CN108067271B - 硫化型加氢催化剂的制备方法 - Google Patents
硫化型加氢催化剂的制备方法 Download PDFInfo
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- CN108067271B CN108067271B CN201611002422.8A CN201611002422A CN108067271B CN 108067271 B CN108067271 B CN 108067271B CN 201611002422 A CN201611002422 A CN 201611002422A CN 108067271 B CN108067271 B CN 108067271B
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- acid
- catalyst
- oil
- added
- liquid mixture
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
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- 239000007788 liquid Substances 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 44
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
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- 238000004073 vulcanization Methods 0.000 claims abstract description 20
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical group CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
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- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 claims 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 1
- 235000014101 wine Nutrition 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 27
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
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- 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 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
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- 239000011609 ammonium molybdate Substances 0.000 description 3
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- 238000004090 dissolution Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
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- 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
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000002285 corn oil Substances 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- 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
- 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
-
- 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
- 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
- B01J35/633—Pore volume less than 0.5 ml/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
- 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
-
- 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
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种硫化型加氢催化剂的制备方法,包括如下内容:(1)将硫化剂、硫化助剂、乳化剂和添加剂颗粒混合均匀,恒温反应,然后加入含有加氢活性金属的水溶液,反应5‑60min,分离除去添加剂颗粒,得到液体混合物I;(2)将胶溶剂、水和尿素混合均匀,得到液体混合物II;(3)将铝源加入到酸性水溶液中打浆,然后加入液体混合物I和II,混合均匀;(4)步骤(3)的浆料进行快速蒸发浓缩得到浓缩浆料,然后进行缓慢干燥处理,得到半干物料;(5)步骤(4)得到的半干物料经碾压,挤出成型,然后焙烧,得到硫化型加氢催化剂。本发明通过催化剂制备和硫化过程同时完成,催化剂孔径分布集中,制备过程简单,具有较为广阔的市场应用前景。
Description
技术领域
本发明涉及一种硫化型加氢催化剂的制备方法。
背景技术
加氢精制、加氢处理和加氢裂化等炼油催化加氢生产工艺过程是环境友好的炼油生产工艺,可广泛应用于生产汽油、煤油、柴油、润滑油、石蜡等清洁石油产品。随着产品质量的不断升级、环保法规的日益严格以及原油日趋劣质化、重质化,加氢技术在全世界范围内都得到广泛重视和应用。我国炼油企业的加氢装置处理能力不断增长,加氢催化剂需求量逐年增加,而这些催化剂大多经硫化后才可获得更好的性能。加氢过程中催化剂的预硫化(活性金属从氧化物状态转化为硫化物状态)是催化剂应用的重要环节之一。因此,催化剂在与烃油接触之前必须先进行预硫化处理,以将催化剂的活性金属从氧化态转化成硫化态。
目前市场提供的加氢催化剂活性金属大多是金属氧化物,国内普遍采用的硫化方法是器内预硫化方法,即在加氢装置内通过严格控制的复杂过程将催化剂的活性金属从氧化态转化为硫化态。加氢催化剂的器内预硫化过程中需要使用和处置一些如二硫化碳CS2等的有毒有害硫化剂;装置需要配套建设仅在新鲜催化剂(或再生催化剂)在开工时才使用的造价较高的硫化系统设施;催化剂反应器内活化过程复杂,硫化剂注入速率、硫化氢浓度和升温速度等控制步骤繁多,使装置开工时间变得漫长,不仅占用了装置有效的生产运行时间,而且加氢催化剂得不到充分的预硫化,催化剂活性金属不能被充分利用,催化剂真正起活性作用的活性中心数所占有的比例不高;催化剂开工现场进行器内预硫化时存在着安全生产隐患及环境污染等问题,如在催化剂硫化期间,加氢装置处于高浓度H2S气氛下,并且在短时间内反复升降温也给炼油企业的安全生产带来隐患;此外,采用器内活化方法,催化剂装填和反应器内构件等众多因素均会严重影响催化剂的活化效果。因此,开发了器外预硫化技术,并在国内外得到广泛的研究和应用。加氢催化剂器外预硫化技术是将新鲜或再生的氧化态催化剂在装入加氢装置反应器之前,在加氢反应器之外对氧化态催化剂进行预硫化处理的工艺方法。采用特殊的工艺过程,将硫化剂提前加到催化剂上,并以硫化物的某种化学形式与催化剂的活性金属组分相结合,将氧化态催化剂制成器外预硫化催化剂,最终将氧化态催化剂转化成硫化态催化剂。
在现有技术中将元素硫引入催化剂的方式一般包括升华吸附、熔化浸渍、分散在有机溶液中浸渍、直接用固体元素硫粉末混合等。CN200510046429.5公开了一种加氢催化剂组合物及其制备方法。该方法通过引入有机氮化合物与硫、有机溶剂共同作用下,可以进一步提高催化剂在活化时的持硫率,减缓集中放热,降低催化剂床层的温升,并且可以提高催化剂活性。
但是,无论采用器内预硫化技术还是器外预硫化技术,催化剂在实际应用之前都必须经历催化剂的载体制备(载体的挤条成型、干燥、焙烧),催化剂活性金属物质的添加,活性金属物质转化为氧化态(催化剂的挤条成型、干燥、焙烧)、活性金属物质由氧化态转化为硫化态的过程(催化剂的器内预硫化或器外预硫化),因此,上述过程复杂,生产过程的影响因素多、催化剂产品的制造成本高。另外,由于经历了多个步骤最终完成催化剂的硫化,使得催化剂的活性金属只能处于催化剂最外表面的能够得到利用,而内层或与催化剂载体形成较强相互作用的部分不能得到充分硫化,从而影响催化剂活性的发挥。
CN201210442769.X公开了一种硫化型加氢催化剂的制备方法,该方法中的方式一:采用载体前驱物与元素硫、辅助剂混合或混捏,成型,干燥,负载加氢活性金属组分,然后进行热处理,得到硫化型加氢催化剂;方式二:将活性金属在制备载体时引入,可混合或混捏加入活性金属盐溶液,也可与活性金属盐与载体前驱物、元素硫、辅助剂、成型助剂混合,成型后干燥和热处理。然后再高温处理。其中,方式一制备的催化剂存在元素硫与加氢活性金属组分是分步加入的,即元素硫和载体前驱物辅及助剂先混合,然后在经过一定的热处理后才与活性金属组分相互作用,因此,元素硫先与载体物质作用,与活性金属组分很难很好地相互作用,不利于活性金属组分的硫化反应,从而影响活性金属的利用率,降低催化剂活性;方式二制备催化剂时,直接将活性金属组分与载体前驱物、元素硫、辅助剂、成型助剂混合,同样存在活性金属组分与元素硫混合的相互作用效果不好的问题。
发明内容
针对现有技术的不足,本发明提供了一种硫化型加氢催化剂的制备方法。本发明通过催化剂制备和硫化过程同时完成,得到适宜孔结构和催化性能,催化剂孔径分布集中,制备过程简单、提高催化剂的催化活性、降低催化剂制备成本,切合了当前国内炼油企业的现实需求,具有较为广阔的市场应用前景。
本发明的硫化型加氢催化剂的制备方法,包括如下内容:
(1)将硫化剂、硫化助剂、乳化剂和添加剂颗粒混合均匀,在90-150℃条件下恒温5-50min,然后加入含有加氢活性金属的水溶液,100-160℃下反应5-60min,分离除去添加剂颗粒,得到液体混合物I;
(2)将胶溶剂、水和尿素混合均匀,得到液体混合物II;
