CN102166520B - 加氢精制催化剂 - Google Patents
加氢精制催化剂 Download PDFInfo
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- CN102166520B CN102166520B CN2010101142567A CN201010114256A CN102166520B CN 102166520 B CN102166520 B CN 102166520B CN 2010101142567 A CN2010101142567 A CN 2010101142567A CN 201010114256 A CN201010114256 A CN 201010114256A CN 102166520 B CN102166520 B CN 102166520B
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- Prior art keywords
- catalyst
- salt
- cobalt
- oxide
- carrier
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000002803 maceration Methods 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- -1 carbonate salt compound Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003657 tungsten Chemical class 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 238000004939 coking Methods 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000002431 foraging effect Effects 0.000 abstract 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 238000003483 aging Methods 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 229940011182 cobalt acetate Drugs 0.000 description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 238000001994 activation Methods 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000002101 lytic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 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
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 229910020515 Co—W Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- BTMQKQSSEQVSAS-UHFFFAOYSA-N cobalt;ethane-1,2-diamine Chemical compound [Co].NCCN BTMQKQSSEQVSAS-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B31/00—Reduction in general
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J35/30—
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- B01J35/615—
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- B01J35/633—
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- B01J35/635—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
本发明涉及一种加氢精制催化剂,通过将载体加入至浸渍液中浸渍后陈化、干燥,活化得到的,含有载体、钼、钴,其特征在于以催化剂重量为100%计,含氧化钼5~25%,氧化钴1~6%,氧化钨0~15%,氧化镍0~4%,碱金属氧化物0~4.5%,催化剂孔容为0.30~0.85ml/g,比表面积为110~380m2/g;催化剂制备中的复合溶剂同时含有氨水和多胺络合剂。本发明的催化剂在加氢脱硫的同时,最大限度地加氢饱和单烯烃,能适应硫含量和双烯含量多变的油品及高空速运转的要求。催化剂加氢活性好,选择性高,运转时间长,抗结焦性能优越。
Description
技术领域
本发明涉及一种加氢精制催化剂,催化剂适用于中低馏分油加氢精制。
背景技术
目前,关于活性组分为Ni-Mo、Co-Mo、Ni-W、Co-W、以及Co-Mo-Ni、W-Mo-Ni的加氢精制催化剂及制备方法的报道很多。采用浸渍法制备含有钴、钼催化剂过程中,存在的主要问题是活性组分Co、Mo溶解困难,特别是在一种溶剂中同时溶解两种活性组分。而采用分步浸渍法制备催化剂会造成催化剂制备成本的增加。采用一步浸渍法制备催化剂,现有技术存在的问题是,需要添加有机酸/碱促进活性组分的溶解,在需要活性组分含量较高时,需要使用大量有机酸/碱,焙烧时温度难控制、容易产生飞温现象,并且会放出大量气体,催化剂损失也较大。
而配制的活性组分浸渍液是否澄清、均匀,直接关系到浸渍后催化剂中活性组分的分散度,从而影响催化剂的活性和选择性。所以选择有效的溶剂及溶解方法成为配制浸渍液的关键。
US4409131公开了一种CoMo/NiMo催化剂的制备方法,是由含有活性组分及氨水的溶液一步浸渍载体制得的,该方法详细的介绍了浸渍液的配制过程,在配制浸渍液过程中,需要加热混合物促进活性组分的溶解。
US6013598公开了一种选择性加氢脱硫催化剂及制备方法,催化剂由活性组分钴、钼及载体氧化铝组成,是由含有活性组分并添加柠檬酸的水溶液等体积浸渍载体制得,该方法得到的催化剂氧化钼含量最高只能达到10wt%。
CN91110935.8公开了一种加氢精制催化剂的制备方法,将乙酸钴溶于水后加入乙二胺,使其形成钴乙二胺的混合溶液,在溶液pH为12~14加入钼酸铵制成含有钴钼金属的共浸液,将多孔载体用此溶液浸渍后制备催化剂。该方法的缺点是需要在无氧或微氧气氛中焙烧得到催化剂产品。
CN94114194.2公开了一种以氧化锌改性的γ-氧化铝作载体,以钴、钼为活性组分的催化剂及制备方法,将一定量浓度为15~28%的氨水,加入所需量钴盐,在不断搅拌下加入一定量的乙二胺,使乙二胺的量为钴盐重量的1/50~1/7,然后在不断搅拌下加入所需量的钼酸胺;制得Co-Mo共浸液,采用该共浸液一次浸渍制备载体1~10小时,于110~150℃干燥2~6小时,于480~600℃焙烧3~8小时,制得催化剂,制得的催化剂的优选组成为:CoO(1~5wt%),MoO8~14wt%,ZnO1~15wt%,其余为γ-Al2O3。
CN00130284.1公开了一种加氢精制催化剂及其制备方法,用含钼、钴、镍活性组分的氨共浸液浸渍加入高聚物和第IVB族金属的氧化铝载体制得,对于浸渍液的配制过程,该方法没有做详细的介绍。制得的催化剂的组成为:CoO(1~9wt%),MoO8~25wt%,IVB 7~22wt%,其余为Al2O3。
目前,以氨水作为溶剂溶解Co、Mo活性组分,是一项公知的技术,但是氨水对于提高活性组分分散度的效果不明显。如何操作简单的配制一种含有活性组分的浸渍液,使其澄清、稳定、表面张力和粘稠度小,并且达到多组分一步等体积浸渍的要求,浸渍后活性组分保持高度分散状态,仍然是个难题。将钴盐直接溶于水或者氨水,在不加热的条件下,如果控制溶剂的用量,往往钴盐不能完全溶解,需要再加入有机酸或碱促进钴的溶解;如果使用加热的方法,虽然在能够控制溶剂的用量的条件下完全溶解活性组分的盐,但是造成催化剂制备过程的能耗增加。
