CN112717962A - 一种加氢处理催化剂及其制备方法和应用 - Google Patents
一种加氢处理催化剂及其制备方法和应用 Download PDFInfo
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- CN112717962A CN112717962A CN201911030761.0A CN201911030761A CN112717962A CN 112717962 A CN112717962 A CN 112717962A CN 201911030761 A CN201911030761 A CN 201911030761A CN 112717962 A CN112717962 A CN 112717962A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 238000005470 impregnation Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 4
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000008139 complexing agent Substances 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007865 diluting Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- JCNHQILGQVWEKA-UHFFFAOYSA-N acetamide;1,1'-biphenyl Chemical group CC(N)=O.C1=CC=CC=C1C1=CC=CC=C1 JCNHQILGQVWEKA-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- -1 VIB group metal compound Chemical class 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 238000005303 weighing Methods 0.000 description 4
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 101000616862 Dendroaspis angusticeps Mambaquaretin-1 Proteins 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 239000001630 malic acid Substances 0.000 description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VKEYBCCRWVJINU-UHFFFAOYSA-N 1-(5-amino-2-phenylphenyl)ethanone Chemical group CC(=O)C1=CC(N)=CC=C1C1=CC=CC=C1 VKEYBCCRWVJINU-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NQIBQILAMKZKFE-UHFFFAOYSA-N 2-(5-bromo-2-fluorophenyl)-3-fluoropyridine Chemical compound FC1=CC=C(Br)C=C1C1=NC=CC=C1F NQIBQILAMKZKFE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QAZHUKSXFSJRQW-UHFFFAOYSA-N 5-amino-2-phenylbenzoic acid Chemical group OC(=O)C1=CC(N)=CC=C1C1=CC=CC=C1 QAZHUKSXFSJRQW-UHFFFAOYSA-N 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 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
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- 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