(3)将铝源加入到酸性水溶液中打浆,然后向浆料中加入液体混合物I、液体混合物II,混合均匀;
(4)步骤(3)的浆料进行快速蒸发浓缩至原体积的44%~83%,优选为50%~70%,得到浓缩浆料,然后进行缓慢干燥处理,得到体积为原体积20%~66%的半干物料;
(5)步骤(3)得到的半干物料经碾压,挤出成型,然后焙烧,得到硫化型加氢催化剂。
本发明方法中,步骤(1)所述的硫化剂为单质硫,二硫化碳,硫化氨,二甲基二硫化物,叔丁基多硫化物,叔壬基多硫,硫脲,正丁基硫醇、乙基硫醇、多硫化物、硫酚、硫醚、环丁砜和二甲亚砜等中的一种或几种。
本发明方法中,步骤(1)所述的硫化助剂为植物油、动物油、汽油、煤油、柴油、白油或润滑油等中的一种或几种;所述的植物油可以为菜子油、豆油、花生油、玉米油、亚麻油、蓖麻油、棉籽油、葵花籽油、茶籽油和椰子油等植物油,所述的动物油为猪油、牛油和羊油等。
本发明方法中,步骤(1)所述的添加剂为加氢领域中常用的加氢精制催化剂和/或加氢裂化催化剂,加氢精制催化剂为加氢脱硫和/或加氢脱氮催化剂,可以是商用的或自行研发制备的。如中国石油化工股份有限公司抚顺石油化工研究院研制开发的催化剂FH-40B、FH-40C、UDS-5、UDS-6、FF-36、FF-46、FC-12、FC-32和FC-50等,以及上述这些氧化态催化剂经过器外预硫化处理的器外预硫化催化剂等中的一种或几种。
本发明方法中,步骤(1)所述的添加剂的颗粒直径为0.1-100mm,较好为0.5-50mm,最好为3-10mm。
本发明方法中,步骤(1)所述的加氢活性金属为第VIB族和/或第VIII族金属,第VIB族金属为Mo和/或W,第VIII族金属为Ni和/或Co;含有加氢活性金属的水溶液浓度以氧化物计:WO3和/或MoO3为5-200g/100ml,优选为10-180g/100ml,更优选为20-100g/100ml,NiO和/或CoO 为1-80g/100ml,优选为5-50g/100ml。例如Mo-Ni-P水溶液浓度为MoO320-100g/100ml,NiO5-40g/100ml,Mo-Co水溶液浓度为MoO320-100g/100ml,CoO5-40g/100ml,W-Ni-P水溶液浓度为WO320-100g/100ml,NiO5-40g/100ml。含有加氢活性金属的水溶液的配制方式为本领技术技术人员熟知,一般采用含有活性金属的盐类等原料进行配制,如硝酸镍、碳酸镍、柠檬酸镍、三氧化钼、七钼酸铵、二钼酸铵、钼酸铵、(偏)钨酸铵、(碱式)碳酸钴、硝酸钴、柠檬酸钴等。
本发明方法中,步骤(1)所述的乳化剂选自阴离子乳化剂、阳离子乳化剂或非离子乳化剂中的一种或几种;其中阴离子乳化剂可以为硫酸化蓖麻油、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠、椰油酸单乙醇酰胺磺基琥珀酸单酯二钠、十二烷基聚氧乙烯醚硫酸钠、十二烷基聚氧乙烯醚羧酸钠、月桂酸钠、十二烷基磺酸钠、二辛基琥珀酸磺酸钠、油酰甲基牛磺酸钠、亚甲基双萘磺酸钠、硬脂酸甲酯聚氧乙烯醚磺酸盐、单十二烷基磷酸酯钾、月桂醇醚磷酸酯、月桂醇醚磷酸酯钾或月桂酸钾皂中的一种或几种;阳离子乳化剂可以为聚乙烯亚胺、聚乙烯基吡咯烷酮、聚马来酰亚胺及其衍生物、季铵化聚丙烯酰胺、聚乙烯基吡啶盐、聚二甲胺环氧氯丙烷、脂肪胺、烷基二胺、烷基多胺、丙烯酰胺、卡洛胺、三乙基胺、十二烷基二甲基苄基氯化铵、烷基三甲基卤化铵、双十八烷基二甲基氯化铵、乙氧化胺、丙氧化胺、吡啶卤化铵、咪唑啉或妥尔油酰胺中的一种或多种;非离子乳化剂可以为水溶性酚醛树脂、聚丙烯酸酯、氨基树脂、聚醚、聚乙烯醇、椰油脂肪酸二乙醇酰胺、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、烷基醇酰胺聚氧乙烯醚、嵌段聚氧乙烯-聚氧丙烯醚、烷基多苷、多元醇硬脂酸酯、山梨醇脂肪酸酯、脂肪酸环氧乙烷缩合物、蓖麻油聚氧乙烯醚或聚乙二醇双油酸酯中的一种或几种。优选采用阴离子与非离子乳化剂组合,或阳离子与非离子乳化剂组合。
本发明方法中,步骤(1)所述液体混合物I各组分的质量百分比为:硫化剂0.2%~25%,硫化助剂0.7%~58%,乳化剂 0.1%~16%,加氢活性金属水溶液1%~99%;优选为:硫化剂1%~15%,硫化助剂4%~35%,乳化剂0.5%~10%,加氢活性金属水溶液20%~85%;更优选为:硫化剂2%~14%,硫化助剂6%~30%,乳化剂2%~6%,加氢活性金属水溶液50%~90%。
本发明方法中,步骤(1)所述的添加剂与液体混合物I中的硫化剂的质量比为1:0.001-50,优选为1:0.01-5,更优选为1:0.04-1.6。
本发明方法中,步骤(2)所述的胶溶剂为无机酸和/或有机酸;其中无机酸选自硝酸、磷酸;有机酸选自草酸、柠檬酸、月桂酸、乳酸、柠檬酸、苹果酸、酒石酸或琥珀酸中的一种或几种;优选无机酸和有机酸两种,无机酸与有机酸的质量比为1:0.1-25,优选为1:0.5-12.5,更优选为1:1-2.5。
本发明方法中,步骤(2)所述的液体混合物II各组分的质量百分比为:胶溶剂0.1%~30%,尿素0.1%~50%,水20%~99.8%;液体混合物II优选组成为:胶溶剂1%~25%,尿素1%~35%,水40%~98%;液体混合物II更优选组成为:胶溶剂3%~14%,尿素2%~16%,水70%~95%。
本发明方法中,步骤(3)所述的铝源为拟薄水铝石、氢氧化铝、氧化铝、氧化铝干胶、高醇铝、铝片、硝酸铝、分子筛或蒙脱土中的一种或几种。
