CN111822023B - 一种活性金属浸渍液及加氢处理催化剂的制备方法 - Google Patents
一种活性金属浸渍液及加氢处理催化剂的制备方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000004185 ester group Chemical group 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
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- 229910052759 nickel Inorganic materials 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 235000005985 organic acids Nutrition 0.000 abstract description 2
- 125000001033 ether group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical group O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-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
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910008947 W—Co Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种活性金属浸渍液及加氢处理催化剂的制备方法，浸渍液包括有机溶剂、活性金属盐和含有苯和/或酯类基团的有机磷化物；所述有机溶剂为醚类、醇类、酮类或有机酸类；所述的活性金属盐为第ⅥB族和/或第Ⅷ族活性金属的可溶性盐。本发明同时提供一种加氢处理催化剂的制备方法，包括如下内容：用上述的活性金属浸渍液将活性组分负载到载体上，得到加氢处理催化剂。本发明的的活性金属浸渍液的性质优良，采用上述浸渍液制备的加氢处理催化剂具有良好的加氢活性。
Description
技术领域
本发明属于催化剂制备技术，具体地涉及一种活性金属浸渍液及加氢处理催化剂的制备方法。
技术背景
对于超深度加氢脱硫催化剂，Co-Mo-S和Ni-Mo-S的Ⅱ类活性中心理论已经被各大研发机构广泛接受，并以此开发了新型高活性加氢处理催化剂。主要的改进方案包括载体的选择、添加助剂的应用、浸渍液络合、硫化过程以及金属组分的调整等。一般来说，浸渍液的络合方式是制备Ⅱ类活性中心催化剂的重要方法。
CN108620081A公开了一种加氢催化剂浸渍液及其制备方法，浸渍液组成：活性金属含量以氧化物计，第Ⅷ族金属氧化物为5~70g/100ml，第Ⅷ族金属氧化物为1~30g/100ml，有机酸与第Ⅷ族金属原子摩尔比为0.1~1，有机胺与第Ⅷ族金属原子摩尔比为0.1~2。制备方法如下：将钴/镍盐和有机酸同时加入水中，缓慢升至一定温度使之完全溶解，保持恒定温度加入有机胺并不停搅拌，保持此温度加入钼/钨盐并不停搅拌，待完全溶解后，得到加氢催化剂浸渍液，保存待用。CN 106607039A、CN108568305A、CN102994141A、CN103769125A、CN103769222A等也公开了类似的添加络合剂/螯合剂等方法制备浸渍液，这些技术用于制备Ⅱ类活性中心催化剂，从而提高催化剂的活性。
现有浸渍液的制备方法，均为水溶液溶解活性组分金属并添加相应的络合剂/螯合剂，为了保证络合剂的溶解性能和络合效果，CN106607097A、CN106607096A、CN103769220B等采用二段络合浸渍法，步骤复杂，且因为溶解度的缘故，存在一定的溶解区间。
CN 107185539 A公开了一种油品加氢铁基催化剂及其制备方法与应用。该浸渍液溶剂为无水乙醇、丙酮和2 ,2-联吡啶混合溶液，相当于仍需添加2,2-联吡啶络合剂络合铁离子，存在氨氮污染的问题。
发明内容
针对现有技术中存在的问题，本发明提供一种活性金属浸渍液及加氢处理催化剂的制备方法。该方法将活性金属盐溶解于有机溶剂中，加入适量的有机磷化物，可得到性质优良的活性金属浸渍液，采用上述浸渍液制备的加氢处理催化剂具有良好的加氢活性。
本发明的活性金属浸渍液，包括有机溶剂、活性金属盐和含有苯和/或酯类基团的有机磷化物；所述有机溶剂为醚类、醇类、酮类或有机酸类，如乙醚、甲醇、乙醇、丙醇、丁醇、乙二醇、丙酮、乙酸或丙酸中的一种或多种，优选乙醇、丙醇、丙酮或乙酸中的一种或多种；所述的活性金属盐为第ⅥB族和/或第Ⅷ族活性金属的可溶性盐，第ⅥB族金属优选为钼和/或钨，第Ⅷ族金属优选为镍和/或钴，可溶性盐如磷钼酸、磷钨酸、磷钼酸铵、钼酸铵、偏钨酸铵、磷钨酸铵、硝酸钴、硝酸镍、乙酸钴、乙酸镍等；所述的可溶性是对上述有机溶剂的可溶性。