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
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Abstract
Description
技术领域
本发明涉及一种加氢处理催化剂及其制备方法和应用,具体地说涉及一种高活性加氢处理催化剂及其制备方法和应用。
背景介绍
磷钼杂多酸和磷钨杂多酸的镍盐在酸性条件下具有较高的溶解度和溶液稳定性,是制备高活性加氢精制催化剂常用的浸渍液,为了提高催化剂活性,工业上通常在浸渍液中加入镍的络合助剂,来协调活性金属镍和钼的分散及硫化速度,提高加氢活性相的表面原子结构。
CN107486216A公开一种以苹果酸、水杨酸、酒石酸等小分子有机酸为络合剂,分步配制浸渍液的方法:(1)配制含有至少一种含第VIII族金属的化合物和至少一种含第一种第VIB金属的化合物的第一溶液;(2)将第一溶液在高温、高压下进行活化处理;(3)待活化处理后的第一溶液温度降至室温后,向其中引入至少一种含第二种第VIB金属的化合物,得到所述浸渍溶液。
CN106475110B公开一种以柠檬酸、苹果酸和乙二胺四乙酸为络合剂,在载体表面负载超高金属的加氢催化剂制备方法:以二氧化为硅载体并对其进行铝改性;再通过分布浸渍和焙烧的方法,将大量的活性金属引入到载体中。
CN103055956 B公开一种以一乙醇胺,二乙醇胺、三乙醇胺等小分子醇胺类为络合剂,分布制备加氢催化剂溶液的方法:以VIIIB族金属化合物和第一种有机络合物配制成溶液A;将VIB族金属化合物配备水溶液B;将上述两种溶液混合后得到加氢催化剂的浸渍液。
US 6239066 B1公开一种以二乙烯三胺五乙酸、乙二醇双(2-氨基乙基醚)四乙酸、N,N-二乙基乙醇胺等多齿配体含氮化合物为络合剂,以介孔氧化铝为载体,制备加氢催化剂的方法。
综上所述,现有技术中络合助剂加入浸渍液中与镍、钴形成的络合物能够提高加氢处理催化剂的活性,但是提高的幅度有限,所述加氢处理催化剂的活性和稠环芳烃的饱和性需要进一步提高。
发明内容
针对现有技术的不足,本发明公开一种加氢处理催化剂及其制备方法和应用。所述方法制备的加氢处理催化剂能够显著提高活性和稠环芳烃的饱和性。
一种加氢处理催化剂的制备方法,所述方法包括如下步骤:
(1)配制活性金属浸渍液,所述活性金属浸渍液中含有化合物,所述化合物具有式(I)的结构;
(2)采用步骤(1)配制的活性金属浸渍液浸渍氧化铝载体,经干燥、焙烧后制得最终加氢处理催化剂;
(I)
其中,式(I)所述化合物中,R1-R8为-H或-COOH中的至少一种。
上述方法中,所述活性金属为至少一种第VIB族金属和至少一种第VIII族金属,所述第VIB族金属优选为钼或钨,所述第VIII族的金属优选为镍或钴,进一步优选为镍。所述第VIB族金属和第VIII族金属来自于所对应的硝酸盐、硫酸盐或氯化盐。
上述方法中,所述配制的活性金属浸渍液中含有式(I)结构化合物的质量含量为5-45%,优选为20-30%。
上述方法中,所述活性金属浸渍液为含有活性金属的磷酸水溶液,磷酸质量浓度为2%-16%,优选4%-8%。
上述方法中,所述活性金属浸渍液的pH值控制在0.5-3.0,优选1.0-2.0。
上述方法中,一种常规的氧化铝载体的制备方法,包括以氢氧化铝干胶粉为原料,经成型、干燥、焙烧后制得氧化铝载体。所述氢氧化铝干胶粉或者含有助剂的氢氧化铝干胶粉可以为市售商品或采用任意一种现有技术制备。优选氢氧化铝干胶粉活化后(500℃焙烧3小时)比表面为150-450 m2/g,优选为250-400 m2/g,孔容为0.5-1.2 ml/g,优选为0.6-1.0ml/g。
上述方法中,所述浸渍可以是等体积浸渍,也可是过量浸渍,可以是分步浸渍,也可是共浸渍,最好是等体积共浸渍。浸渍方法是技术人员所熟知的。所述浸渍溶液通过用第ⅥB族和Ⅷ族金属的化合物来制备,其溶液浓度可通过各化合物的加量来调节,从而制备指定活性组分含量的催化剂,溶液的配制方法为本领域技术人员所公知。
上述方法中,所述干燥温度为50°C-250°C,优选为135-175°C,干燥时间为4.0 h-72.0 h,优选为12.0 h-48.0 h;焙烧温度为450°C-650°C,优选为500-550°C,焙烧时间为2.0 h-12.0 h,优选为4.0-6.0 h。
一种采用上述方法制备的加氢处理催化剂,以最终催化剂的重量计,第VIB族金属(以金属氧化物计)的含量为8.0%-32%,优选 15-25%,进一步优选 20-23% ,第VIII族金属(以金属氧化物计)的含量为2.0%-8.0%,优选 3.0-6.0%,进一步优选4.0-5.0% 。