裂解汽油经两段加氢后一般用作芳烃抽提的原料,因此催化剂不仅需要具有优异的加氢活性(产品溴价<1.0gBr2/100g)和脱硫活性(产品硫<1.0μg/g),还需要具有良好的加氢选择性(防止芳烃加氢损失)和长周期运转性能。而目前工业装置使用的裂解汽油二段加氢催化剂普遍存在加氢活性及脱硫活性较好,但长周期运转能力不足,芳烃加氢损失率较高(>2%),高负荷运转能力不强,催化剂生产成本较高等缺点,影响装置经济效益。
存在上述问题的主要原因有以下几个方面:
(1)催化剂上活性金属组分分散性不好,存在着过强的活性中心点,导致芳烃加氢尤其是苯加氢损失率高;
(2)催化剂上存在一定数量的B酸中心,而L酸中强L酸中心较多,致使催化剂在高温下容易结焦,使床层压降增大,影响氢气流通,氢气压缩机运转困难,加氢产品不合格,被迫停车再生。
(3)催化剂比表面积和孔体积尤其孔径分布在很大程度上影响催化剂的活性,适宜的比表面积、孔体积和分布集中的孔径对于传质、传热及扩散十分重要。
(4)为了提高催化剂活性,一个办法是提高活性组分含量,但是提高活性组分含量会带来分散性不好的问题。为了解决这一问题,在催化剂制备过程中可采用多步浸渍来实现,即一步浸渍后干燥、焙烧再进行下一步浸渍,这使得制备流程复杂,能源浪费严重,导致催化剂生产成本增高。
虽然有在配制浸渍液时通过添加有机酸或氨、乙二胺等络合剂进行一步浸渍的报道,但是大量添加大分子有机酸碱会给后续焙烧过程增加难度,而氨由于挥发性较强,其添加会给浸渍液的配制过程带来更多的麻烦,而且对提高活性组分的分散度也不是很明显。
发明内容
本发明的目的是提供一种制备方法节能简单的催化剂,制备的催化剂强酸及B酸减弱,活性组分分散度明显提高,在加氢脱硫、脱氮的同时,能够减少苯加氢反应的发生,降低结焦速率,催化剂活性及选择性好,稳定性高。
本发明加氢精制催化剂是通过将载体加入至浸渍液中浸渍后陈化、干燥,活化得到的,含有载体、钼、钴,其特征在于以催化剂重量为100%计,含氧化钼5~25%,氧化钴1~6%,氧化钨0~15%,氧化镍0~4%,碱金属氧化物0~4.5%,催化剂孔容为0.30~0.85ml/g,比表面积为110~380m2/g;在制备浸渍液时将含有活性组分钴的盐加入至复合溶剂中,复合溶剂同时含有氨水和多胺络合剂。
更具体地说,应用本发明,获得最优化的催化剂是首先将氨水和多胺络合剂混合配制成复合溶剂;通过将含有活性组分钴的盐加入复合溶剂中,使钴盐溶解后,再加入钼盐或者钼盐和其它活性组分或助剂的盐类,并使之溶解,制成浸渍液,浸渍载体后陈化、干燥,活化后得到的。
本发明中对催化剂的载体并不特别加以限制,普通负载型加氢精制催化剂所用载体,特别是钴、钼系负载型加氢精制催化剂所用载体均可适用,如耐高温无机氧化物,如氧化铝、氧化硅、氧化铝-氧化硅,载体还可以是经过改性的,最好载体为氧化铝系载体。
本发明提供一种采用复合溶剂配制的碱性浸渍液,通过一步浸渍制备催化剂的方法。
在氨水中加入多胺络合剂配制成的复合溶剂在溶解钼、钴盐时,最好是先溶解钴盐,钴不需要先在氨水中溶解再与络合剂络合,而是直接与复合溶剂形成钴配位络合物,更利于催化剂活性组分的溶解。
本方法在配制浸渍液时,根据需要还可以加入镍盐、钨盐和/或IA族的可溶性碱或碳酸盐化合物,一般最好调节pH值到10以上,配制的浸渍液澄清、稳定、表面张力和粘稠度小。
浸渍液在20~30℃下即可完成配制,不需要加热过程。本发明特别适用于多种活性组分、高活性组分含量,特别是高钴、钼含量催化剂的制备,尤其是采用一步等体积浸渍将活性组分负载到载体上的催化剂制备方法,活性组分在催化剂上呈高度分散状态,并有效消除了催化剂上的B酸中心,减弱了强L酸中心。本发明所述的等体积浸渍是指浸渍液的加入量为催化剂载体孔容的70~130%。
