CN108786930B - A kind of body phase hydrotreating catalyst and its preparation method - Google Patents
A kind of body phase hydrotreating catalyst and its preparation method Download PDFInfo
- Publication number
- CN108786930B CN108786930B CN201710299558.8A CN201710299558A CN108786930B CN 108786930 B CN108786930 B CN 108786930B CN 201710299558 A CN201710299558 A CN 201710299558A CN 108786930 B CN108786930 B CN 108786930B
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- catalyst
- tank
- active metal
- solution
- salt solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 143
- 239000002184 metal Substances 0.000 claims abstract description 142
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 238000009826 distribution Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 94
- 230000032683 aging Effects 0.000 claims description 93
- 239000002253 acid Substances 0.000 claims description 80
- 239000012266 salt solution Substances 0.000 claims description 73
- 239000002608 ionic liquid Substances 0.000 claims description 72
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 42
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 39
- 159000000013 aluminium salts Chemical class 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- -1 alkyl ammonium halide Chemical class 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 24
- 229910052593 corundum Inorganic materials 0.000 claims description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 20
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- HGSHBQLEBLRBJS-UHFFFAOYSA-N N.[Mo].[Ni] Chemical compound N.[Mo].[Ni] HGSHBQLEBLRBJS-UHFFFAOYSA-N 0.000 claims description 3
- HLLDCWDCVRXWPL-UHFFFAOYSA-N N.[Ni].[W] Chemical compound N.[Ni].[W] HLLDCWDCVRXWPL-UHFFFAOYSA-N 0.000 claims description 3
- ACVSDIKGGNSZDR-UHFFFAOYSA-N [P].[W].[Ni] Chemical compound [P].[W].[Ni] ACVSDIKGGNSZDR-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- TUCBLWPBHKALLL-UHFFFAOYSA-N N.[Co].[W] Chemical compound N.[Co].[W] TUCBLWPBHKALLL-UHFFFAOYSA-N 0.000 claims description 2
- BOWNUAQMFDGHCC-UHFFFAOYSA-N N.[Mo].[Co] Chemical compound N.[Mo].[Co] BOWNUAQMFDGHCC-UHFFFAOYSA-N 0.000 claims description 2
- NMVXOYKMHMQNDK-UHFFFAOYSA-N N.[Ni].[Co].[Mo] Chemical compound N.[Ni].[Co].[Mo] NMVXOYKMHMQNDK-UHFFFAOYSA-N 0.000 claims description 2
- FEBFYWHXKVOHDI-UHFFFAOYSA-N [Co].[P][W] Chemical compound [Co].[P][W] FEBFYWHXKVOHDI-UHFFFAOYSA-N 0.000 claims description 2
- AXFKVYBBROZOGA-UHFFFAOYSA-N [P].[Mo].[Co] Chemical compound [P].[Mo].[Co] AXFKVYBBROZOGA-UHFFFAOYSA-N 0.000 claims description 2
- WYWPWLUDBKATGV-UHFFFAOYSA-N [P].[Mo].[Ni].[Co] Chemical compound [P].[Mo].[Ni].[Co] WYWPWLUDBKATGV-UHFFFAOYSA-N 0.000 claims description 2
- FIOBDUSJUICPHU-UHFFFAOYSA-N [P].[W].[Ni].[Co] Chemical compound [P].[W].[Ni].[Co] FIOBDUSJUICPHU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 8
- ZNJFJXIVBHBQFQ-UHFFFAOYSA-N N.[Co].[Ni].[W] Chemical compound N.[Co].[Ni].[W] ZNJFJXIVBHBQFQ-UHFFFAOYSA-N 0.000 claims 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract description 6
- 239000008187 granular material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 3
- 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 description 17
- 239000011259 mixed solution Substances 0.000 description 14
- 238000005352 clarification Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000026030 halogenation Effects 0.000 description 8
- 238000005658 halogenation reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- GUPIWSVHCZDPCH-UHFFFAOYSA-M dibutyl(dipropyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCC)(CCC)CCCC GUPIWSVHCZDPCH-UHFFFAOYSA-M 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- ZRVJNMZHHALBIB-UHFFFAOYSA-N n-butyl-2-methylpentan-2-amine Chemical compound CCCCNC(C)(C)CCC ZRVJNMZHHALBIB-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- BKILWHYRLBCASZ-UHFFFAOYSA-M 2-[bis(2-hydroxyethyl)amino]ethanol;2-hydroxypropanoate;phenylmercury(1+) Chemical compound CC(O)C([O-])=O.[Hg+]C1=CC=CC=C1.OCCN(CCO)CCO BKILWHYRLBCASZ-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKVQMFQSQWKAGT-UHFFFAOYSA-M CCCC[Mg+].N.[Cl-] Chemical compound CCCC[Mg+].N.[Cl-] OKVQMFQSQWKAGT-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- OJJATAQZZRDKQR-UHFFFAOYSA-N N-butyl-4-propylheptan-4-amine Chemical compound C(CC)C(CCC)(NCCCC)CCC OJJATAQZZRDKQR-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- FPWHKJDNPLBNSI-UHFFFAOYSA-N [OH-].[NH4+].[Ni].[Mo] Chemical compound [OH-].[NH4+].[Ni].[Mo] FPWHKJDNPLBNSI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HDITUCONWLWUJR-UHFFFAOYSA-N diethylazanium;chloride Chemical compound [Cl-].CC[NH2+]CC HDITUCONWLWUJR-UHFFFAOYSA-N 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- KSFUSYZPOPLNKH-UHFFFAOYSA-N n,n-dibutylpentan-2-amine Chemical class CCCCN(CCCC)C(C)CCC KSFUSYZPOPLNKH-UHFFFAOYSA-N 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses a kind of body phase hydrotreating catalyst and its preparation method, which is spheric granules, and pore-size distribution has the property that the average pore size d at catalyst granules center to x*R range1It is average pore size d of 0.1 ~ 0.9, the x*R to catalyst external surface for 50 ~ 100nm, x2For 120 ~ 180nm, d2‑d1=40~130nm；Wherein R is the particle radius of body phase hydrogenation catalyst.Body phase hydrotreating catalyst has the property that specific surface area is 250~350m20.8~1.0mlg of/g, Kong Rongwei‑1；Average pore size is 50~150nm.Active metal and assistant concentration are gradually increased by granular center to outer surface.Body phase hydrotreating catalyst pores of the invention are held and aperture is larger, it is greater than internal aperture with outer surface aperture simultaneously, catalyst table phase active metal density is bigger, and hydrogenation active metals utilization rate and catalytic inner utilization rate are higher, catalyst deactivation rate is reduced, catalyst life is improved.The method of the present invention realizes the continuous production of hydrogenation catalyst simultaneously, improves production efficiency, reduces production cost.
Description
Technical field
The present invention relates to distillate hydrogenation fields, more particularly to a kind of body phase hydrotreating catalyst and its preparation method.
Background technique
The aperture of residual oil hydrocatalyst is generally concentrated at 8-15nm, and catalyst has very high initial activity.Residual oil raw material
Middle gum asphaltic content is higher and molecular diameter is from 10nm to several hundred nm, and the metal impurities in gum asphalt are deposited on
Uneven distribution is presented in catalyst particles intragranular more, more, the few trend of outside deposition of internal deposition is presented along catalyst particle size, mainly
It is due to the random arrangement in different size duct in catalyst, metal impurities deposit to outer surface and aperture is caused to block, to lead
Cause internal effective macropore and active phase metal to be unable to get effective use, greatly reduce catalyst utilization rate and
Service life.In order to realize desulfurization, denitrogenation, de- carbon residue catalyst long-term operation, catalyst guarantee desulfurization, denitrogenation, take off it is residual
While charcoal, it is necessary to improve the appearance metal ability of catalyst, it is necessary to improve 30nm to micron-sized duct ratio, while control hole
Distribution of the diameter inside catalyst granules can be improved the utilization rate of catalyst and prolong the service life.