上述催化剂中,所述催化剂的比表面积为120-320 m2/g,优选180-260,进一步优选210-230,孔容为0.2-0.7 ml/g,优选0.3-0.65,进一步优选0.50-0.55。
本发明方法中采用结构式为式(I)的特定结构化合物,化合物中的胺基可以与浸渍液中的镍(钴)离子配位,形成稳定的络合物,结合化合物的特定结构把镍或钴引入到氧化铝载体中的特定部位,进而提高催化剂的活性和稠环芳烃的饱和性。
具体实施方式
本发明一个或多个具体实施方式中,氧化铝载体的具体制备过程如下:氢氧化铝干胶粉中加入胶溶剂与助挤剂,经混捏、碾压、成型、干燥、焙烧步骤后,经干燥焙烧制备γ-Al2O3载体。所述的胶溶剂为硝酸、醋酸、草酸的一种或多种。助挤剂为柠檬酸、田菁粉或淀粉的一种或多种。
本发明一个或多个具体实施方式中,式(I)化合物对胺基联苯为市售商品,羧基的引入可由将胺基联苯经公知的卤化,水解,酰胺化,氧化,水解这些步骤后,得到含有羧酸的胺基联苯的混合物。
本发明方法中,所述活性组分的原料一般为盐类、氧化物或酸类型的化合物,如钼一般来自氧化钼、钼酸铵、仲钼酸铵中的一种或几种,钨一般来自偏钨酸铵,镍来自硝酸铵、碳酸镍、碱式碳酸镍中的一种或几种,钴来自硝酸钴、碳酸钴、碱式碳酸钴中的一种或几种。
下面结合实施例及比较例来进一步说明本发明方法的作用及效果,但以下实施例不构成对本发明方法的限制。
实施例1
本实施例介绍以对胺基联苯为络合助剂,制备含络合剂的加氢催化剂。
称取干胶粉400.0 g,加入柠檬酸6.0 g,田菁粉7.0 g,混合均匀后,加入质量分数为2.0 %的硝酸340.0 g。碾压20.0 min后,用直径1.7 mm的三叶草孔板挤条。120°C干燥4.0h后500°C焙烧4.0 h。焙烧后的载体记为S-0。
称取S-0载体100.0g,用三氧化钼、碳酸镍、质量分数为85%的磷酸混合,配制每100ml含有Mo(0.46mol)、Ni (0.22mol)、P(0.12mol)的水溶液,记为MQ-0,称取18.0g 对胺基联苯,溶于50.0ml的MQ-0并稀释至88.0ml,此时溶液pH值为2,得到的溶液记为MQ-1。用MQ-1浸渍S-0载体,经150°C干燥4.0 h,500°C焙烧2.0 h后,获得的催化剂记为Mo-1。
称取S-0载体100.0g,用偏钨酸铵、碳酸镍、质量分数为85%的磷酸混合,配制每100ml含有W (0.46mol)、Ni (0.22mol)、P(0.12mol)的水溶液,记为WQ-0,称取18.0g 对胺基联苯,溶于50.0ml的 WQ-0并稀释至88.0ml,此时溶液pH值为1,所得到的浸渍液记为WQ-1。用WQ-1浸渍S-0载体,经150°C干燥4.0 h,500°C焙烧2.0 h后,获得的催化剂记为W-1。
实施例2
本实施例介绍制备含较少羧基的对胺基联苯为络合助剂,以及相应加氢催化剂的制备过程。氧化铝载体S-0的制备同实施例1。
称取100.0g 对胺基联苯,用60.0g 冰醋酸,和2.0g 锌粉,加热至105°C,加热过程中分离水,回流醋酸和胺基联苯,2小时后了冷却分离,洗涤后得到乙酰对胺基联苯与胺基联苯的混合物(记作B-1)。
称取80.0g M-1,溶于300.0 g异丙醇,加入30.0 g无水三氯化铝,控制反应温度20.0 °C,反应时间8.0 h。反应结束后,将反应液倾入含有冰水的浓盐酸烧杯中,分出水层,将有机层进行干燥丙基乙酰胺联苯与乙酰胺联苯的混合物(记作B-2)。
称取70.0g M-2,与200g含2.0%的吡啶水溶液混合,加热至65°C后,缓慢加入100.0g的高锰酸钾。用甲苯萃取反应物,蒸发溶剂后得到含羧基的乙酰胺联苯、丙基乙酰胺联苯与乙酰胺联苯混合物(记作B-3)。
称取60.0g M-3,与100g 质量分数20%的浓硫酸混合加热并回流0.5 h,分离水层并用甲苯萃取,蒸干后得到的主要产物为含有羧基的对胺基联苯的混合物(记作B-4)
取MQ-0溶液50.0ml,取混合物B-4 12.70g,混合并稀释至88.0ml,此时溶液pH为1,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-2。
取WQ-0溶液50.0ml,取混合物B-4 12.70g,混合并稀释至88.0ml,此时溶液pH为2,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为W-2。
实施例3