本发明方法中,步骤(3)所述的除了铝源之外,还可以加入硅、钛、锆等助剂。其中,硅源为硅溶胶、水玻璃、 硅酸、二氧化硅、四氟硅酸铵、硅酸钠、正硅酸乙酯、分子筛、白碳黑和蒙脱土中的一种或几种;钛源为二氧化钛、三氯化钛、四氯化钛、硝酸钛和硫酸钛的一种或几种;锆源为二氧化锆、氧氯化锆、氯化锆、硝酸锆和硫酸锆的一种或几种。助剂的加入方式可以在步骤(1)、步骤(2)和步骤(3)任意的步骤中加入;如果助剂以液态的形式加入,可以加入液体混合物I和/或液体混合物II之中;如果助剂以固态物质加入,可以在步骤(3)的混合或混捏过程中加入。铝源与助剂质量比为1:0.001-0.8,优选为1:0.05-0.5,更优选为1:0.01-0.15。
本发明方法中,步骤(3)所述的铝源:液体混合物I:液体混合物II质量比为:1:0.1-33:0.1-155,优选为1:0.1-16:0.2-78,更优选为1:0.1-3.3:0.3-15.5。
本发明方法中,步骤(3)所述的酸性水溶液为硝酸水溶液,以H+计酸性水溶液的浓度为:0.01-10mol/L,优选为0.1-3.0mol/L,更优选为0.2-1.5 mol/L;铝源与酸性水溶液的质量比为1:0.1-100,优选为1:1.0-50,更优选为1:1.0-10。
本发明方法中,步骤(4)所述的快速蒸发浓缩条件为:温度为100-700℃,优选150-350℃,时间为0.05-1.5h,优选0.1-0.5h。
本发明方法中,步骤(4)所述的所述的缓慢干燥处理条件为:缓慢干燥温度为40-200℃,优选为60-120℃;缓慢干燥温度时间为2-15h,优选为3-8.0h。
本发明方法中,步骤(5)所述的焙烧条件为350-600℃焙烧2-8小时。
本发明方法中,还可以在步骤(1)、步骤(2)或步骤(3)中加入扩孔剂,如聚环氧乙烷、环氧树脂、聚乙二醇(PET)、聚乙烯醇、丙二醇、甘油、三甘醇、聚丙酰胺、田菁粉、淀粉、纤维素、季铵盐。扩孔剂在步骤(1)中加入时,扩孔剂与液体混合物I质量为1:2-100。扩孔剂在步骤(2)中加入时,扩孔剂与液体混合物II质量比为1:1-410。扩孔剂在步骤(3)中加入时,铝源与扩孔剂质量比为为1:0.02-0.5。
本发明方法中,上述所加入的活性金属、铝源、助剂、扩孔剂等物质可以采用多样加入方式。如果这些物质是可溶解与水中的物质、或是可以水相和(/或)与油相溶的液态物质,则可以在液态的形式加入液体混合物I、液体混合物II之中;如果这些物质是固态物质,可以加入固体混合物之中。本发明方法中,步骤(3)中加入的液体混合物II,也可以在步骤(5)中与半干物料混合加入。
所述的步骤(3)也可以将铝源、酸性水溶液、液体混合物I和液体混合物II混合后,在进行打浆;或将铝源、酸性水溶液和液体混合物II进行打浆后,再与液体混合物I混合;或将铝源、酸性水溶液中的酸、液体混合物II中的胶溶剂和尿素共同加入到水中,进行打浆,得到的浆料再与液体混合物I混合,其中水量为酸性水溶液中的水量和液体混合物II中的水量之和。
本发明方法制备的催化剂在柴油加氢脱硫反应和加氢脱氮反应中的应用,一般的反应条件为:反应压力4.0-8.0MPa、反应温度340-360℃、氢油体积比200-500、体积空速1-4h-1。
本发明与现有技术相比具有如下优点:
(1)发明人在研究中发现,无论是活性金属的金属氧化物、硫化剂与氧化铝前身物这种混捏方式,还是完全硫化后的金属硫化物再与氧化铝前身物混捏,即使存在助挤剂、胶溶剂的情况下,物料之间的结合度并不是很好,物料之间很容易发生松散,而通过控制金属与硫的硫化程度,使二者之间交联缩合反应时,硫处于双键的交联键合之中,此时这种活性半硫化金属硫化物(没有完全硫化生成金属硫化物)与氢氧化铝很容易结合在一起,混捏之后,得到的催化剂的强度大大提高,同时活性组分分布更加均匀;
本发明在制备液体混合物I时,添加了乳化剂,形成水包油状态,使得液体混合物中的油相和水相更好的混合,易于催化物质与硫化剂、硫化助剂的相互作用,使得催化剂最终能够更好的硫化,从而提高催化剂加氢活性;水包油态的液体混合物I与水相的液体混合物II混合更加充分,有利于物料之间的结合;混合物前驱物(浆料)中含有大量的水,打浆混合过程中,物料充分混合、打磨并形成细小粒子,物料在水体系中处于膨胀状态,然后采用先快速蒸发脱水,然后再缓慢干燥的方式,膨胀的物料经历瞬间收缩再缓慢收缩的过程,易于形成4-10nm的集中的孔经分布区间,有利于提高催化剂的加氢活性。
(2)本发明在制备过程中加入的尿素,通过调节尿素与胶溶剂的比例,使活性金属逐步均匀沉淀,同时与氢氧化铝结合,促进了活性金属硫化物的均匀分布,避免产生活性金属团聚的现象,然后经过干燥与焙烧过程时,尿素或是水解反应生成NH3和CO2,或是缩合反应生成缩二脲,这两种反应最终都有利于催化剂孔道的生成;在挤条过程中,保存下来的孔促使在催化剂自然断裂开,形成催化剂的自然断条;本发明在制备过程中加入氧化型催化剂或器外预硫化催化剂等添加剂,促进了活性金属的金属氧化物与硫化剂形成活性半硫化金属硫化物。
(3)本发明催化剂具有多级孔道,有利于催化剂的加氢脱硫和加氢脱氮反应的进行,有利于加氢反应过程中反应物在催化剂孔道内的扩散,提高催化剂的活性。而且,硫化剂同时作为扩孔剂,可以使得催化剂的制备催化剂的孔刚好形成于催化剂表面活性金属所在处,有利于反应物扩散在此反应,因而提高了催化剂的加氢活性,同时提高催化剂的活性金属利用率。
(4)本发明催化剂开工时可以直接活化,不需要再硫化,节省加氢装置的开工时间,提高炼油厂的经济效益。
具体实施方式
下面结合实施例进一步说明本发明的制备过程,但并不因此限制本发明。
实施例1
