝酸盐溶液;
(4)将(2)和(3)并流加入(1)中,持续通风搅拌;
(5)控制步骤(4)成胶温度50~90℃,成胶pH值7~10;
(6)成胶结束后,经老化、过滤、洗涤、干燥制得含镍拟薄水铝石。
2.根据权利要求1所述的镍-银系加氢催化剂,其特征在于:含镍拟薄水铝石的比表面积300~420m2/g,孔容为0.7~1.2cm3/g,孔径为5~10nm;以含镍拟薄水铝石总重量为100wt%计,镍含量为0.1~10wt%。
3.根据权利要求1所述的镍-银系加氢催化剂,其特征在于:以含镍氧化铝载体总重量为100%计,含镍氧化铝载体的镍含量为0.1~10wt%,比表面积25~250m2/g,孔容为0.15~0.85cm3/g,孔径为8~40nm。
4.根据权利要求1所述的镍-银系加氢催化剂,其特征在于:含镍氧化铝载体由含镍拟薄水铝石经成型、焙烧而得到,含有δ-Al2O3、δ-NiAl26O40和NiAl2O4晶型,且XRD谱图中0.45≤B1/B2≤0.85,B1是指XRD谱图中2θ为34.2~39.8°的峰的积分强度,B2是指XRD谱图中2θ为43.3~48.5°的峰的积分强度。
5.根据权利要求1所述的镍-银系加氢催化剂,其特征在于:含镍氧化铝载体中δ-Al2O3、δ-NiAl26O40和NiAl2O4占含镍氧化铝载体总重量的30~100wt%。
6.根据权利要求1所述的镍-银系加氢催化剂,其特征在于:含镍氧化铝载体中还含有θ-Al2O3、α-Al2O3和/或γ-Al2O3。
7.根据权利要求4所述的镍-银系加氢催化剂,其特征在于:含镍氧化铝载体焙烧条件为:800~1200℃焙烧4~10h。
8.根据权利要求1所述的镍-银系加氢催化剂,其特征在于,以催化剂重量为100wt%计,含有氧化镍14.5~18.2wt%,氧化银0.05~1.5wt%,氧化铈和/或氧化镧0.2~1.2wt%,碱金属和/或碱土金属氧化物0.5~3wt%。
9.根据权利要求2所述的镍-银系加氢催化剂,其特征在于,以含镍拟薄水铝石总重量为100wt%计,镍含量为0.5~5wt%。
10.根据权利要求3所述的镍-银系加氢催化剂,其特征在于,以含镍氧化铝载体总重量为100%计,含镍氧化铝载体的镍含量为0.5~5wt%。
11.根据权利要求6所述的镍-银系加氢催化剂,其特征在于,含镍氧化铝载体中α-Al2O3含量低于30wt%。
12.根据权利要求7所述的镍-银系加氢催化剂,其特征在于,含镍氧化铝载体焙烧温度为850~1100℃。
13.一种权利要求1所述的镍-银系加氢催化剂的制备方法,其特征在于:用含镍和银的溶液通过一步或多步浸渍含镍氧化铝载体,后经干燥、焙烧而得催化剂;含镍氧化铝载体由含镍拟薄水铝石经成型、焙烧而得到;其中含镍拟薄水铝石由下述方法得到,具体过程包括如下步骤:
(1)中和釜中加入底水,底水为去离子水,加热到50~90℃;
(2)分别配制酸性铝盐水溶液、酸性镍盐水溶液,将酸性铝盐水溶液和酸性镍盐水溶液混合均匀,得到含铝盐和镍盐的酸性水溶液,调节其溶液温度为50~90℃;
(3)配制碱金属铝酸盐溶液;
(4)将(2)和(3)并流加入(1)中,持续通风搅拌;
(5)控制步骤(4)成胶温度50~90℃,成胶pH值7~10;
(6)成胶结束后,经老化、过滤、洗涤、干燥制得含镍拟薄水铝石。
14.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(1)中的中和釜的釜底通入空气。
15.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(2)中调节所述酸性水溶液的温度为50~70℃。
16.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(5)中,成胶温度50~70℃;成胶pH值7.5~9.5。
17.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(3)中碱金属铝酸盐溶液的pH值为9~14。
18.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:酸性铝盐水溶液为氯化铝、硫酸铝及硝酸铝中的一种或几种的混合溶液;酸性镍盐水溶液是氯化镍、硫酸镍、溴化镍及硝酸镍中的一种或几种的混合溶液;碱金属铝酸盐溶液是指偏铝酸钠或偏铝酸钾溶液。
19.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(2)中,酸性铝盐和酸性镍盐水溶液混合,得到含铝盐和镍盐的酸性水溶液,pH值为2~5。
20.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:步骤(6)中,老化温度为50~80℃,老化时间为10~60min。
21.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于:用含镍和银的溶液通过一步或多步浸渍含镍氧化铝载体,后经干燥、焙烧制得催化剂;其焙烧条件为:300~500℃下焙烧3~8h。
22.根据权利要求13所述的镍-银系加氢催化剂的制备方法,其特征在于,酸性铝盐水溶液浓度为10~80g Al2O3/L,酸性镍盐水溶液浓度为3~50g NiO/L;碱金属铝酸盐溶液浓度为50~300g Al2O3/L。
23.根据权利要求17所述的镍-银系加氢催化剂的制备方法,其特征在于,步骤(3)中碱金属铝酸盐溶液的pH值为12~14。
24.根据权利要求18所述的镍-银系加氢催化剂的制备方法,其特征在于,酸性铝盐水溶液为硫酸铝溶液;酸性镍盐水溶液是硝酸镍溶液。
25.根据权利要求19所述的镍-银系加氢催化剂的制备方法,其特征在于,含铝盐和镍盐的酸性水溶液pH值为2~4。
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