本实施例介绍在含较少羧基的对胺基联苯混合物的基础上,制备含适中羧基的对胺基联苯为络合助剂,以及相应加氢催化剂的过程。氧化铝载体S-0的制备同实施例1。含有少量乙酰胺联苯、丙基乙酰胺联苯与乙酰胺联苯混合物(B-3)的制备方法如实施例2。将B-3继续与150g含2.0%的吡啶水溶液混合,加热至70°C后,缓慢加入100.0 高锰酸钾。并溶甲苯萃取反应物,蒸发溶剂后得到含有羧基的乙酰胺联苯、丙基乙酰胺联苯与乙酰胺联苯混合物(记作B-5)。称取60.0g M-6,与100g 质量分数20%的浓硫酸混合加热并回流0.5 h,分离水层并用甲苯萃取,蒸干后得到的主要产物为含有中量羧基的对胺基联苯的混合物(记作B-6)。
取MQ-0溶液50.0ml,取混合物B-6 12.70g,混合并稀释至88.0ml,此时溶液pH为1,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-3。
取WQ-0溶液50.0ml,取混合物B-6 12.70g,混合并稀释至88.0ml,此时溶液pH为1.5,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为W-3。
实施例4
本实施例介绍在含适中羧基的对胺基联苯混合物的基础上,制备含较多羧基的对胺基联苯为络合助剂,和相应加氢催化剂的过程。氧化铝载体S-0的制备同实施例1。含有适中乙酰胺联苯、丙基乙酰胺联苯与乙酰胺联苯混合物(B-5)的制备方法如实施例3。将B-5继续与100g含2.0的吡啶水溶液混合,加热至75°C后,缓慢加入100.0 高锰酸钾,得到的含有羧基的乙酰胺联苯、丙基乙酰胺联苯与乙酰胺联苯混合物(记作B-7)。
称取60.0g B-7,与100g 质量分数20%的浓硫酸混合加热并回流0.5 h,分离水层并用甲苯萃取,蒸干后得到的主要产物为含较多羧基的对胺基联苯的混合物(记作B-8)。
取MQ-0溶液50.0ml,取混合物B-6 12.70g,混合并稀释至88.0ml,此时溶液pH为1,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-4。
取WQ-0溶液50.0ml,取混合物B-8 12.70g,混合并稀释至88.0ml,此时溶液pH为1,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为W-4。
对比例 1
本对照例介绍未含助剂的加氢处理催化剂的制备。氧化铝载体S-0的制备同实施例1。
取MQ-0溶液50.0ml,稀释至88.0ml,用稀释后的溶液浸渍S-0,后经120°C干燥4.0h,450°C焙烧2.0 h后,获得的催化剂记为Mo-5。
取WQ-0溶液50.0ml,稀释至88.0ml,用稀释后的溶液浸渍S-0,后经120°C干燥4.0h,450°C焙烧2.0 h后,获得的催化剂记为W-5。
对比例2
本对照例介绍以小分子有机胺为助剂的加氢处理催化剂的制备。氧化铝载体S-0的制备同实施例1。
取二乙醇胺与Mo、Ni溶液配制为浸渍液,使溶液中二乙醇胺与Ni元素的质量比为2:1,等体积浸渍S-1,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-6。
取MQ-0溶液50.0ml,取二乙醇胺 12.70g,混合并稀释至88.0ml,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-6。
取WQ-0溶液50.0ml,取二乙醇胺 12.70g,混合并稀释至88.0ml,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为W-6。
对比例3
本对照例介绍以大分子有机胺为助剂的加氢处理催化剂的制备。氧化铝载体S-0的制备同实施例1。
取MQ-0溶液50.0ml,取二乙烯三胺五乙酸 12.70g,混合并稀释至88.0ml,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为Mo-7。
取WQ-0溶液50.0ml,取二乙烯三胺五乙酸 12.70g,混合并稀释至88.0ml,等体积浸渍S-0,经120°C干燥4.0 h,450°C焙烧2.0 h后,获得的催化剂记为W-7。
其中实施例和对比例的催化剂性质如表1和表2所示。
表1 制备的Mo、Ni系催化剂的主要理化性质
表2 制备的W、Ni系催化剂的主要理化性质
实施例5
本实施例为催化剂的活性评价实验
催化剂活性评价实验在50 ml小型加氢装置上进行,活性评价前对催化剂进行预硫化。催化剂评价条件为在总反应压力6.0 MPa,体积空速1.0 h-1,氢油比900:1,反应温度为370°C。活性评价实验原料油性质见表3,活性评价结果见表4和表5.