本发明中多胺络合试剂可以是EDTA、三乙撑四胺、三乙醇胺、乙二胺中的一种或多种,优选乙二胺。多胺络合剂的加入量根据钴的加入量的高低而变化,本发明并不特别加以限制,最好为浸渍液量的5~10%(体积含量),过高容易造成焙烧过程中大量有机物分解,过低无法达到促进活性组分溶解、提高活性组分分散度的效果。配制浸渍液时,对氨水的浓度本发明不作特别限定,根据活性组分加入量,达到能使各活性组分完全溶解即可,此时活性组分与多胺络合试剂形成较稳定的络合物。一般活性组分完全溶解后,还可加入一定量的氨水,使浸渍液的剂量达到等体积浸渍的要求。催化剂经热活化处理后,部分氨分子仍吸附在强L酸性位上,减弱催化剂酸性,提高了催化剂的加氢选择性及稳定性能,尤其降低了催化剂在反应过程中的结焦速率。采用本发明的方法完成载体的浸渍之后,经陈化、干燥,活化制得催化剂。催化剂在热活化过程中无有毒性气体产生,实现了一步法“绿色”制备。陈化、干燥,活化均采用现有技术中的条件,本发明并无特殊要求,活化温度最好是350~600℃。
本发明溶解活性组分用的溶剂是添加多胺络合剂的氨水,采用这种复合溶剂一方面提高活性组分在氨水中的溶解性、减少氨水的用量,另一方面由于多胺络合剂的添加明显提高了催化剂活性组分的分散度。
本发明采用的浸渍液为碱性浸渍液,在活性组分溶解后需要调节浸渍液pH值到10以上,优选10~12。这样配制的浸渍液澄清、稳定、粘稠度小,活性金属分散性好。
本发明中活性组分钼最好以钼酸铵的形式加入,活性组分钴可以以硫酸盐、卤化物、硝酸盐或醋酸盐的形式加入,优选硝酸盐或/和醋酸盐,因为硝酸盐、醋酸盐溶解性好,有利于活性组分在载体上的分布。碱金属助剂,可以选择锂、钠、钾、铷、铯的可溶性碱,可以选择锂、钠、钾、铷、铯的可溶性碳酸盐,本发明优选钾助剂,并且优选氢氧化物,氢氧化物的加入使浸渍液碱性增强,从而使金属活性组分更好地与多胺络合剂络合,提高浸渍溶液的稳定性,同时碱金属助剂的加入,还起到调节催化剂酸性,提高催化剂抗结焦性能的作用。
本发明中对催化剂制备的温度条件并不加以限制,最好是在20~40℃下,用上面所述的浸渍液对成型的氧化铝载体进行一步浸渍,在80~120℃下干燥4~5小时,350~600℃焙烧3~8小时制得。
采用本发明的方法制得的催化剂在加氢脱硫的同时,能最大限度地加氢饱和单烯烃,特别适应硫含量和双烯含量多变的油品及高空速运转的要求。催化剂加氢活性好,选择性高,运转时间长,抗结焦性能优越。
附图说明
附图为具体实施方式中催化剂A、E活性组分分散度对比图,其中图1为应用本发明的催化剂A的透射电镜图,图2为对比催化剂E的透射电镜图,图中黑色线状物对应活性组分的片晶,条纹的长度为片晶长度,堆积的条纹条数代表片晶的层数。为从催化剂的TEM照片统计MoS2片晶在载体表面的分散与堆积情况,对催化剂表面不同的区域进行观察,拍摄出了大量的电镜照片,图1、2为具有代表性的透射电镜图。从图中可以看出:催化剂A活性组分片晶长度均一,分布均匀;催化剂B活性组分片晶长短差异较大,分布不均匀。
具体实施方式
制备催化剂所用主要原料来源及主要物性参数:
γ-Al2O3:
淄博万霖化工科技有限公司提供,孔容0.90~0.95ml/g,比表面积300~320m2/g;
改性γ-Al2O3:
淄博万霖化工科技有限公司提供,二氧化硅含量3.5%,孔容0.90~0.95ml/g,比表面积300~320m2/g;
α-Al2O3:
淄博万霖化工科技有限公司提供,孔容0.85~0.90ml/g,比表面积280~300m2/g;
氨水:白银良友化学试剂有限公司,浓度25~30wt%
分析方法及标准:
催化剂的金属含量测定方法:采用原子吸收测定催化剂中金属含量;
溴价:SH/T 0630-1996石油产品溴价、溴指数测定法(电量法);
双烯:UOP326-07马来酸酐法;
催化剂积碳量/%:元素分析仪测定催化剂中碳元素;
氮含量:SH/T 0657、ASTM D4629液态石油烃中痕量氮测定法
硫含量:SH/T 0253-92轻质石油产品中总硫含量测定法(电量法)
加氢原料:兰州石化提供,油品性质如表1所述。
表1、加氢原料油指标
油品 | 颜色 | 溴价×10-2(g/g) | 双烯×10-2(g/g) | 馏程(℃) | 密度(g/ml) | 氮含量(μg/g) | 硫含量(μg/g) |