Residual catalyst is mostly load hydrogenation catalyst at present, and Ti Xiang hydrotreating catalyst active center density is wanted
It is much higher, there is superelevation desulfurization, denitrogenation and metal removal activity, however coprecipitation prepares bulk phase catalyst technology, using difference
Coprecipitation mode, Gelation Conditions etc. can add active metallic content on channel surfaces in catalyst and activated centre density, difference
Interaction relationship has a great impact between the distribution of hydrogen activity metal and different hydrogenation active metals, while catalyst is small
Hole ratio is more.The distribution of different hydrogenation active metals can be made to be not easily controlled using coprecipitation, to influence different plus hydrogen
The distribution of active metal reduces the interaction between active metal, while table phase active metallic content is small and living in catalyst
Property density metal it is lower, the final Hydrogenation for influencing catalyst.Therefore, the distribution for how regulating and controlling hydrogenation active metals makes to add
There is suitable mating reaction between hydrogen activity metal component, how to increase in catalyst in table phase active metallic content and activity
Heart density improves the utilization rate of hydrogenation active metal component, is the key that improve catalyst hydrogenation performance.
CN101927197A is related to a kind of active metal and acidic assistant concentration reduces the hydrogenation catalyst of distribution in gradient
And preparation method.This method is by preparing denseer active metal solution and acid additive solution, during carrier impregnation, by
Step addition deionized water or the method for ammonium hydroxide dilute solution are saturated spray-stain carrier；This method is using repeatedly dipping, dry and roasting
Burning process, the dipping of multiple active metal and roasting easily cause the blocking of catalyst pore structure and the destruction in duct.
The invention discloses a kind of bulk phase catalysts and preparation method thereof by CN200910011648.8.The bulk phase catalyst is
It respectively obtains inorganic oxide precursor hydroxide gel and active metal hydroxide gel is that raw material roasts after forming
It obtains.In the bulk phase catalyst preparation process, due in hydroxide gel contain surfactant and hydrocarbon component, through at
After type and roasting, make the nanometer oxide particle formed after the hydroxide abjection moisture of polymerization that still there is rodlike basic knot
Structure, and it is piled into frame structure in disorder, making the Kong Rong great of the catalyst, aperture is big, and porosity is high, and outer surface orifice is larger,
Duct penetrability is good, is conducive to the deposition for increasing impurity, extends the operation cycle of catalyst.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of body phase hydrotreating catalyst and its preparation method.Of the invention
Body phase hydrotreating catalyst pores are held and aperture is larger, and outer surface aperture is greater than internal aperture, and active metal and auxiliary agent edge are urged
Agent partial size is in the trend that gradually increases from inside to outside, and catalyst table phase active metal density is bigger, hydrogenation active metals utilization rate
And catalytic inner utilization rate is higher, reduces catalyst deactivation rate, improves catalyst life.The method of the present invention is realized simultaneously
The continuous production of hydrogenation catalyst, improves production efficiency, reduces production cost.
Body phase processor hydrogenation catalyst of the invention is spheric granules, and pore-size distribution has the property that catalyst granules
Center (centre of sphere) to x*R range average pore size d1For 50 ~ 100nm, wherein x is 0.1 ~ 0.9, preferably 0.2 ~ 0.8, more preferably
It is 0.3 ~ 0.7；Catalyst granules x*R to catalyst external surface average pore size d2For 120 ~ 180nm, d2-d1=40~130nm ；
Wherein R is the particle radius of body phase hydrogenation catalyst.
Body phase hydrotreating catalyst of the invention has the property that specific surface area is 250~350m2/ g, Kong Rongwei
0.8~1.0mlg-1；Average pore size is 50~150nm, and wherein the pore size distribution of < 50nm accounts for total pore volume 2% ~ 8%, 50~100nm
The pore size distribution of pore size distribution 45% ~ 55%, the > 100nm that accounts for total pore volume account for total pore volume 35% ~ 45%.The aperture of catalyst external surface is big
In bulk phase catalyst average pore size, difference is 30 ~ 50nm.The pore structure of catalyst is measured using mercury injection method.
Body phase hydrotreating catalyst of the invention includes alumina support, active metal and auxiliary agent, wherein active metal
Selected from VIII group and/or group vib metallic element；On the basis of catalyst weight, the concentration of active metal and auxiliary agent is with oxide
Meter, gradually increased from catalyst granules center to outer surface, wherein 1/3R at active metal concentration be 6wt%~10wt%, 2/
The concentration of active metal is 10wt%~20wt% at 3R, and the concentration of active metal is 20wt%~30wt% at R；Assistant concentration is from urging
Catalyst particles center is gradually increased to outer surface, and wherein auxiliary agent content is 0.5wt%~1.0wt% at 1/3R, and auxiliary agent contains at 2/3R
Amount is 1.5wt%~2.0wt%, and auxiliary agent content is 2.5%wt~3.0wt% at R；R is that catalyst granules center is transversal to catalyst
The distance at face outer most edge any point.
In body phase hydrotreating catalyst of the invention, active metal in terms of oxide, group VIII metal be 1wt%~
9wt%, preferably 1.0wt%~5.0wt%, group vib metal are 5wt%~25wt%, and preferably 10wt%~20wt%, auxiliary agent is based on the element
For 2wt% ~ 5wt%, alumina support is 61wt% ~ 92wt%.
In body phase hydrotreating catalyst of the invention, when auxiliary agent is I, fluorine accounts for the 50%~55% of auxiliary agent quality, and phosphorus, which accounts for, to be helped
The 45%~50% of agent gross mass；When auxiliary agent is II, fluorine accounts for the 50%~55% of auxiliary agent quality, boron account for auxiliary agent gross mass 45%~
50%；When auxiliary agent is III, fluorine accounts for the 50%~55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, and boron accounts for auxiliary agent total amount
15%~20%.Active metal concentrations are measured using field emission scanning electron microscope on catalyst cross section.
Body phase hydrotreating catalyst of the invention, active metal is in terms of oxide, the weight of table phase active metal component
The ratio of content and the weight content of body phase active metal component is 3.0 ~ 15.0:1, preferably 3.0 ~ 14.0:1；Auxiliary agent based on the element,
The ratio of the weight content of table phase auxiliary agent and the weight content of body phase auxiliary agent is 3.0 ~ 10.0:1, preferably 3.0 ~ 5.0:1；The present invention urges
Agent one kind preferably constitutes are as follows: the weight content ratio of the active metal of table phase VIII group and body phase VIII group active metal is 2.0:
1 ~ 6.0:1, preferably 2.0 ~ 5.0:1, the weight content ratio of table phase VIB active metal and body phase VIB active metal be 2.0:1 ~
8.0:1, preferably 2.0:1 ~ 6.0:1.
In body phase hydrotreating catalyst of the invention, the weight content of table phase VIII group active metal is VIII in table phase
The weight content of race's active metal, the weight content of body phase VIII group active metal component are VIII group active metal in catalyst
Weight content；The weight content of table phase VIB active metal component is the weight content of VIB active metal in table phase, body phase VIB
The weight content of active metal is the weight content of VIB active metal in catalyst.Catalyst table phase active metallic content uses
X-ray photoelectron spectroscopy (XPS) measurement, caltalyst phase active metallic content use inductively coupled plasma body atomic emissions
Spectrum (ICP-AES) measurement.
The preparation method of body phase hydrotreating catalyst of the invention, including following content:
(1) bottom water of certain volume is added in reactor tank, swing tank and ageing can, is heated to certain temperature, then opens
Dynamic blender, charging I and charging II are continuous with the acid solution feed inlet of certain flow rate difference autoreaction tank top and lye feed inlet
It is added, adjusting pH value is 9.0 ~ 11.0, after a period of stabilisation, opens the overflow port of reaction pot bottom, makes to generate liquid stream to pendulum
In dynamic tank；Wherein the charging I is the mixture of acid aluminium salt solution I, acid active metal solution I and ionic liquid I, into
Material II is the mixture of basic aluminium salt solution I, basic activated metallic solution I；
(2) after the overflow port trickle of reactor tank, the acid solution feed inlet for swinging tank upper end, stream plus a certain concentration are opened
Acid aluminium salt solution II, acid active metal solution II and ionic liquid II, adjust pH value between 3.0~5.0, reaction one
After the section time, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into swing tank；
(3) after the overflow port trickle for swinging tank, the lye feed inlet of ageing can upper end, stream plus a certain concentration are opened
Basic aluminium salt solution II, basic activated metallic solution II and ionic liquid III, adjust pH value between 7.0~8.0, aging
After a period of time, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting
It burns, obtains body phase hydrotreating catalyst.