1. 配制Mo-Ni-P溶液:首先在配制容器内加入净水50ml,启动搅拌器,缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g,最后缓慢加入磷酸1.27g,避免碱式碳酸盐加热分解出二氧化碳突沸,物料加完盖紧盖,然后加热升温至>100℃,恒温1~2h,至氧化钼和碱式碳酸镍全部溶解,制备得到Mo-Ni-P溶液。Mo-Ni-P溶液浓度为MoO3 57.1g/100ml;NiO 9.8 g/100ml;P 4.0 g/100ml;
2. 取单质硫10.9 g、煤油2g、菜子油22g进行混合15min;加入Mo-Ni 型EPRES器外预硫化催化剂UDS-6(Φ3.0)5g,升温至100-120℃,恒温5-15min;然后,加入聚乙烯亚胺0.5g,加入上述Mo-Ni-P溶液64ml,并在120℃恒温25min,然后,冷却并分离除掉器外预硫化催化剂UDS-6,得到液体混合物I;
3. 取水50ml,加入浓硝酸4.6ml稀释后得到稀硝酸;然后,再加入柠檬酸5g和尿素4g,然后,加入甘油2g,搅拌混匀,得到液体混合物II;
4. 取水150ml,加入浓硝酸(质量百分浓度65%)4ml稀释后得到稀硝酸;将稀硝酸加入打浆罐,将醇铝法制备的拟薄水铝石66.7g、硫酸铝法制备的氢氧化铝71.4g和田菁粉3g加入打浆罐中,充分打浆混合60min;并在搅拌同时加入液体混合物I、液体混合物II,混合20min,得到浆料;
5. 浆料在400℃烘干30min,浓缩至原体积的40%;然后将浓缩浆料在200℃烘干2.5h,得到半干物料;
6. 然后将半干物料加入碾压机中进行碾压30min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm-3.0mm),得到催化剂前驱物;
7. 催化剂前驱物在500℃焙烧3h,得到催化剂A,该催化剂内活性金属组分的含量为MoO3 24.0%,NiO 4.10%。
实施例2
1. 首先在配制容器内加入净水25ml,启动搅拌器,缓慢加入碱式碳酸钴9.8g,柠檬酸14g,然后加热升温至>100℃,恒温10~20min,自然冷却至室温,得到Co-柠檬酸溶液,浓度为CoO 14.5g/100ml;
2. 取二甲基二硫化物15.6g、柴油2g、豆油22g、甘油3g进行混合5min;加入Co-Mo型EPRES器外预硫化催化剂FH-40B(Φ3.0)5g,升温至100-120℃,恒温25min;然后,加入十二烷基苯磺酸钠5g,加入上述Co-柠檬酸溶液65ml,并在120℃恒温25min。然后,冷却并分离除掉器外预硫化催化剂FH-40B,得到液体混合物I;
3. 取水50ml,加入浓硝酸4.6ml稀释后得到稀硝酸;然后,再加入柠檬酸5g和尿素4g,然后,再加入硅溶胶20g,搅拌均匀,得到液体混合物II;
4.氢氧化铝140.0g、淀粉3.5g、三氧化钼42.6g加入混捏机中,混合20min,得到固体混合物;
5. 取水100ml,加入浓硝酸(质量百分浓度65%)1.4ml稀释后得到稀硝酸;将稀硝酸加入上述固体混合物中,充分打浆混合300min;加入将液体混合物I、液体混合物II,混合25 min,得到浆料;
6. 浆料在350℃烘干5min,浓缩至原体积的50%,然后110℃烘干2.5h,得到半干物料;
7. 然后将半干物料加入碾压机中进行碾压30min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm-3.0mm),得到催化剂前驱物;
8. 催化剂前前驱物在450焙烧3h,得到催化剂B,该催化剂内活性金属组分的含量为MoO3 42.0%,CoO 3.7%。
实施例3
1. 首先在配制容器内加入净水25ml,启动搅拌器,缓慢加入碱式碳酸钴9.8g,柠檬酸14g,然后加热升温至>100℃,恒温10~20min,自然冷却至室温,溶液体积35ml。制备得到Co-柠檬酸溶液。然后加入七钼酸铵18.2g,再加入氨水(比重0.94g/ml)50ml,配制得到Co-Mo柠檬酸溶液浓度为MoO3, 21.1g/100ml;CoO,3.90g/100ml;
2. 取单质硫12.9 g、白油2.2g、猪油24g进行混合15min;加入氧化态Co-Mo催化剂UDS-5(Φ3.0)5.0g,升温至100-120℃,恒温5-15min;加入十二烷基三甲基溴化铵和椰油脂肪酸二乙醇酰胺各2.5 g,然后,加入上述Co-Mo柠檬酸溶液66ml,并在120℃恒温25min,然后,冷却并分离除掉催化剂UDS-5,得到液体混合物I;
3. 取水52ml,然后加入柠檬酸5g和尿素4g,搅拌均匀,得到液体混合物II;
4.醇铝法氢氧化铝140.0g和田菁粉3.0g加入混捏机中,混合20min,得到铝源混合物;
5. 取水200ml,加入浓硝酸(质量百分浓度65%)5ml稀释后得到稀硝酸;将稀硝酸加入上述铝源混合物中,充分打浆混合30 min;加入将液体混合物I,混合25 min,得到浆料;
6. 浆料在700℃烘干35min,浓缩至原体积50%;然后将催化剂在70℃烘干4h,得到半干物料;
7. 然后将半干物料、液体混合物II加入碾压机中进行碾压30min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ 0.9mm),得到催化剂前驱物;
8. 催化剂前驱物在500℃焙烧3h,得到催化剂C。该催化剂内活性金属组分的含量为MoO3 18.0%,CoO 3.70%。
实施例4