裂解汽油 | 淡黄色 | 75 | 2.5 | 45~180 | 0.825 | / | 80~100 |
柴油 | 褐色 | / | / | 60~190 | 0.940 | 250~300 | 800~1000 |
实施例1
在30℃下,将14.21g醋酸钴加入到60ml的氨水和5ml乙二胺的混合溶液中,搅拌溶解,再加入钼酸铵31.97g、硝酸镍9.32g搅拌溶解后,加入氢氧化钾3.49g,加入氨水将溶液体积调整到80ml,浸渍于100g的γ-Al2O3载体上,陈化12h,120℃下干燥4小时,580℃焙烧4h,制得催化剂A。
实施例2
在25℃下,将28.01g醋酸钴加入到50ml的氨水和7ml乙二胺的混合溶液中,搅拌溶解,再加入钼酸铵14.21g、偏钨酸铵18.8g搅拌溶解后,加入氢氧化锂2.38g,加入氨水将溶液体积调整到100ml,浸渍于100g的α-Al2O3载体上,陈化12h,100℃下干燥5小时,350℃焙烧5h,制得催化剂B。
实施例3
在20℃下,将7.1g硝酸钴加入到55ml氨水和6mlEDTA的混合溶液中,搅拌溶解,再加入钼酸铵42.67g、醋酸镍7.8g、硝酸锶6.60g搅拌溶解后,加入碳酸锂6.84g,加入氨水将溶液体积调整到110ml,浸渍于100g的改性γ-Al2O3载体上,陈化12h,200℃下干燥4小时,400℃焙烧3.5h,制得催化剂C。
实施例4
改性γ-Al2O3粉体300g,加入磷酸8.4ml,加水140ml,捏合挤条成型,在空气中120℃烘干,560℃焙烧6小时,制得含磷的改性γ-Al2O3载体。
在25℃下,将28.01g醋酸钴加入到50ml的氨水和9ml三乙撑四胺的混合溶液中,搅拌溶解,再加入钼酸铵14.21g、偏钨酸铵18.8g搅拌溶解后,加入氨水将溶液体积调整到95ml,浸渍于100g的含磷的改性γ-Al2O3载体上,陈化12h,100℃下干燥5小时,350℃焙烧5h,制得催化剂D。
对比例1
在30℃下,将14.2lg醋酸钴加入到60ml的氨水中,搅拌至多半醋酸钴溶解,再加入5ml乙二胺继续搅拌至醋酸钴完全溶解,再加入钼酸铵31.97g、硝酸镍9.32g搅拌溶解后,加入氢氧化钾3.49g,加入氨水将溶液体积调整到80ml,浸渍于100g的γ-Al2O3载体上,陈化12h,120℃下干燥4小时,580℃焙烧4h,制得催化剂E。
催化剂A、E活性组分分散度对比如附图中图1、图2所示。
对比例2
在25℃下,将28.01g醋酸钴加入到20ml乙二胺和80ml水的混合溶液中,搅拌溶解,再加入钼酸铵14.21g、偏钨酸铵18.8g搅拌溶解后,加入氢氧化锂2.38g,浸渍于100g的α-Al2O3载体上,陈化12h,100℃下干燥5小时,350℃焙烧5h,制得催化剂F。
对比例3
在20℃下,将7.1g硝酸钴加入到110ml氨水中,搅拌溶解,浸渍于100g的改性γ-Al2O3载体上,陈化12h,200℃下干燥4小时,400℃焙烧3.5h;将钼酸铵42.67g、醋酸镍7.8g、硝酸锶6.60g加入到110ml氨水中搅拌溶解后,加入碳酸锂6.84g,浸渍于100g的改性γ-Al2O3载体上,陈化12h,200℃下干燥4小时,400℃焙烧3.5h,制得催化剂G。
催化剂B、D酸性对比结果如表2所示:
表2催化剂B、D酸性对比结果
实施例5
对上面制备的催化剂A、E分别进行200小时评价,采用裂解汽油一段加氢产品为原料,原料性质见表1,催化剂评价是在100ml绝热床加氢反应装置上进行的。每6小时取样分析产品碘价、硫含量。催化剂200小时评价的平均数据见表4。
催化剂预硫化条件为:在环己烷中添加二硫化碳配成硫化油(硫含量1000μg/g),在2.8MPa压力下,通氢气,将催化剂床层温度升到240℃开始进硫化油,继续升温到325℃,维持30小时后,降温到240℃,硫化结束。
评价条件:反应压力2.6MPa,入口温度240℃,新鲜原料油体积空速3.0h-1,以新鲜油计,氢与油体积比300∶1。
实施例6
对催化剂B、D、F进行1000小时评价,评价原料、催化剂预硫化条件、评价条件及原料与实施例4相同。催化剂评价中产品碘价、硫含量的平均数据见表5。
实施例7