In the method for the present invention, the reactor tank, the volume for swinging bottom water in tank and ageing can account for the 1/5 of the tank volume
~1/4, the temperature of reactor tank is less than the temperature for swinging tank, and the temperature for swinging tank is less than the temperature of ageing can, the temperature of reactor tank
It is 50~80 DEG C, the temperature for swinging tank is 80~100 DEG C, and the temperature of ageing can is 100~120 DEG C；Reactor tank and swing tank it
Between temperature difference be 10~30 DEG C, swinging the temperature difference between tank and ageing can is 10~30 DEG C.The stirring rate of reactor tank is wanted
Higher than the stirring rate for swinging tank, the stirring rate for swinging tank is higher than the stirring rate of ageing can, the stirring rate of reactor tank
For 600~800rad/min, the stirring rate of agitator tank is 300~500rad/min, the stirring rate of ageing can is 100~
200rad/min, reactor tank and the rotational speed difference swung between tank are 50~150rad/min.
In the method for the present invention, the acid aluminium salt solution I, II can be AlCl3、Al2(SO4)3Or Al (NO)3It is water-soluble
One or more of liquid, preferably Al2(SO4)3、AlCl3Aqueous solution, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 10~
100g/100ml, the flow of acid aluminium salt solution are 5~50ml/min.
In the method for the present invention, the basic aluminium salt solution I, II are selected from NaAlO2Or KAlO2One of aqueous solution or two
Kind, preferably NaAlO2Aqueous solution, the concentration of basic aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/100ml, basic aluminium salt solution
Flow be 5~50ml/min.
In the method for the present invention, aluminium salt concentration is along Flow of Goods and Materials direction, reactor tank, swing tank and ageing can with Al2O3Meter is in
The trend gradually successively decreased, amplitude of successively decreasing are 20~50g/100ml.
In the method for the present invention, active metal salinity is along Flow of Goods and Materials direction, reactor tank, swing tank and ageing can with gold
Belong to oxide meter in gradually incremental trend, the amplitude that is incremented by is 20~50g/100ml.
In the method for the present invention, the concentration of acid aluminium salt solution I and basic aluminium salt solution I in step (1) is preferably identical, with
Al2O3Meter.
In the method for the present invention, the preferred phase of concentration of acid metal salt solution I and basic metal salt solutions I in step (1)
Together, in terms of metal oxide.
In the method for the present invention, the ionic liquid I is carbon atom number 1 ~ 4 alkyls ionic liquid, and alkyl is preferred
For one or more of methyl, ethyl, further preferably dimethyl and/or ethyl class ionic liquid, ionic liquid adds
Enter 0.5wt%~1.0wt% that amount accounts for step (1) inlet amount in terms of auxiliary element, wherein inlet amount is with aluminium oxide and active metal
The sum of oxide meter.
In the method for the present invention, one of alkyl ammonium halide that the ionic liquid II is carbon atom number 4 ~ 8 or several
Kind, further preferably triethyl group class and/or the positive class D of methyl three, the positive class D of dimethyl two, methylbenzene base class, 3,5-dimethylphenyl
One or more of class, trimethylbenzene base class ionic liquid etc., the additional amount of ionic liquid accounts for step (2) in terms of auxiliary element
1.5wt%~2.0wt% of inlet amount, wherein inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides.
In the method for the present invention, the ionic liquid III is in the alkyls ionic liquid that carbon atom number is 8 ~ 12
One or more, the preferably positive class D of methyl three, the positive class D of dimethyl two, methylbenzene base class, dimethyl benzene base class, trimethylphenyl
Class ionic liquid, three normal-butyl class of propyl, dipropyl di-n-butyl class ionic liquid.One or more of Deng, ionic liquid
Additional amount 2.5wt%~3.0wt% of step (3) inlet amount is accounted in terms of auxiliary element, wherein inlet amount is with aluminium oxide and activity
The sum of metal oxide meter.
In the method for the present invention, ionic liquid I, II and III preparation method can be used conventional method and carry out M generally1And M2
It is added to the water, is heated to reaction temperature under agitation, isothermal reaction, after reaction, cooling, centrifugation obtains ionic liquid
Body；Wherein M1With M2Molar ratio be 1:1~1:2, reaction condition be generally reaction temperature be 60~150 DEG C, preferably 70~100
DEG C, the isothermal reaction time is 1~4h, preferably 1~2h.The M1For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, six
One or more of fluorophosphoric acid ammonium, sodium hexafluoro phosphate and Potassium Hexafluorophosphate etc., preferably ammonium hexafluorophosphate and/or tetrafluoro boric acid
Ammonium.The M2One or more of the alkyl ammonium halide for being 1 ~ 13 for carbon atom number, alkyl are preferably methyl, in ethyl
One or more, the preferred chlorine of halogen, further preferably dimethy lammonium chloride and/or diethyl ammonium halide, halogenation triethyl group
Ammonium, halogenation tetraethyl ammonium, ethyl ammonium halide, halogenated methyl tri-n-butylamine, halogenation dimethyl di-n-butylamine, the positive fourth of halogenation propyl three
One of amine, halogenation dipropyl di-n-butylamine, halogenated methyl puratized agricultural spray, halogenation dimethyl puratized agricultural spray and halogenation trimethyl puratized agricultural spray etc. or
It is several, preferably one or more of halogenated methyl puratized agricultural spray and/or halogenation dimethyl di-n-butylamine, the preferred chlorine of halogen.
In the method for the present invention, described acid active metal salt solution I, II are molybdenum nickel phosphorus, molybdenum cobalt phosphorus, molybdenum cobalt nickel phosphorus, tungsten
One of nickel phosphorus, tungsten nickel phosphorus, tungsten nickel cobalt phosphorus or tungsten cobalt phosphorus aqueous solution, the concentration of acid active metal salt solution is with oxygen
Compound is calculated as 15~100g/100ml, and pH value is 1.0~4.0, and acid active metal saline solution flow is 5~50ml/min；
Described basic activated metal salt solution I, the II is molybdenum nickel ammonia, molybdenum cobalt ammonia, molybdenum cobalt nickel ammonia, tungsten nickel ammonia, tungsten nickel ammonia, tungsten nickel cobalt
One of ammonia or tungsten cobalt ammonia spirit, the concentration of basic activated metal salt solution is calculated as 15~100g/ with oxide
100ml, pH value are 10.0~12.0, and basic activated aqueous metal salt flow is 5~50ml/min.
The preparation method of acid active metal salt solution belongs to content well known to those skilled in the art, water-soluble with molybdenum nickel phosphorus
It is illustrated for liquid, the preparation method is as follows: molybdenum oxide and basic nickel carbonate is taken to be put into more mouthfuls of flasks, a certain amount of go is added
After ionized water, be stirred until vial matter is in pulpous state, be then slowly added phosphoric acid, wait startings reaction later again slowly plus
Heat, being kept for 90~110 DEG C of times of solution temperature is 1~3 hour, after stopping heating, filters to acquired solution, is then added while hot
Phosphoric acid adjusts the pH value of solution to 1.0~4.0 to arrive molybdenum nickel phosphorus aqueous solution.
The preparation method of basic activated metal salt solution belongs to content well known to those skilled in the art.It is molten with molybdenum nickel ammonium hydroxide
It is illustrated for liquid, specific preparation process is as follows: ammonium molybdate and nickel nitrate being taken to be put into more mouthfuls of flasks, a certain amount of go is added
After ionized water, be stirred until vial matter is in pulpous state, be then slowly added ammonium hydroxide, wait startings reaction later again slowly plus
Heat, being kept for 70~80 DEG C of times of solution temperature is 1~2 hour, after stopping heating, filters to acquired solution, is then added while hot
Ammonium hydroxide adjusts the pH of solution to 10.0~12.0 to arrive molybdenum nickel ammonia solution.
In the method for the present invention, acid aluminium salt solution and acid active metal salt solution in charging I described in step (1)
Volume flow ratio is 40:1~80:1, feeds II neutral and alkali aluminum salt solution and the volume flow ratio of basic activated metal salt solution is
40:1~80:1.
In the method for the present invention, acid aluminium salt solution and the volume flow ratio of acid active metal salt solution are in step (2)
15:1~35:1.
In the method for the present invention, step (3) neutral and alkali aluminum salt solution and the volume flow ratio of basic activated metal salt solution are
5:1~10:1.