以活性金属浸渍液各组分的质量浓度如下：活性金属盐以氧化物计，第ⅥB族金属氧化物为1~100g/100mL，优选2~70g/100mL，第Ⅷ族金属氧化物为1~90g/100mL，优选2~60g/100mL；含有苯和/或酯类基团的有机磷化物以磷元素计为1-60g/100mL，优选2~50g/100mL。
含有苯和/或酯类基团的有机磷化物为磷酸三甲酚酯、亚磷酸三苯酯、三苯基氧化膦、磷酸三苯酯、亚磷酸二正丁酯中的一种或或多种。
本发明的活性金属浸渍液的制备方法，包括如下内容：先将第VIB族的活性金属盐加入有机溶剂中，再加入有机磷化物后，缓慢升至度15~90℃，优选20~65℃使之完全溶解，保持温度恒定加入第VIII族活性金属盐并不停搅拌，待完全溶解后得到活性金属浸渍液，保存待用。
本发明同时提供一种加氢处理催化剂的制备方法，包括如下内容：用上述的活性金属浸渍液将活性组分负载到载体上，得到加氢处理催化剂。所述载体可以为本领域常用的各种成型的多孔载体，没有特别限定。例如可以选自氧化铝、氧化硅、氧化钛、氧化镁、氧化锆及其氧化铝-氧化硅、氧化铝-氧化钛等组合复合载体中的一种或多种。其中所述的负载过程可以为浸渍或混捏，均为本领域技术人员熟知，如饱和浸渍或过饱和浸渍，优选过饱和浸渍，其中过饱和度表示成浸渍液/吸液率*100，为>1.05；所述的干燥条件为60~140℃，干燥过程亦为本领域技术人员熟知，如常规干燥或真空干燥，优选真空干燥；所述的焙烧条件为300~800℃。
本发明方法得到的加氢处理催化剂，组成如下：以催化剂的重量为基准，加氢活性金属以氧化物计的重量含量为3wt%~60wt%，磷元素质量分数为0.1wt%~8wt%；其中第VIB族金属为Mo和/或W，第VIII族金属为Ni和/或Co；第VIII族金属/（第VIB族金属+第VIII族金属）以氧化物计的重量比为0.01~0.90；P与第VIII族金属氧化物质量比为0.2~6。
与现有技术相比，本发明具有如下优点：
1. 本发明的活性金属浸渍液的配方能够溶剂为有机溶剂，所添加磷化物为有机磷化物，因此能够在更大的组分含量和比例范围内配置Mo/W-Co/Ni-P溶液，从而避免常规水溶液浸渍液存在的不可配范围区间。
2. 本发明浸渍液中无需添加有机络合剂/螯合剂，仍有提高活性组分本征活性的作用，无需多次浸渍和后续处理步骤，降低生产工艺复杂性。
具体实施方式
下面通过实施例进一步说明本发明方案及效果，但并不构成对本发明的限制。
实施例1
取60g磷钼酸放入多口烧瓶中，加入60g无水乙醇和40g磷酸三甲酚酯后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度35℃，时间为0.1～2h，溶液转变为澄清后，加入40g乙酸镍并不停搅拌，待完全溶解后，将溶液用无水乙醇稀释至100ml备用，命名为溶液L-1。
实施例2
取20g磷钼酸铵放入多口烧瓶中，加入60g乙酸和30g亚磷酸三苯酯后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度30℃，时间为0.1～2h，溶液转变为澄清后，加入160g乙酸镍并不停搅拌，待完全溶解后，将溶液用乙酸稀释至100ml备用，命名为溶液L-2。
实施例3
取50 g磷钼酸铵放入多口烧瓶中，加入60g丙酮和60g亚磷酸二正丁酯后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度40℃，时间为0.1～2h，溶液转变为澄清后，加入80g硝酸镍并不停搅拌，待完全溶解后，将溶液用丙酮稀释至100ml备用，命名为溶液L-3。
实施例4
取40g磷钼酸放入多口烧瓶中，加入60g无水乙醇和20g磷酸三甲酚酯后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度35℃，时间为0.1～2h，溶液转变为澄清后，加入30g乙酸镍并不停搅拌，待完全溶解后，将溶液用无水乙醇稀释至100ml备用，命名为溶液L-4。
实施例5
取40g磷钼酸放入多口烧瓶中，加入60g无水乙醇和20g三苯基氧化膦后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度35℃，时间为0.1～2h，溶液转变为澄清后，加入25g乙酸镍并不停搅拌，待完全溶解后，将溶液用无水乙醇稀释至100ml备用，命名为溶液L-5。
比较例1
同实施例1，但将无水乙醇胺改为去离子水，得到溶液L-6。
比较例2