1. 配制Mo-Ni-P溶液:首先在配制容器内加入净水50ml,启动搅拌器,缓慢加入偏钨酸61.0g、碱式碳酸镍16.0g,最后缓慢加入磷酸1.27g,避免碱式碳酸盐加热分解出二氧化碳突沸,物料加完盖紧盖,然后加热升温至>100℃,恒温1~2h,至氧化钼和碱式碳酸镍全部溶解,然后,加入三氯化钛3g,制备得到Mo-Ni-P溶液。Mo-Ni-P溶液浓度为MoO3,62.1g/100ml;NiO,10.8 g/100ml;P,4.0 g/100ml;
2. 取单质硫11.3 g、煤油2.4g、花生油22.5g进行混合35min;加入Ni-Mo型催化剂UDS-6(Φ3.0)15.0g,升温至100-120℃,恒温25min;加入硫酸化蓖麻油3.0g,然后,加入上述Mo-Ni-P溶液65ml,并在120℃恒温25min,然后,冷却并分离除掉催化剂UDS-6,得到液体混合物I;
3. 取水50ml,加入浓硝酸4.8ml稀释后得到稀硝酸,然后加入柠檬酸8g、尿素7g、甘油2g,搅拌均匀,得到液体混合物II;
4.拟薄水铝石143.0g、碱式碳酸镍8.4g和田菁粉7g加入混捏机中,混合20min,得到固体混合物;
5. 取水100ml,加入浓硝酸(质量百分浓度65%)1ml稀释后得到稀硝酸;将稀硝酸加入上述固体混合物中,充分打浆混合90 min;加入将液体混合物I、液体混合物II,混合20min,得到浆料;
6.浆料在350℃烘干40min,浓缩至原体积的50%,然后在70℃烘干5h,得到半干物料;
7. 将半干物料加入碾压机中进行碾压40min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm-3.0mm),得到催化剂前驱物;
8. 催化剂前驱物在500焙烧3h,得到催化剂D,该催化剂内活性金属组分的含量为MoO3 25.0%,NiO 4.20%。
实施例5
1. 配制W-Ni溶液:首先在配制容器内加入净水60L,启动搅拌器,缓慢加入偏钨酸铵58.0kg、硝酸镍38.7kg,搅拌1h,至偏钨酸铵和硝酸镍全部溶解,制备得到W-Ni溶液。W-Ni溶液浓度为WO3,49.0g/100ml;NiO,10.2 g/100ml;
2. 取单质硫10.4 kg、煤油2.3kg、菜子油21.5kg进行混合55min;加入W-Ni 型FC-32催化剂(Φ1.5)5kg,升温至100-120℃,恒温25min;然后,加入山梨醇脂肪酸酯10kg,加入上述W-Ni溶液65L,并在120℃恒温25min,然后,冷却并分离除掉催化剂FC-32,得到液体混合物I;
3. 取水170L,加入浓硝酸4.6L稀释后得到稀硝酸;然后,再加入柠檬酸4.5g和尿素3.5kg,然后加入甘油4kg,搅拌均匀,得到液体混合物II;
4. 液体混合物I、液体混合物II、氢氧化铝66.2kg、氧化铝70.9kg、田菁粉7.0kg加入混合罐中,充分打浆混合115min,得到浆料;
5. 浆料在500℃烘干15min,浓缩至原体积的55%,然后在150℃烘干5h,得到半干物料;
6. 然后将半干物料加入碾压机中进行碾压35min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ 0.9mm),得到催化剂前驱物;
7. 烘干物在500℃焙烧3h,得到催化剂E,该催化剂内活性金属组分的含量为WO321.0%,NiO 4.9%。
实施例6
1. 配制W-Mo-Ni-P溶液:首先在配制容器内加入净水50L,启动搅拌器,缓慢加入氧化钼47.6 kg、碱式碳酸镍22.4kg,最后缓慢加入磷酸1.27kg,避免碱式碳酸盐加热分解出二氧化碳突沸,物料加完盖紧盖,然后加热升温至101℃,恒温1~2h,至氧化钼和碱式碳酸镍全部溶解,冷却后缓慢加入偏钨酸铵16.8kg,制备得到W-Mo-Ni-P溶液。W-Mo-Ni-P溶液浓度为WO3,13.5 g/100ml;MoO3, 42.8g/100ml;NiO,9.8 g/100ml;
2. 取单质硫16.9kg、煤油8kg、花生油28kg进行混合15min;加入EPRES器外预硫化催化剂FH-40C(Φ3.0)25.5kg,升温至140℃,恒温15min;边搅拌边加入十六烷基三甲基溴化铵100g,然后,加入上述W-Mo-Ni-P溶液120L,并在120℃恒温25min, 然后,冷却并分离除掉器外预硫化催化剂FH-40C,得到液体混合物I;
3. 取水100L,加入浓硝酸10.6L稀释后得到稀硝酸;将稀硝酸加入打浆罐,加入氢氧化铝150.0kg、田菁粉9.0kg,然后加入液体混合物II(水50L、柠檬酸11kg、尿素10kg),充分打浆混合180min;
4. 液体混合物I与步骤(3)的得到的物料混合20min,得到浆料;
5. 浆料在700℃烘干30min,浓缩至原体积的40%,然后在80℃烘干8.0h,得到半干物料;
6. 将半干物料加入碾压机中进行碾压15min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm-3.0mm),得到催化剂前驱物;
7. 催化剂前驱物在400℃焙烧3h,得到催化剂F,该催化剂内活性金属组分的含量为WO3 8.0%;MoO3 18.5%,NiO 4.50%。
对比例1
1. 配制Mo-Ni-P溶液:首先在配制容器内加入净水50ml,启动搅拌器,缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g,最后缓慢加入磷酸1.27g,避免碱式碳酸盐加热分解出二氧化碳突沸,物料加完盖紧盖,然后加热升温至>100℃,恒温1~2h,至氧化钼和碱式碳酸镍全部溶解,制备得到Mo-Ni -P溶液。Mo-Ni -P溶液浓度为MoO3,57.1g/100ml;NiO,9.8 g/100ml;P,4.0 g/100ml;