In the method for the present invention, ageing time described in step (3) is 0.5~2.0h, preferably 0.5~1.5h.Step (4)
The drying temperature is 40~200 DEG C, preferably 60~150 DEG C；Drying time is 1~5 hour, preferably 2~4 hours.
In the method for the present invention, step (2) can be repeated as many times, and preferably 1 ~ 4 time；When odd-times repeats, swing in tank
Charging be basic aluminium salt solution II, acidity active metal salt solution II and ionic liquid II, adjusting pH value to 9.0~11.0 it
Between, remaining same step (2)；When even-times repeats, same to step (2).
Body phase hydrotreating catalyst of the invention can be used for distillate hydrogenation reaction, be particularly suitable for wax oil residual oil etc.
It is reacted in raw material as hydrogenation denitrogenation, removal of ccr by hydrotreating.
Present invention simultaneously provides the continuous production device of body phase hydrotreating catalyst, including reactor tank, swing tank and
Ageing can is composed in series；Setting acid solution feed inlet and lye feed inlet at the top of the reactor tank, centre are blender, and bottom is set
There is overflow port, overflow port is connected to through pipeline with tank top is swung；It swings tank top and acid/base liquid feed inlet is set, centre is stirring
Device, bottom are equipped with overflow port, and overflow port at the top of pipeline and ageing can through being connected to；Acid/base liquid feed inlet, bottom are set at the top of ageing can
Portion is equipped with discharge port；The acid/base liquid feed inlet connects corresponding material pipeline.
In apparatus of the present invention can also as needed after swinging tank increase certain amount swing tank, preferably 1 ~ 4
A swing tank swings serial communication between tank, the last one swings tank and is connected to ageing can.Apparatus of the present invention can also be according to need
It is in parallel that multiple ageing cans are set.
In apparatus of the present invention, swinging setting acid/base liquid feed inlet at the top of tank and ageing can is same feed inlet, when addition acid
Then it is acid feed inlet when property solution, is then alkaline feed inlet when alkaline solution is added.
Flow control valve is installed in the respective lines of the connection reactor tank, the overflow port for swinging tank and ageing can,
For controlling the flow of disengaging material.
Compared with prior art, body phase hydrotreating catalyst of the invention and continuous production method and device,
It has the advantage that
1, the method for the present invention utilizes different ionic liquid using different types of ionic liquid is added in coprecipitation process
With different space sizes, urged so that the aperture of the inward-facing certain thickness range of prepared hydrogenation catalyst appearance is greater than
Aperture inside agent effectively increases the aperture outside catalyst, and external aperture is not easy to plug, impurity can be easier into
Enter and deposit to catalytic inner, avoid the blocking in catalyst aperture, improve catalytic inner utilization rate, extends catalyst
Service life.
2, hydrogenation catalyst prepared by the method for the present invention, active metal and ionic liquid are introduced into using co-precipitation mode
In catalyst, after the auxiliary element and active metal coordination in ionic liquid, particle surface is deposited to by coprecipitation, is generated
Novel active metal phase precursor, active phase periphery can effectively be modified, improve active phase surface activity, weaken and live
Property metal and aluminium oxide between mutual rental, it is easier to be sulfided into the II class activity phase with higher hydrogenation activity, reduce
Do not have the formation of spinelle with hydrogenation efficiency；Furthermore the presence of ionic liquid and active metal ligand, it is more after roasting
Active metal can be exposed in catalyst channel surfaces, to improve the density of table phase active metal, bigger table is mutually lived
Property density metal substantially increase hydrodemetallization, desulfurization and the denitrification activity of catalyst, and the preparation method is simple, is produced into
This is low.
3, the method for the present invention catalyst is with bigger aperture, the bore diameter gradient optimized from inside to outside distribution and activity gold
Belong to and assistant concentration gradient distribution, the variation in one side bigger aperture and bore diameter gradient are that macromolecular is spread to catalytic inner
Straightway effective channel is provided, so that hydrogenation reaction is easier to enter catalytic inner reaction, improves internal benefit
With rate, solve the problems, such as that current catalyst utilization is not high；The active metal density of another aspect channel surfaces is bigger, activity
Higher, for hydrogenation reaction more in internal-response, more metal impurities deposit to catalytic inner, avoid impurity deposition and make
It is blocked at catalyst aperture, the problem of rapid deactivation；Furthermore the gradient distribution of active metal and assistant concentration is to entire catalyst
The activity distribution of particle has carried out the optimization of system, and active metal and auxiliary agent are in increasing trend from inside to outside, can make it difficult to
The macromolecular of reaction generates the small molecule for being easier to reaction first in the biggish extexine reaction in catalyst aperture, and then small point
Son enters the lesser inside in catalyst aperture and is further reacted, so that reactant outside catalyst to interior by carrying out reasonably
Gradation reaction, to optimize catalyst hydrogenation activity, improves the utilization rate of catalyst entirety.
4, the method for the present invention realizes pH value swing method continuous production spherical hydrogenation catalyst, improves the life of catalyst
Produce efficiency, while can the excellent hydrogenation catalyst of processability, it is more time saving and energy saving than intermittent, substantially increase plus hydrogen urge
The output of agent reduces production cost, and economic, environmental protection.
5, in the method for the present invention, the method swung using pH value, the hydrogenation catalyst aperture of preparation and hole hold larger, aperture
Distribution is concentrated, and the hydrodenitrogeneration and de- carbon residue for inferior raw materials such as wax oil, residual oil are well suited for.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of body phase hydrotreating catalyst continuous production device of the invention.
Wherein, 1- reactor tank；2- swings tank；3-ageing cans；1-1- acid solution feed inlet；1-2- lye feed inlet；1-3- overflows
Head piece；2-1- acid/base liquid feed inlet；3-1- acid/base liquid feed inlet.
Fig. 2 is the N of product in the embodiment of the present invention 22Absorption figure.
Fig. 3 is 2 gained catalyst SEM electromicroscopic photograph of the embodiment of the present invention.
Fig. 4 is SEM electromicroscopic photograph at 2 gained catalyst sectional view center of the embodiment of the present invention.
Fig. 5 is 2 gained catalyst sectional view proximity SEM electromicroscopic photograph of the embodiment of the present invention.
Specific embodiment
It is described in more detail below by preparation method of the specific embodiment to hydrogenation catalyst of the invention.Implement
Example is not only to the specific embodiment of the method for the present invention for example, constitute the limitation of the scope of the present invention.This hair
In bright method, the particle diameter distribution of catalyst is measured using laser fineness gage.The pore structure of catalyst uses mercury injection method
It is measured, catalyst table phase active metallic content is measured using x-ray photoelectron spectroscopy (XPS), and mutually activity is golden for caltalyst
Belong to content to measure using inductively coupled plasma atomic emission spectrum (ICP-AES).Outside catalyst granules center to catalyst
The measuring method of the average pore size of different location between surface: the Kong Rong of sample is first measured with low-temperature nitrogen adsorption method (BET), compares table
Then area and average pore size take a certain amount of sample to be placed in attrition of catalyst instrument, carry out grinding process to sample, add simultaneously
Add a certain amount of quartz sand to increase the rate of wear.When sample reduces to a certain extent by polishing partial size, sample weight is measured
Its pore structure is lost and measured again to amount, and the relationship of the sum of each section, Ke Yiji are equal to by the total Kong Rong of sample and specific surface area
The Kong Rong and specific surface area of the part polished off are calculated, and then calculates average pore size.Thus it determines from outer surface to particle
The average pore size of center different parts.
In the method for the present invention, swing the feed rate of tank and ageing can according to swing pH value that tank and ageing can require and
The concentration of each material is adjusted.Wherein the additional amount percentage of the ionic liquid in each tank of embodiment and comparative example is ion
Liquid accounts for the mass percent of each tank inlet amount in terms of auxiliary element, and inlet amount is with the sum of aluminium oxide and reactive metal oxides
Meter.Active component of the additional amount of active metal salt solution in each tank in terms of reactive metal oxides according to final catalyst contains
Amount requires.
Embodiment 1
The present embodiment introduces the preparation method of Mo, Ni original solution.The present embodiment only prepare a kind of concentration and ratio Mo,
Ni original solution can prepare the solution of other ratios and concentration according to the method introduced.