同实施例1，但将加入磷酸三甲酚酯改为加入磷酸，得到溶液L-7。下表1为配制溶液的组成及性质
表1 Mo-Co溶液的组成及性质。
由表1可知采用有机溶剂和有机磷配制的金属溶液溶解范围比水溶液和磷酸范围更广。
实施例5
取30g磷钼酸放入多口烧瓶中，加入60g无水乙醇和15g磷酸三甲酚酯后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度35℃，时间为0.1～2h，溶液转变为澄清后，加入15g乙酸镍并不停搅拌，待完全溶解后，将溶液用无水乙醇稀释至100ml备用，命名为溶液L-8。
比较例3
按照常规配置Mo-Co-P溶液的方法，取28.4g氧化钼、7.55g碱式碳酸镍放入多口烧瓶中，加入5.6g磷酸和80ml去离子水后，进行搅拌。待搅拌均匀后缓慢加热，保持溶液温度90℃，时间为0.5～2h，溶液转变为澄清。自然降温后稀释至100ml，得到溶液L-9。
比较例4
按照专利CN 103769220B中实施例1所述方法，将100 g氧化铝载体置于滚锅中，在转动条件下，向滚锅中的氧化铝载体以雾化方式喷入80ml含有28.4g三氧化钼，1.12g乙烯乙二醇的水溶液，溶液喷完后，在滚锅中继续转动30分钟，然后放置18小时，在110℃下干燥5小时。称取重量后再置于滚锅中，在转动条件下，向滚锅中再以雾化方式喷入35ml含有7.55g碱式碳酸镍1.53g柠檬酸的水溶液，溶液喷完后，在滚锅中继续转动30分钟，然后放置18小时，在110℃下干燥5小时，制得成品催化剂CL-9。
选用市售γ-Al2O3为载体，采用实施例溶液L-7和对比例L-8进行过饱和浸渍，过饱和度为1.45。于95℃真空干燥4h，350℃焙烧2h 后得到催化剂CL-7、CL-8，催化剂的组成见表2。
表2 催化剂的组成
催化剂评价在100ml小型加氢装置上进行，活性评价前先对催化剂进行预硫化。催化剂评价工艺条件为压力6.0 MPa，液时体积空速2.0h-1，氢油体积比300:1，反应温度为350℃。活性评价原料油性质见表3，活性评价结果见表4。
表3原料油性质。
表4活性评价结果。
Claims (8)
1.一种活性金属浸渍液，其特征在于：包括有机溶剂、活性金属盐和含有苯和/或酯类基团的有机磷化物；所述有机溶剂为乙醇、丙醇、丙酮或乙酸中的一种或多种；所述的活性金属盐为第ⅥB族和/或第Ⅷ族活性金属的可溶性盐；所述含有苯和/或酯类基团的有机磷化物为磷酸三甲酚酯、亚磷酸三苯酯、三苯基氧化膦、磷酸三苯酯、亚磷酸二正丁酯中的一种或多种；活性金属浸渍液各组分的质量浓度如下：活性金属盐以氧化物计，第ⅥB族金属氧化物为1~100g/100mL，第Ⅷ族金属氧化物为1~90g/100mL，含有苯和/或酯类基团的有机磷化物以磷元素计为1~60g/100mL。
2.根据权利要求1所述的活性金属浸渍液，其特征在于：活性金属浸渍液各组分的质量浓度如下：活性金属盐以氧化物计，第ⅥB族金属氧化物为2~70g/100mL，第Ⅷ族金属氧化物为2~60g/100mL，含有苯和/或酯类基团的有机磷化物以磷元素计为2~50g/100mL。
3.根据权利要求1所述的活性金属浸渍液，其特征在于：第ⅥB族金属选为钼和/或钨，第Ⅷ族金属为镍和/或钴。
4.一种权利要求1~3任一所述的活性金属浸渍液的制备方法，其特征在于包括如下内容：先将第VIB族活性金属盐加入有机溶剂中，再加入含有苯和/或酯类基团的有机磷化物后，缓慢升至15~90℃，使之完全溶解，保持温度恒定加入第VIII族活性金属盐并不停搅拌，待完全溶解后得到活性金属浸渍液，保存待用。
5.根据权利要求4所述的制备方法，其特征在于包括如下内容：先将第VIB族活性金属盐加入有机溶剂中，再加入含有苯和/或酯类基团的有机磷化物后，缓慢升至20~65℃，使之完全溶解，保持温度恒定加入第VIII族活性金属盐并不停搅拌，待完全溶解后得到活性金属浸渍液，保存待用。
6.一种加氢处理催化剂的制备方法，其特征在于包括如下内容：用权利要求1~3任一所述的活性金属浸渍液将活性组分负载到载体上，得到加氢处理催化剂。
7.根据权利要求6所述的方法，其特征在于：所述载体选自氧化铝、氧化硅、氧化钛、氧化镁或氧化锆中的一种或多种。
8.根据权利要求6所述的方法，其特征在于：加氢处理催化剂组成如下：以催化剂的重量为基准，加氢活性金属以氧化物计的质量百分含量为3wt%~60wt%，磷元素质量百分含量为0.1wt%~8wt%；其中第VIB族金属为Mo和/或W，第VIII族金属为Ni和/或Co；第VIII族金属/（第VIB族金属+第VIII族金属）以氧化物计的质量比为0.01~0.90；P与第VIII族金属氧化物质量比为0.2~6。
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