2. 取单质硫10.9 g、煤油2g、菜子油22g进行混合15min;加入Mo-Ni 型EPRES器外预硫化催化剂UDS-6(Φ3.0)5g,升温至100-120℃,恒温5-15min;然后,加入上述Mo-Ni-P溶液64ml,并在120℃恒温25min,然后,冷却并分离除掉器外预硫化催化剂UDS-6,得到液体混合物I;
3. 取水50ml,加入浓硝酸4.6ml稀释后得到稀硝酸;然后,再加入柠檬酸5g和尿素4g,然后,加入甘油2g,搅拌混匀,得到液体混合物II;
4. 将液体混合物I、液体混合物II、将醇铝法制备的拟薄水铝石66.7g、硫酸铝法制备的氢氧化铝71.4g和田菁粉3g加入混捏机中,混合20min;然后将混合物料加入碾压机中进行碾压30min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm-3.0mm),得到催化剂的前驱物;
5. 催化剂的前驱物在120℃烘干4h,500℃焙烧3h,得到催化剂G,该催化剂内活性金属组分的含量为MoO3 24.1%,NiO 4.05%。
对比例2
1. 取水48ml,加入浓硝酸4.6ml稀释后得到稀硝酸;然后,再加入柠檬酸5g和尿素4g,搅拌混匀,得到液体混合物;
2. 将液体混合物、拟薄水铝石66.7g、硫酸铝法制备的氧化铝71.4g、田菁粉3g加入混捏机中,混合20min;然后将混合物料加入碾压机中进行碾压30min,取出混合物料,在F-75型挤条机进行挤条(挤条 模具的孔径Φ0.9mm),得到催化剂的载体湿料,载体湿料在110℃烘干4h,然后再600℃焙烧3h,得到载体;
5. 配制Mo-Ni -P溶液:首先在配制容器内加入净水50ml,启动搅拌器,缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g,最后缓慢加入磷酸1.27g,避免碱式碳酸盐加热分解出二氧化碳突沸,物料加完盖紧盖,然后加热升温至>100℃,恒温1~2h,至氧化钼和碱式碳酸镍全部溶解,制备得到Mo-Ni-P溶液;
6. 取载体100g,采用饱和浸渍法进行喷淋上述Mo-Ni-P溶液80ml,得到催化剂湿料,催化剂湿料在110℃烘干4h,然后在600℃焙烧3h,得到催化剂H。该催化剂活性金属组分的含量为MoO3 24.3%,NiO 4.30%。
对比例3
1. 称取拟薄水铝石(山东氧化铝厂生产,干基为73wt%)900g,田菁粉19g,柠檬酸32g,己烯54ml,硝酸(重量浓度30%)48ml,硅胶(以重量计含二氧化硅30%)159ml,硫代硫酸铵溶液250ml(含硫60g/100ml)混合均匀,在挤条机上挤成1.2mm三叶草条,在鼓风干燥箱中于120℃干燥3小时,即得载体;
2. 取含钼酸铵和硝酸镍溶液(含氧化钼30g/100ml,含氧化镍5g/100ml)浸渍载体A后于120℃干燥3小时,之后在氮气保护下进行热处理,首先升温至200℃,恒温2小时,之后再升温至280℃,恒温1小时,最后升温至450℃恒温3小时,得到催化剂I,该催化剂内活性金属组分的含量为MoO3 24.1%,NiO 4.07%。
对比例4
称取拟薄水铝石(山东氧化铝厂生产,干基为73wt%)900g,田菁粉19g单质硫100g,柠檬酸32g,十二烯30ml,钼酸铵245g,硝酸镍127g,硝酸(重量浓度30%)48ml,硅胶(以重量计含二氧化硅30%)159ml,去离子水250ml混合均匀,在挤条机上挤成1.2mm三叶草条,在鼓风干燥箱中于120℃干燥5小时,之后在氢气保护下热处理,先在290℃恒温2小时,再在400℃恒温3小时即得催化剂J,该催化剂内活性金属组分的含量为MoO3 24.0%,NiO 4.00%。
实施例7
以混合柴油为原料油,在反应压力6.0MPa、氢油体积比350:1、体积空速2.5h-1、反应温度350℃的工艺条件下,对比评价了实施例的催化剂A~F和对比例催化剂G、H、I和J的加氢活性,其中催化剂H、I和J的开工过程涉及下列步骤:(1) 用氮进行系统的吹扫直至氧的浓度低于0.5 vol%然后在3.4 MPa压力下进行气动试验;(2) 在200℃下用氮气干燥催化剂4h;(3) 在150℃用CS2和轻柴油的混合物湿处理2h进行催化剂的预硫化;(4) 以10-25℃/h的速率持续升温至230℃,然后保持温度10h;(5) 以相同速率进一步升温至320℃并再保持10h。当H2S在循环氢气的浓度为1.0 vol%时,硫化结束;(6) 逐渐引入反应油物料并结束开工过程参比催化剂的后续活性评价在上述工艺条件下进行。
催化剂A~J的性质见表1,催化剂A~J活性对比结果见表2。结果表明,本发明催化剂具有较高的加氢脱硫和加氢脱氮活性。本发明催化剂活性稳定性在一个长时间的反应中进行了考察,本发明催化剂在至少1000小时反应中具有较好活性稳定性。
表1催化剂的性质。
表2本发明催化剂和参比催化剂的加氢活性对比。
Claims (13)