对上面制备的催化剂C、G分别进行1000小时加氢评价,采用柴油为原料,原料性质见表1,催化剂评价是在100ml绝热床加氢反应装置上进行的。每6小时取样分析产品氮、硫含量。催化剂1000小时评价的平均数据见表6。
催化剂预硫化条件为:在环己烷中添加二硫化碳配成硫化油(硫含量1000μg/g),在2.8MPa压力下,通氢气,将催化剂床层温度升到240℃开始进硫化油,继续升温到325℃,维持30小时后,降温到240℃,硫化结束。
评价条件:反应压力2.8MPa,入口温度280℃,新鲜原料油体积空速3.0h-1,以新鲜油计,氢与油体积比300∶1。
从表4的评价结果来看,采用本发明提供的催化剂活性组分的分散度高,具有更好的加氢活性及加氢选择性。
从表5的评价结果来看,采用本发明提供的催化剂,改善了催化剂酸性,具有优良的抗积碳性能及加氢稳定性。
从表6的评价结果来看,采用本发明提供的催化剂具有更高的加氢脱硫、脱氮活性。
表4催化剂A、E 1000小时评价平均数据
表5催化剂B、D、F 1000小时评价平均数据
表6催化剂C、G 1000小时评价平均数据
Claims (10)
1.一种加氢精制催化剂,通过将载体加入至浸渍液中浸渍后陈化、干燥,活化得到的,含有载体、钼、钴,其特征在于以催化剂重量为100%计,含氧化钼5~25%,氧化钴1~6%,氧化钨0~15%,氧化镍0~4%,碱金属氧化物0~4.5%,催化剂孔容为0.30~0.85ml/g,比表面积为110~380m2/g;在制备浸渍液时将含有活性组分钴的盐加入至复合溶剂中,复合溶剂同时含有氨水和多胺络合剂。
2.根据权利要求1所述的加氢精制催化剂,其特征在于催化剂通过将含有活性组分钴的盐加入复合溶剂中,使钴盐溶解后,再加入钼盐或者钼盐和其它活性组分的盐类或者钼盐和其它助剂的盐类,并使之溶解,制成浸渍液,浸渍载体后陈化、干燥,活化后得到的。
3.根据权利要求1所述的加氢精制催化剂,其特征在于载体为耐高温无机氧化物。
4.根据权利要求3所述的加氢精制催化剂,其特征在于载体为氧化铝、氧化硅、氧化铝-氧化硅或者是上述物质经过改性的。
5.根据权利要求1所述的加氢精制催化剂,其特征在于浸渍液配制过程中,加入镍盐、钨盐和/或IA族的可溶性碱或可溶性碳酸盐化合物。
6.根据权利要求1所述的加氢精制催化剂,其特征在于浸渍液pH值为10以上。
7.根据权利要求1所述的加氢精制催化剂,其特征在于多胺络合剂是EDTA、三乙撑四胺、三乙醇胺、乙二胺中的一种或多种。
8.根据权利要求1所述的加氢精制催化剂,其特征在于多胺络合剂的加入量为浸渍液量的5~10体积%。
9.根据权利要求2所述的加氢精制催化剂,其特征在于钴盐为钴的硫酸盐、卤化物、硝酸盐或醋酸盐。
10.根据权利要求1或2所述的加氢精制催化剂,其特征在于浸渍载体后陈化,在80~120℃下干燥4~5小时,350~600℃焙烧3~8小时制得。
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WO2014047752A1 (zh) * | 2012-09-28 | 2014-04-03 | 中国石油天然气股份有限公司 | 一种不饱和化合物选择加氢催化剂 |
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FR3014707B1 (fr) | 2013-12-13 | 2017-03-31 | Ifp Energies Now | Procede de preparation d'un catalyseur, catalyseur et son utilisation dans un procede d'hydroconversion et/ou d'hydrotraitement |
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CN105457664A (zh) * | 2015-12-05 | 2016-04-06 | 辽宁石油化工大学 | 一种加氢精制催化剂 |
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