386g molybdenum oxide is taken, 123g basic nickel carbonate is put into more mouthfuls of flasks, after a certain amount of deionized water is added, is carried out
Stirring is in pulpous state up to vial matter, is then slowly added 86g phosphoric acid, waits startings reaction to be slowly heated again later, keeps solution
90~110 DEG C of times of temperature are 1~3 hour, after stopping heating, are filtered while hot to acquired solution, and phosphoric acid is then added by solution
PH value adjust to 1.0~4.0 to get arrive clear bottle green original solution.Solution composition is MoO3: 69.27g/100ml；
NiO:12.49g/100ml.
296g ammonium molybdate is taken, 105g nickel nitrate is put into more mouthfuls of flasks, after a certain amount of deionized water is added, is stirred
Until vial matter is in pulpous state, it is then slowly added 150g ammonium hydroxide, waits startings reaction to be slowly heated again later, keeps solution temperature
70~80 DEG C of times are 1~2 hour, after stopping heating, are filtered while hot to acquired solution, and ammonium hydroxide is then added by the pH tune of solution
It saves to 10.0~12.0 to get required solution is arrived.Solution composition is MoO3: 58.2g/100ml；NiO:10.5g/100ml.
Embodiment 2
Alkyl dimethyl ammonium chloride 300g, ammonium tetrafluoroborate 190g, pure water 450g, mixing are heated to 80 DEG C, constant temperature under stiring
After 1h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, yield
73wt%。
Triethyl ammonium chloride 400g, sodium hexafluoro phosphate 220g, pure water 450g, mixing are heated to 90 DEG C, constant temperature under stiring
After 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain II 450g of ionic liquid, aqueous about 3.5wt%, yield
72wt%。
Propyl three n-butylmagnesium chloride ammonium 600g, sodium hexafluoro phosphate 360g, pure water 550g, mixing, are heated to 90 under stiring
DEG C, after constant temperature 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains III 750g of ionic liquid, it is aqueous about
3.7wt%, yield 76wt%.
The bottom water of 2L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 60 DEG C, swings tank
90 DEG C are heated to, ageing can is heated to 120 DEG C, and reactor tank stirring rate is adjusted to 600rad/min, swings tank speed of agitator
It is adjusted to 400rad/min；Ageing can speed of agitator is adjusted to 200rad/min；I(concentration will be fed with the flow velocity of 60ml/min
For 100g/100mlAl2O3Aluminum sulfate solution, 60g/100ml acidity active metal salt solution and ionic liquid I(additional amount with
Auxiliary element is calculated as 0.5%) being added from acid solution feed inlet, and will feed II(concentration with the flow velocity of 60ml/min is 100g/100ml
Al2O3Sodium aluminate solution, the basic activated metal salt solution of 60g/100ml) be added from lye feed inlet, adjust pH value to 9.5
Between, after stablizing 10min, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank；It opens and swings tank upper end
Acid feed inlet, addition concentration be 80g/100mlAl2O3Aluminum sulfate solution, 80g/100ml acidity active metal salt solution
With the mixed solution of ionic liquid II (additional amount is calculated as 1.5% with auxiliary element), pH value is adjusted to 3.0, after reacting 20min, is opened
The overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, aging is opened
The alkaline feed inlet of tank upper end, addition concentration are 60g/100ml Al2O3Sodium aluminate solution, 100g/100ml it is basic activated
The mixed solution of metal salt solution and ionic liquid III (additional amount is calculated as 2.7% with auxiliary element), adjusting pH value to 8.0, aging
After 2h, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting, is obtained
To body phase hydrotreating catalyst A.
As seen from Figure 2, the average pore size of each work-in-process gradually increases in preparation process, wherein I generation in Fig. 2
Particle, the II of table 0.3R represents the particle of 0.7R, III represents final catalyst prod.
Embodiment 3
Diethylammonium chloride 250g, ammonium tetrafluoroborate 180g, pure water 400g, mixing are heated to 90 DEG C, constant temperature under stiring
After 1.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 260g, aqueous about 3.5wt%, receives
Rate 73wt%.
Triethyl ammonium chloride 300g, sodium hexafluoro phosphate 160g, pure water 350g, mixing are heated to 100 DEG C, perseverance under stiring
After warm 2.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain II 420g of ionic liquid, aqueous about 3.7wt%,
Yield 72wt%.
Dipropyl di-n-butyl ammonium chloride 400g, sodium hexafluoro phosphate 340g, pure water 600g, mixing, are heated under stiring
90 DEG C, after constant temperature 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains III 710g of ionic liquid, it is aqueous about
3.8wt%, yield 72wt%.
The bottom water of 3L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 80 DEG C, swings tank
100 DEG C are heated to, tank is swung and is heated to 110 DEG C, reactor tank stirring rate is adjusted to 700rad/min, swings tank speed of agitator
It is adjusted to 500rad/min；Ageing can speed of agitator is adjusted to 200rad/min；Reactor tank upper end feed inlet is opened, with 80ml/
It is 95g/100mlAl that the flow velocity of min, which will feed I(concentration,2O3Aluminum sulfate solution, 55g/100ml acid metal solution and ion
1.0%) liquid I(additional amount is calculated as with auxiliary element) it is added from acid solution feed inlet, II will will be fed with the flow velocity of 30ml/min
(concentration is 95g/100ml Al2O3Sodium aluminate solution, 55g/100ml alkalinous metal solution) from lye feed inlet be added, adjust
PH value is saved between 11.0, after stablizing 20min, opens the overflow port of reaction pot bottom, makes to generate liquid stream to swinging in tank；It opens
The acid feed inlet for swinging tank upper end is opened, addition concentration is 75g/100mlAl2O3Aluminum sulfate, the acid activity gold of 75g/100ml
Belong to salting liquid and ionic liquid II(additional amount and mixed solution 2.0%) is calculated as with auxiliary element, adjusts pH value to 3.5, react
After 15min, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；The overflow port trickle of tank to be aging
Afterwards, the alkaline feed inlet of ageing can upper end is opened, addition concentration is 50g/100ml Al2O3Sodium aluminate solution, 90g/
The mixed solution of 100ml acidity active metal salt solution and ionic liquid III (additional amount is calculated as 3.0% with auxiliary element) is adjusted
PH value is to 7.5, after aging 1.5h, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, is passed through
Required body phase hydrotreating catalyst B is obtained after filter, dry and roasting.
Embodiment 4
Ammonio methacrylate 250g, ammonium tetrafluoroborate 150g, pure water 300g, mixing are heated to 90 DEG C, constant temperature under stiring
After 1.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, receives
Rate 73wt%.
Etamon chloride 450g, sodium hexafluoro phosphate 250g, pure water 500g, mixing are heated to 90 DEG C, constant temperature under stiring
After 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain II 650g of ionic liquid, aqueous about 3.9wt%, yield
75wt%。
Dipropyl di-n-butyl ammonium chloride 400g, sodium hexafluoro phosphate 340g, pure water 600g, mixing, are heated under stiring
90 DEG C, after constant temperature 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains III 710g of ionic liquid, it is aqueous about
3.8wt%, yield 72wt%.
The bottom water of 5L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 70 DEG C, swings tank
80 DEG C are heated to, ageing can is heated to 90 DEG C, and reactor tank stirring rate is adjusted to 650rad/min, swings tank speed of agitator tune
It is whole to arrive 500rad/min；Ageing can speed of agitator is adjusted to 200rad/min；Reactor upper end feed inlet is opened, with 90ml/min
Flow velocity will feed I(concentration be 100g/100mlAl2O3Aluminum sulfate solution, 50g/100ml acid metal salting liquid and ion
0.7%) liquid I(additional amount is calculated as with auxiliary element) it is added from acid solution feed inlet, it is dense that II(will be fed with the flow velocity of 50ml/min
Degree is 100g/100ml Al2O3Sodium aluminate solution, 50g/100ml basic metal salt solutions) from lye feed inlet be added, adjust
PH value is saved between 10.5, after stablizing 20min, opens the overflow port of reaction pot bottom, makes to generate liquid stream to swinging in tank；It opens
The acid feed inlet for swinging tank upper end is opened, addition concentration is 75g/100mlAl2O3Aluminum sulfate solution, 75g/100ml acidity it is living
Property metal salt solution and ionic liquid II(additional amount mixed solution 1.9%) is calculated as with auxiliary element, adjust pH value to 4.5, instead
After answering 20min, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；The overflow port efflux of tank to be aging
After body, the alkaline feed inlet of ageing can upper end is opened, addition concentration is 55g/100ml Al2O3Aluminum sulfate solution, 98g/
The mixed solution of 100ml acidity active metal salt solution and ionic liquid III (additional amount is calculated as 2.8% with auxiliary element) is adjusted
PH value is to 8.3, and after aging 2h, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, through filtering,
Required body phase hydrotreating catalyst C is obtained after dry and roasting.