表 3 原料油性质
表4 Mo、Ni系催化剂活性评价结果
表5W、Ni系催化剂活性评价结果
从催化剂表征结果和评价结果中可以看出,本发明通过引入大分子络合助剂,增大了载体的平均孔径,说明络合剂抑制了Ni原子在小孔中的沉积,同时提高了Ni原子在载体表面的分散均匀度,使载体表面Ni-Mo原子比更高。
羧酸引入深度的不同,对油品的加氢处理效果也不同,对于处理饱和度较高,芳烃含量较低的减压瓦斯油,需要催化剂具有较强的氢解活性选择性,需要活性相表面有多的Mo、W原子,而Ni原子则需要更多的分散在载体与Mo、W原子之间,因此,需要Ni原子先于Mo、W原子沉淀,此时选用络合剂需要较低的羧基引入率,来降低溶液中Ni的溶解度,实现Ni原子的优先沉淀和吸附;从反应结果中可以看出,由浅度处理络合剂制备的加氢催化剂Mo-1、Mo-2、W-1和W-2对处理VGO具有较高的加氢脱硫、脱氮性能。
对于处理饱和度较低的、芳烃含量较高的焦化蜡油来说,需要催化剂具有较强的加氢活性选择性,需要活性相表面具有较高的Ni原子比例,而需要Mo、W原子更多的起到活性相体相骨架的作用,此时,需要溶液中的Ni原子后于Mo、W原子沉淀,此时选用络合剂的需要较高的羧基引入率,来提高溶液中Ni的溶解度,实现Ni原子的滞后沉淀和吸附。从反应结果中可以看出,由深度处理络合剂制备的加氢催化剂Mo-3、Mo-4、W-3和W-4对处理CGO具有较高的加氢脱硫、脱氮性能及芳烃饱和性能。
Claims (12)
2.根据权利要求1所述的方法,其特征在于:所述活性金属为至少一种第VIB族金属和至少一种第VIII族金属。
3.根据权利要求2所述的方法,其特征在于:所述第VIB族金属为钼或钨,所述第VIII族的金属为镍或钴,所述第VIB族金属和第VIII族金属来自于所对应的硝酸盐、硫酸盐或氯化盐。
4.根据权利要求1所述的方法,其特征在于:所述配制的活性金属浸渍液中含有式(I)结构化合物的质量含量为5-45%。
5.根据权利要求1所述的方法,其特征在于:所述活性金属浸渍液为含有活性金属的磷酸水溶液,磷酸质量浓度为2%-16%。
6.根据权利要求1所述的方法,其特征在于:所述活性金属浸渍液的pH值控制在0.5-3.0。
7.根据权利要求1所述的方法,其特征在于:所述浸渍为等体积浸渍或过量浸渍,所述浸渍液通过用第ⅥB族和Ⅷ族金属的化合物来制备。
8.根据权利要求1所述的方法,其特征在于:所述干燥温度为50°C-250°C,干燥时间为4.0 h-72.0 h;焙烧温度为450°C-650°C,焙烧时间为2.0 h-12.0 h。
9.一种采用权利要求1至8任一方法制备的加氢处理催化剂,其特征在于:以最终催化剂的重量计,第VIB族金属以金属氧化物计的含量为8.0%-32%,第VIII族金属以金属氧化物计的含量为2.0%-8.0%。
10.根据权利要求9所述的催化剂,其特征在于:以最终催化剂的重量计,第VIB族金属以金属氧化物计的含量为15-25%,第VIII族金属以金属氧化物计的含量为3.0-6.0%。
11.根据权利要求9所述的催化剂,其特征在于:所述催化剂的比表面积为120-320 m2/g,孔容为0.2-0.7 ml/g。
12.权利要求9所述催化剂在加氢处理中的应用。
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