1.一种硫化型加氢催化剂的制备方法,其特征在于包括如下内容:(1)将硫化剂、硫化助剂、乳化剂和添加剂颗粒混合均匀,在90-150℃条件下恒温5-50min,然后加入含有加氢活性金属的水溶液,100-160℃下反应5-60min,分离除去添加剂颗粒,得到液体混合物I;(2)将胶溶剂、水和尿素混合均匀,得到液体混合物II;(3)将铝源加入到酸性水溶液中打浆,然后向浆料中加入液体混合物I、液体混合物II,混合均匀;(4)步骤(3)的浆料进行快速蒸发浓缩至原体积的44%~83%,得到浓缩浆料,然后进行缓慢干燥处理,得到体积为原体积20%~66%的半干物料;(5)步骤(4)得到的半干物料经碾压,挤出成型,然后焙烧,得到硫化型加氢催化剂;步骤(1)所述的硫化剂为单质硫、二硫化碳、硫化氨、二甲基二硫化物、叔丁基多硫化物、叔壬基多硫、硫脲、正丁基硫醇、乙基硫醇、多硫化物、硫酚、硫醚、环丁砜和二甲亚砜中的一种或几种;步骤(1)所述的硫化助剂为植物油、动物油、汽油、煤油、柴油、白油或润滑油中的一种或几种;步骤(1)所述的乳化剂选自阴离子乳化剂、阳离子乳化剂或非离子乳化剂中的一种或几种;其中阴离子乳化剂为硫酸化蓖麻油、十二烷基苯磺酸钠、十二烷基硫酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚磺基琥珀酸单酯二钠、椰油酸单乙醇酰胺磺基琥珀酸单酯二钠、十二烷基聚氧乙烯醚硫酸钠、十二烷基聚氧乙烯醚羧酸钠、月桂酸钠、十二烷基磺酸钠、二辛基琥珀酸磺酸钠、油酰甲基牛磺酸钠、亚甲基双萘磺酸钠、硬脂酸甲酯聚氧乙烯醚磺酸盐、单十二烷基磷酸酯钾、月桂醇醚磷酸酯、月桂醇醚磷酸酯钾或月桂酸钾皂中的一种或几种;阳离子乳化剂为聚乙烯亚胺、聚乙烯基吡咯烷酮、聚马来酰亚胺及其衍生物、季铵化聚丙烯酰胺、聚乙烯基吡啶盐、聚二甲胺环氧氯丙烷、脂肪胺、烷基二胺、烷基多胺、丙烯酰胺、卡洛胺、三乙基胺、十二烷基二甲基苄基氯化铵、烷基三甲基卤化铵、双十八烷基二甲基氯化铵、乙氧化胺、丙氧化胺、吡啶卤化铵、咪唑啉或妥尔油酰胺中的一种或多种;非离子乳化剂为水溶性酚醛树脂、聚丙烯酸酯、氨基树脂、聚醚、聚乙烯醇、椰油脂肪酸二乙醇酰胺、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、烷基醇酰胺聚氧乙烯醚、嵌段聚氧乙烯-聚氧丙烯醚、烷基多苷、多元醇硬脂酸酯、山梨醇脂肪酸酯、脂肪酸环氧乙烷缩合物、蓖麻油聚氧乙烯醚或聚乙二醇双油酸酯中的一种或几种;步骤(1)所述的添加剂为加氢精制催化剂和/或加氢裂化催化剂,加氢精制催化剂为加氢脱硫和/或加氢脱氮催化剂;步骤(1)所述液体混合物I各组分的质量百分比为:硫化剂0.2%~25%,硫化助剂0.7%~58%,乳化剂 0.1%~16%,加氢活性金属水溶液1%~99%;步骤(1)所述的添加剂与液体混合物I中的硫化剂的质量比为1:0.001-50;步骤(2)所述的液体混合物II各组分的质量百分比为:胶溶剂0.1%~30%,尿素0.1%~50%,水20%~99.8%。
2.按照权利要求1所述的方法,其特征在于:所述的植物油为菜子油、豆油、花生油、玉米油、亚麻油、蓖麻油、棉籽油、葵花籽油、茶籽油和椰子油中的一种或几种;所述的动物油为猪油、牛油和羊油中的一种或几种。
3.按照权利要求1所述的方法,其特征在于:步骤(1)所述的添加剂的颗粒直径为0.1-100mm。
4.按照权利要求1所述的方法,其特征在于:步骤(2)所述的胶溶剂为无机酸和/或有机酸;其中无机酸选自硝酸、磷酸;有机酸选自草酸、柠檬酸、月桂酸、乳酸、柠檬酸、苹果酸、酒石酸或琥珀酸中的一种或几种。
5.按照权利要求1所述的方法,其特征在于:步骤(3)所述的铝源为拟薄水铝石、氢氧化铝、氧化铝、氧化铝干胶、高醇铝、铝片、硝酸铝、分子筛或蒙脱土中的一种或几种。
6.按照权利要求1所述的方法,其特征在于:步骤(3)中加入硅、钛或锆中一种或几种助剂;其中,硅源为硅溶胶、水玻璃、 硅酸、二氧化硅、四氟硅酸铵、硅酸钠、正硅酸乙酯、分子筛、白碳黑和蒙脱土中的一种或几种;钛源为二氧化钛、三氯化钛、四氯化钛、硝酸钛和硫酸钛的一种或几种;锆源为二氧化锆、氧氯化锆、氯化锆、硝酸锆和硫酸锆的一种或几种;助剂的加入方式在步骤(1)、步骤(2)和步骤(3)任意的步骤中加入;铝源与助剂质量比为1:0.001-0.8。
7.按照权利要求1所述的方法,其特征在于:步骤(3)所述的铝源:液体混合物I:液体混合物II质量比为:1:0.1-33:0.1-155。
8.按照权利要求1所述的方法,其特征在于:步骤(3)所述的酸性水溶液为硝酸水溶液,以H+计酸性水溶液的浓度为:0.01-10mol/L;铝源与酸性水溶液的质量比为1:0.1-100。
9.按照权利要求1所述的方法,其特征在于:步骤(4)所述的快速蒸发浓缩条件为:温度为100-700℃,时间为0.05-1.5h。
10.按照权利要求1所述的方法,其特征在于:步骤(4)所述的缓慢干燥处理条件为:温度为40-200℃,时间为2-15h。
11.按照权利要求1所述的方法,其特征在于:步骤(5)所述的焙烧条件为350-600℃焙烧2-8小时。
12.按照权利要求1所述的方法,其特征在于:在步骤(1)、步骤(2)或步骤(3)中加入扩孔剂,扩孔剂选自聚环氧乙烷、环氧树脂、聚乙二醇、聚乙烯醇、丙二醇、甘油、三甘醇、聚丙酰胺、田菁粉、淀粉、纤维素或季铵盐中的一种或几种;扩孔剂在步骤(1)中加入时,扩孔剂与液体混合物I质量为1:2-100;扩孔剂在步骤(2)中加入时,扩孔剂与液体混合物II质量比为1:1-410;扩孔剂在步骤(3)中加入时,铝源与扩孔剂质量比为为1:0.02-0.5。
13.按照权利要求1~12任一权利要求所述的方法制备的催化剂在柴油加氢脱硫反应和加氢脱氮反应中的应用,反应条件为:反应压力4.0-8.0MPa、反应温度340-360℃、氢油体积比200-500、体积空速1-4h-1。
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