Embodiment 5
Ammonio methacrylate 250g, ammonium tetrafluoroborate 150g, pure water 300g, mixing are heated to 90 DEG C, constant temperature under stiring
After 1.5h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I 300g, aqueous about 3.5wt%, receives
Rate 73wt%.
Etamon chloride 450g, sodium hexafluoro phosphate 250g, pure water 500g, mixing are heated to 90 DEG C, constant temperature under stiring
After 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain II 650g of ionic liquid, aqueous about 3.9wt%, yield
75wt%。
Dipropyl di-n-butyl ammonium chloride 400g, sodium hexafluoro phosphate 340g, pure water 600g, mixing, are heated under stiring
90 DEG C, after constant temperature 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtains III 710g of ionic liquid, it is aqueous about
3.8wt%, yield 72wt%.
The bottom water of 4L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 80 DEG C, swings tank
90 DEG C are heated to, ageing can is heated to 120 DEG C, and reactor tank stirring rate is adjusted to 700rad/min, swings tank speed of agitator
It is adjusted to 450rad/min, ageing can speed of agitator is adjusted to 150rad/min；Reactor upper end feed inlet is opened, with 110ml/
It is 100g/100mlAl that the flow velocity of min, which will feed I(concentration,2O3Aluminum sulfate solution, 55g/100ml acid metal salting liquid and from
0.6%) sub- liquid I(additional amount is calculated as with auxiliary element) it is added from acid solution feed inlet, II will be fed with the flow velocity of 80ml/min
(concentration is 100g/100ml Al2O3Sodium aluminate solution, 55g/100ml basic metal salt solutions) from lye feed inlet be added
PH value is adjusted between 11.0, after stablizing 10min, opens the overflow port of reaction pot bottom, makes to generate liquid stream to swinging in tank；
The acid feed inlet for swinging tank upper end is opened, addition concentration is 75g/100mlAl2O3Aluminum sulfate solution, 75g/100ml it is acid
Active metal salt solution and ionic liquid II(additional amount are calculated as mixed solution 1.8%) with auxiliary element, adjust pH value to 3.6,
After reacting 20min, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；The overflow port of tank to be aging flows out
After liquid, the alkaline feed inlet of ageing can upper end is opened, addition concentration is 80g/100ml Al2O3Sodium aluminate solution, 97g/
The mixed solution of the basic activated metal salt solution of 100ml and ionic liquid III (additional amount is calculated as 2.7% with auxiliary element) is adjusted
PH value is to 7.5, after aging 2.5h, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, is passed through
Required body phase hydrotreating catalyst D is obtained after filter, dry and roasting.
Comparative example 1
The bottom water of 2L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 60 DEG C, swings tank
90 DEG C are heated to, ageing can is heated to 90 DEG C；Reactor tank stirring rate is adjusted to 800rad/min, reactor tank speed of agitator tune
Whole to arrive 400rad/min, ageing can speed of agitator is adjusted to 200rad/min；Reactor upper end feed inlet is opened, with 60ml/min
Flow velocity will feed I(concentration be 98g/100mlAl2O3Aluminum sulfate solution and 57g/100ml acidity active metal solution) from acid
Liquid feed inlet is added, and will feed II(concentration with the flow velocity of 40ml/min as 98g/100ml Al2O3Sodium aluminate solution and
The basic activated metallic solution of 57g/100ml) it is added from lye feed inlet, between adjusting pH value to 9.0, after stablizing 10min, open
The overflow port for opening reaction pot bottom makes to generate liquid stream into swing tank；The acid feed inlet for swinging tank upper end is opened, concentration is added
For 69g/100mlAl2O3Aluminum sulfate solution and 78g/100ml acidity active metal salt solution mixed solution, adjust pH value to
3.0, after reacting 20min, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；The overflow port of tank to be aging
After trickle, the alkaline feed inlet of ageing can upper end is opened, addition concentration is 42g/100ml Al2O3Aluminum sulfate solution and
The mixed solution of 100g/100ml acidity active metal salt solution adjusts pH value to 8.0, after aging 2h, by the spherical shape of preparation
Catalyst precursor is discharged from the discharge port of aging pot bottom, obtains required body after roasting through filtering, drying and is added at hydrogen
Manage catalyst E.
Comparative example 2
The bottom water of 4L is added in reactor tank, swing tank and ageing can, the temperature of reactor tank is heated to 80 DEG C, swings tank
90 DEG C are heated to, ageing can is heated to 90 DEG C, and reactor tank stirring rate is adjusted to 700rad/min, swings tank speed of agitator tune
Whole to arrive 450rad/min, ageing can speed of agitator is adjusted to 200rad/min；Reactor upper end feed inlet is opened, with 110ml/
It is 100g/100mlAl that the flow velocity of min, which will feed I(concentration,2O3Aluminum sulfate solution and 55g/100ml acid metal solution) from acid solution
Feed inlet is added, and will feed II(concentration with the flow velocity of 80ml/min as 100g/100ml Al2O3Sodium aluminate solution and 55g/
The basic activated metallic solution of 100ml) it is added from lye feed inlet, between adjusting pH value to 3.5, after stablizing 10min, open anti-
The overflow port for answering pot bottom makes to generate liquid stream into swing tank；The alkaline feed inlet for swinging tank upper end is opened, concentration, which is added, is
80g/100mlAl2O3Sodium aluminate solution and the basic activated metallic solution of 74g/100ml adjust pH value to 11.0, react 20min
Afterwards, the overflow port for swinging pot bottom is opened, makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, open
The acid feed inlet of ageing can upper end is opened, addition concentration is 60g/100ml Al2O3Sodium aluminate solution and 95g/100ml alkali
Property active metal solution, pH value is adjusted to 7.5, after aging 2.5h, by the spheric catalyst presoma of preparation from ageing can bottom
The discharge port in portion is discharged, and required body phase hydrotreating catalyst F is obtained after filtering, drying and roasting.
Comparative example 3
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 100 DEG C, reactor tank stirring rate is adjusted to
800rad/min；Reactor upper end feed inlet is opened, will feed I(concentration with the flow velocity of 110ml/min is 85g/100mlAl2O3
Aluminum sulfate solution, 50g/100ml acid active metal solution and ionic liquid (additional amount is calculated as 2.0% with auxiliary element))
It is added from acid solution feed inlet, II(concentration will be fed as 100g/100ml Al with the flow velocity of 80ml/min2O3Sodium metaaluminate it is molten
The basic activated metallic solution and ionic liquid of liquid, 60g/100ml) it is added from lye feed inlet, between adjusting pH value to 8.2,
Stop feeding after reaction 2h, progress aging, after aging 2.5h, by the catalyst precursor of preparation unloading from aging pot bottom
Material mouth discharge, obtains required body phase hydrotreating catalyst G after filtering, drying and roasting.
Comparative example 4
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 80 DEG C, reactor tank stirring rate is adjusted to
250rad/min；Reactor upper end feed inlet is opened, will feed I(concentration with the flow velocity of 110ml/min is 85g/100mlAl2O3
Aluminum sulfate solution and 50g/100ml acid active metal solution mixed solution) from acid solution feed inlet be added, with 80ml/
It is 100g/100ml Al that the flow velocity of min, which will feed II(concentration,2O3Sodium aluminate solution and 60g/100ml basic activated gold
Belong to the mixed solution of solution) it is added from lye feed inlet, between adjusting pH value to 8.2, stop feeding after reaction 2h, carry out old
Change, after aging 2.5h, the catalyst precursor of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting
Required body phase hydrotreating catalyst H is obtained after burning.
Comparative example 5
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 100 DEG C, reactor tank stirring rate is adjusted to
500rad/min；Reactor upper end feed inlet is opened, will feed I(concentration with the flow velocity of 120ml/min is 90g/100mlAl2O3
Aluminum sulfate solution and 60g/100ml acid active metal solution mixed solution) from acid solution feed inlet be added, with 100ml/
It is 90g/100ml Al that the flow velocity of min, which will feed II(concentration,2O3Sodium aluminate solution and 80g/100ml basic activated metal
The mixed solution of solution) it is added from lye feed inlet, between adjusting pH value to 7.5, stop feeding after reaction 2h, carry out old
Change, after aging 2.5h, the catalyst precursor of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting
Required body phase hydrotreating catalyst I is obtained after burning.
Above-described embodiment and the hydrogenation catalyst property of comparative example preparation are shown in Table 1, and Examples and Comparative Examples preparation adds hydrogen
Catalyst activity metal and auxiliary agent gradient distribution, the reactive metal oxides of table Xiang Yuti phase and auxiliary agent distributional analysis the results are shown in Table
2。
The hydrogenation catalyst property of 1 Examples and Comparative Examples of table preparation
The activity of hydrocatalyst metal and auxiliary agent gradient distribution of 2 Examples and Comparative Examples of table preparation analyze result
The appearance of the hydrogenating catalyst composition hole prepared by the method for the present invention it can be seen from the data of Tables 1 and 2, aperture
Larger, crystal grain distribution is concentrated, and active metal concentrations and auxiliary agent are in gradually increase trend on catalyst granules edge from inside to outside, very suitable
It shares in the preparation of the hydrogenation catalyst of the raw materials such as diesel oil, wax oil.
The reactive metal oxides and auxiliary agent of 2 (Continued) table Xiang Yuti phase of table are distributed
Embodiment 7
Catalyst activity evaluation experimental carries out on 100mL small hydrogenation device, carries out before activity rating to catalyst pre-
Vulcanization.Catalyst is in reaction stagnation pressure 15.5MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 800:1, reaction temperature is 380 DEG C, into
Gone 2000h steady running evaluation, raw material oil nature and evaluation result are shown in Table 3 ~ table 5 respectively.
3 raw material oil nature of table.
4 catalyst activity evaluation result of table
| A | B | C | D | E | F | G | H | I | |
| Opposite denitrification activity | 151 | 150 | 152 | 149 | 112 | 111 | 102 | 100 | 103 |
| Relatively de- carbon residue activity | 142 | 141 | 140 | 145 | 121 | 115 | 109 | 100 | 102 |
The catalyst prepared by the method for the present invention it can be seen from the data of table 4 is under the conditions of same process, due to auxiliary agent
And active metal concentrations increase distribution in gradient in the catalyst, can effectively improve the hydrogenation activity of catalyst.
Claims (15)
1. a kind of body phase hydrotreating catalyst, it is characterised in that: the average hole of catalyst granules center (centre of sphere) to x*R range
Diameter d1For 50 ~ 100nm, wherein x is average pore size d of 0.1 ~ 0.9, the x*R to catalyst external surface2For 120 ~ 180nm, d2-d1=
40~130nm；Wherein R is the particle radius of body phase hydrogenation catalyst；Catalyst includes alumina support, active metal and auxiliary agent,
Wherein active metal is selected from VIII group and/or group vib metallic element；On the basis of catalyst weight, the concentration of active metal with
Oxide meter, gradually increases from catalyst granules center to outer surface, wherein at 1/3R active metal concentration be 6wt%~
The concentration of active metal is 10wt%~20wt% at 10wt%, 2/3R, and the concentration of active metal is 20wt%~30wt% at R；Wherein
Auxiliary agent is one of several combinations of following I, II and III: I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron；Auxiliary agent is with member
Element meter, assistant concentration gradually increases from catalyst granules center to outer surface, wherein 1/3R at auxiliary agent content for 0.5%wt~
Auxiliary agent content is 1.5wt%~2.0wt% at 1.0wt%, 2/3R, and auxiliary agent content is 2.5wt%~3.0wt% at R；R is catalyst particles
Distance of the grain center to catalyst cross section outer most edge any point；The preparation method of the body phase hydrotreating catalyst, packet
It includes following content: (1) bottom water of certain volume being added in reactor tank, swing tank and ageing can, is heated to certain temperature, then
Start blender, charging I and charging II to connect with the acid solution feed inlet and lye feed inlet of certain flow rate difference autoreaction tank top
Continuous addition, adjusting pH value is 9.0 ~ 11.0, after a period of stabilisation, opens the overflow port of reaction pot bottom, arrives generation liquid stream
It swings in tank；Wherein the charging I is the mixture of acid aluminium salt solution I, acid active metal solution I and ionic liquid I,
Charging II is the mixture of basic aluminium salt solution I, basic activated metallic solution I；(2) to the overflow port trickle of reactor tank
Afterwards, the acid solution feed inlet for swinging tank upper end, stream plus certain density acid aluminium salt solution II, acid active metal solution II are opened
With ionic liquid II, pH value is adjusted to 3.0~5.0, after reacting a period of time, the overflow port for swinging pot bottom is opened, makes to generate
Liquid stream is into swing tank；(3) after the overflow port trickle for swinging tank, the lye feed inlet of ageing can upper end is opened, stream adds
Certain density basic aluminium salt solution II, basic activated metallic solution II and ionic liquid III, adjusting pH value to 7.0~8.0, always
After changing a period of time, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting
It burns, obtains body phase hydrotreating catalyst；Along Flow of Goods and Materials direction, reactor tank, swing along tank and ageing can aluminium salt concentration with
Al2O3For meter in the trend gradually decreased, reduction amplitude is 20~50g/100mL；Along Flow of Goods and Materials direction, reactor tank, swing tank and
For active metal salinity in gradually incremental trend in terms of metal oxide, the amplitude that is incremented by is 20~50g/100mL in ageing can；
The alkyls ionic liquid that the ionic liquid I is carbon atom number 1 ~ 4；The ionic liquid II is carbon atom number 4 ~ 8
One or more of a alkyl ammonium halide；The ionic liquid III is the alkyls ionic liquid that carbon atom number is 8 ~ 12
One or more of body；The additional amount of ionic liquid I accounts for 0.5wt%~1wt% of step (1) inlet amount in terms of auxiliary element,
The additional amount of ionic liquid II accounts for 1.5wt%~2wt% of step (2) inlet amount, the addition of ionic liquid III in terms of auxiliary element
Amount accounts for 2.5wt%~3wt% of step (3) inlet amount in terms of auxiliary element, and wherein inlet amount is aoxidized with aluminium oxide and active metal
The sum of object meter；The preparation method of ionic liquid I, II and III is to be added to the water M1 and M2, is heated to reacting under agitation
Temperature, isothermal reaction, after reaction, cooling, centrifugation obtains ionic liquid；Wherein the molar ratio of M1 and M2 is 1:1~1:2,
It is 60~150 DEG C that reaction condition, which is generally reaction temperature, and the isothermal reaction time is 1~4h;The M1 is ammonium tetrafluoroborate, tetrafluoro
One or more of Boratex, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluoro phosphate and Potassium Hexafluorophosphate；The M2 is
One or more of the alkyl ammonium halide that carbon atom number is 1 ~ 13；In charging I described in step (1) acid aluminium salt solution with
The volume flow ratio of acid active metal salt solution is 40:1~80:1, charging II neutral and alkali aluminum salt solution and basic activated metal
The volume flow ratio of salting liquid is 40:1~8:1；The volume of acid aluminium salt solution and acid active metal salt solution in step (2)
Flow-rate ratio is 15:1~35:1；The volume flow ratio of step (3) neutral and alkali aluminum salt solution and basic activated metal salt solution is 5:1
~10:1.
2. catalyst described in accordance with the claim 1, it is characterised in that: body phase hydrotreating catalyst has the property that ratio
Surface area is 250~350m20.8~1.0mLg of/g, Kong Rongwei-1；Average pore size is 50~150nm, wherein the hole of < 50nm
Distribution accounts for total pore volume 2% ~ 8%, and the pore size distribution that the pore size distribution of 50~100nm accounts for 45% ~ 55%, the > 100nm of total pore volume accounts for total pore volume
35%~45%。
3. catalyst according to claim 1 or 2, it is characterised in that: the aperture of catalyst external surface is greater than body Xiang Cuihua
Agent average pore size, difference are 30 ~ 50nm.
4. catalyst according to claim 1 or 2, it is characterised in that: in terms of oxide, group VIII metal is active metal
1wt%~9wt%, group vib metal are 5wt%~25wt%, and auxiliary agent is 2wt% ~ 5wt% based on the element, alumina support be 61wt% ~
92wt%。
5. catalyst according to claim 1 or 2, it is characterised in that: the active metal in catalyst is in terms of oxide, table
The ratio of the weight content of phase active metal component and the weight content of body phase active metal component is 3.0 ~ 15.0:1.
6. catalyst according to claim 1 or 2, it is characterised in that: the active metal of the table phase VIII group of catalyst with
The weight content ratio of body phase VIII group active metal is 2.0:1 ~ 6.0:1.
7. catalyst according to claim 1 or 2, it is characterised in that: table phase VIB active metal and body phase VIB activity gold
The weight content ratio of category is 2.0:1 ~ 8.0:1.
8. a kind of preparation method of body phase hydrotreating catalyst of any of claims 1 or 2, it is characterised in that in following
Hold: (1) bottom water of certain volume being added in reactor tank, swing tank and ageing can, is heated to certain temperature, then starting stirring
Device, charging I and is fed II and is continuously added to the acid solution feed inlet and lye feed inlet of certain flow rate autoreaction tank top respectively, is adjusted
Section pH value is 9.0 ~ 11.0, after a period of stabilisation, opens the overflow port of reaction pot bottom, makes to generate liquid stream into swing tank；
Wherein the charging I is the mixture of acid aluminium salt solution I, acid active metal solution I and ionic liquid I, and charging II is
The mixture of basic aluminium salt solution I, basic activated metallic solution I；(2) after the overflow port trickle of reactor tank, pendulum is opened
The acid solution feed inlet of dynamic tank upper end, stream plus certain density acid aluminium salt solution II, acid active metal solution II and ionic liquid
Body II adjusts pH value to 3.0~5.0, after reacting a period of time, opens the overflow port for swinging pot bottom, make to generate liquid stream to pendulum
In dynamic tank；(3) after the overflow port trickle for swinging tank, the lye feed inlet of ageing can upper end, stream plus a certain concentration are opened
Basic aluminium salt solution II, basic activated metallic solution II and ionic liquid III, pH value is adjusted to 7.0~8.0, at one section of aging
Between after, by the spheric catalyst presoma of preparation from the discharge port of aging pot bottom be discharged, through filtering, drying and roasting, obtain
Body phase hydrotreating catalyst；Aluminium salt concentration is along Flow of Goods and Materials direction, reactor tank, swing tank and ageing can with Al2O3Meter in by
Decrescence few trend, reduction amplitude are 20~50g/100mL；Along Flow of Goods and Materials direction, reactor tank swings in tank and ageing can and lives
Property metal salt concentrations in terms of metal oxide in gradually incremental trend, the amplitude that is incremented by is 20~50g/100mL；The ion
The alkyls ionic liquid that liquid I is carbon atom number 1 ~ 4；The alkyl halide that the ionic liquid II is carbon atom number 4 ~ 8
Change one or more of ammonium；The ionic liquid III is one of the alkyls ionic liquid that carbon atom number is 8 ~ 12
Or it is several；The additional amount of ionic liquid I accounts for 0.5wt%~1wt% of step (1) inlet amount, ionic liquid II in terms of auxiliary element
Additional amount 1.5wt%~2wt% of step (2) inlet amount is accounted in terms of auxiliary element, the additional amount of ionic liquid III is with auxiliary agent member
Element meter accounts for 2.5wt%~3wt% of step (3) inlet amount, and wherein inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides；From
The preparation method of sub- liquid I, II and III is to be added to the water M1 and M2, is heated to reaction temperature under agitation, constant temperature is anti-
It answers, after reaction, cooling, centrifugation obtains ionic liquid；Wherein the molar ratio of M1 and M2 is 1:1~1:2, and reaction condition is general
It is 60~150 DEG C for reaction temperature, the isothermal reaction time is 1~4h;The M1 is ammonium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoro
One or more of potassium borate, ammonium hexafluorophosphate, sodium hexafluoro phosphate and Potassium Hexafluorophosphate；The M2 be carbon atom number be 1 ~
13 one or more of alkyl ammonium halides；Acid aluminium salt solution and acid active metal in charging I described in step (1)
The volume flow ratio of salting liquid is 40:1~80:1, feeds the volume of II neutral and alkali aluminum salt solution and basic activated metal salt solution
Flow-rate ratio is 40:1~8:1；The volume flow ratio of acid aluminium salt solution and acid active metal salt solution is 15:1 in step (2)
~35:1；The volume flow ratio of step (3) neutral and alkali aluminum salt solution and basic activated metal salt solution is 5:1~10:1.
9. according to the method for claim 8, it is characterised in that: the reactor tank swings bottom water in tank and ageing can
Volume accounts for the 1/5~1/4 of the tank volume, and the temperature of reactor tank is less than the temperature for swinging tank, and the temperature for swinging tank is less than aging
The temperature of tank, the temperature of reactor tank are 50~80 DEG C, and the temperature for swinging tank is 80~100 DEG C, the temperature of ageing can is 100~
120℃；Reactor tank and the temperature difference swung between tank are 10~30 DEG C, and swinging the temperature difference between tank and ageing can is 10~30
℃。
10. according to the method for claim 8, it is characterised in that: the stirring rate of reactor tank is higher than the stirring speed for swinging tank
Rate, the stirring rate for swinging tank are higher than the stirring rate of ageing can, and the stirring rate of reactor tank is 600~800rad/min, is stirred
The stirring rate for mixing tank is 300~500rad/min, and the stirring rate of ageing can is 100~200rad/min, reactor tank and pendulum
Rotational speed difference between dynamic tank is 50~150rad/min.
11. according to the method for claim 8, it is characterised in that: the acid aluminium salt solution I, II AlCl3、Al2
(SO4)3Or Al (NO)3One or more of aqueous solution, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/
100mL, the flow of acid aluminium salt solution are 5~50mL/min.
12. according to the method for claim 8, it is characterised in that: the basic aluminium salt solution I, II are selected from NaAlO2With/
Or KAlO2Aqueous solution, the concentration of basic aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/100mL, the flow of basic aluminium salt solution
For 5~50mL/min.
13. according to the method for claim 8, it is characterised in that: described acid active metal salt solution I, the II is molybdenum nickel
One of phosphorus, molybdenum cobalt phosphorus, molybdenum cobalt nickel phosphorus, tungsten nickel phosphorus, tungsten nickel phosphorus, tungsten nickel cobalt phosphorus or tungsten cobalt phosphorus aqueous solution, acidity are living
Property metal salt solution concentration 15~100g/100mL is calculated as with oxide, pH value is 1.0~4.0, acid active metal salt water
Liquid inventory is 5~50mL/min；Described basic activated metal salt solution I, the II is molybdenum nickel ammonia, molybdenum cobalt ammonia, molybdenum cobalt nickel ammonia, tungsten
One of nickel ammonia, tungsten nickel ammonia, tungsten nickel cobalt ammonia or tungsten cobalt ammonia spirit, the concentration of basic activated metal salt solution is with oxygen
Compound is calculated as 15~100g/100mL, and pH value is 10.0~12.0, and basic activated aqueous metal salt flow is 5~50mL/
min。
14. according to the method for claim 8, it is characterised in that: step (2) is repeated as many times；When odd-times repeats, swing
Charging in tank is basic aluminium salt solution II, acid active metal solution II and ionic liquid II, adjust pH value to 9.0~
11.0, remaining same step (2)；When even-times repeats, same to step (2).
15. a kind of application of body phase hydrotreating catalyst of any of claims 1 or 2 in distillate hydrogenation reaction.
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| CN1421511A (en) * | 2001-11-30 | 2003-06-04 | 中国石油天然气集团公司 | Prepn process of paraffin hydrofining catalyst |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal and acid additive concentration in gradient increasing distribution and preparation method thereof |
| CN105820296A (en) * | 2016-05-10 | 2016-08-03 | 嘉兴艾尔瑞环境科技有限公司 | Preparation method for crosslinking acrylamide grafted starch |
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| CN1421511A (en) * | 2001-11-30 | 2003-06-04 | 中国石油天然气集团公司 | Prepn process of paraffin hydrofining catalyst |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal and acid additive concentration in gradient increasing distribution and preparation method thereof |
| CN105820296A (en) * | 2016-05-10 | 2016-08-03 | 嘉兴艾尔瑞环境科技有限公司 | Preparation method for crosslinking acrylamide grafted starch |
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