CN111097489A - Paraffin hydrofining catalyst and its preparation - Google Patents
Paraffin hydrofining catalyst and its preparation Download PDFInfo
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- CN111097489A CN111097489A CN201811257297.4A CN201811257297A CN111097489A CN 111097489 A CN111097489 A CN 111097489A CN 201811257297 A CN201811257297 A CN 201811257297A CN 111097489 A CN111097489 A CN 111097489A
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- catalyst
- active metal
- carboxyl
- carrier
- drying
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004927 clay Substances 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 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 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021647 smectite Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 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 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000001935 peptisation Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 239000001993 wax Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 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
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- -1 nitric acid Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012169 petroleum derived wax Substances 0.000 description 2
- 235000019381 petroleum wax Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 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
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J35/635—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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 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
-
- 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
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
- C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a paraffin hydrofining catalyst and a preparation method thereof. The carrier of the catalyst comprises alumina, layered clay and a Y-type molecular sieve, wherein nickel and molybdenum are used as active metal components, the mass of the catalyst is used as a reference, the content of the molybdenum oxide is 2.0-35.0 percent, the content of the nickel oxide is 0.5-20.0 percent, and the dispersity of the active metal components is IMo/IAl0.15 to 0.30, INi/IAl0.07 to 0.15. The paraffin hydrorefining catalyst has high utilization rate of active metal, high dispersion degree of the active metal and high activity of the catalyst.
Description
Technical Field
The invention relates to a paraffin hydrofining catalyst and a preparation method thereof.
Background
Paraffin wax is mainly composed of normal paraffinThe molecular weight is 300-500, and the carbon number is C20-C30. The hydrorefining of paraffin wax includes mixing material wax with hydrogen in certain proportion at certain temperature, reaction of hydrogen with S, N, O and other hetero atoms in the material wax to produce H2S、NH3、H2O, etc. to remove impurities. As for the paraffin wax hydrorefining catalyst, molybdenum is generally used as a main metal component, and tungsten is also used as a main metal component. In addition to the primary metal component, the hydrotreating catalyst employs a secondary metal component such as nickel or cobalt.
The raw material cost of the active metals in paraffin hydrofinishing catalysts is a large proportion of the cost of the catalyst, particularly in recent years the price of molybdenum (also including tungsten) has continued to rise. Molybdenum has been the most significant component of the price of paraffin hydrofinishing catalysts. Therefore, how to increase the utilization rate of the active metal and reduce the cost of the paraffin hydrofining catalyst is one of the important issues in the field.
US4186078A is prepared by adding a large amount of silicon to a carrier (containing SiO)25 to 25 wt%) to prepare SiO2- Al2O3Carrier to ensure that the carrier has larger specific surface, larger pore diameter and more concentrated pore distribution. However, the catalyst prepared by this method has a low active metal utilization rate because the amount of the active metal dispersed on the carrier is not sufficiently high.
CN 1249329A discloses a petroleum wax hydrofining catalyst and a preparation method thereof, and the method uses a mixed solution containing molybdenum, nickel and phosphorus to dip gamma-Al2O3Then drying and roasting, wherein the gamma-Al2O3The preparation of the carrier is that α -AlO (OH) of acid sol is kneaded, extruded to form, dried and roasted to prepare the carrier, the concentration of the mixed solution of molybdenum, nickel and phosphorus used in the preparation of the method is high, especially the mass concentration of molybdenum, in addition, the method can not reduce the distribution of active metal in catalyst pores and can not improve the dispersion degree of the active metal nickel, thereby the utilization rate of the active metal is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a paraffin hydrofining catalyst and a preparation method thereof. The paraffin hydrorefining catalyst has high utilization rate of active metal, high dispersion degree of the active metal and high activity of the catalyst.
The invention provides a paraffin hydrorefining catalyst, wherein a carrier of the catalyst comprises alumina, layered clay and a Y-type molecular sieve, nickel and molybdenum are used as active metal components, the content of the molybdenum oxide is 2.0-35.0%, preferably 12.0-25.0%, further preferably 15.0-25.0%, the content of the nickel oxide is 0.5-20.0%, preferably 4.0-10.0%, further preferably 4.0-9.0%, and the dispersity of the active metal components is IMo/IAl0.15 to 0.30, preferably 0.20 to 0.25, INi/IAlIs 0.07 to 0.15, preferably 0.08 to 0.10.
The paraffin hydrofining catalyst also contains phosphorus, and the content of the phosphorus is 0.1-8.0 percent, preferably 0.1-5.0 percent by mass of the catalyst.
The paraffin hydrofining catalyst disclosed by the invention takes the mass of a carrier as a reference, the content of alumina is 50-95%, the content of layered clay is 3-40%, and the content of a Y-type molecular sieve is 1-10%.
In the present invention, the above-mentioned IMo/IAl、INi/IAlRespectively represent the number ratio of active metal atoms and aluminum atoms on the surface of the catalyst.
The active metal dispersion degree is obtained by analyzing the active metal components on the surface of the catalyst by an X photoelectron spectrometer, in particular to an American MultilAB2000 photoelectron spectrometer. The larger the value of the dispersion, the more uniform the dispersion of the active metal.
In the present invention, the layered clay is preferably a smectite clay having a single-layered mineral structure and/or a regular interlayer mineral structure clay having swelling properties. The smectite clay with a single-layer mineral structure with expansibility is preferably one or more of montmorillonite, bentonite, hankelite and beidellite. The regular interstratified mineral structure clay is preferably one or more of rectorite, mica-smectite, glauconite-smectite and chlorite-smectite.
In the invention, the properties of the Y-type molecular sieve are as follows: SiO 22/Al2O3The molar ratio is 3.0-10.0. The Y-type molecular sieve is preferably a hydrogen Y-type molecular sieve.
The second aspect of the present invention provides a preparation method of a paraffin hydrorefining catalyst, comprising:
(1) uniformly mixing pseudo-boehmite and layered clay;
(2) mixing and pulping the Y-shaped molecular sieve and water to obtain uniformly dispersed slurry;
(3) adding the slurry obtained in the step (2) into the mixture obtained in the step (1), kneading and molding, and drying and roasting to obtain a carrier;
(4) spraying and soaking the carrier obtained in the step (3) by using an organic solution containing span surfactant, and then drying;
(5) preparing an active metal solution impregnation liquid containing a carboxyl polymer;
(6) and (4) dipping the carrier obtained in the step (4) by using the dipping solution prepared in the step (5), and then drying and roasting to prepare the paraffin hydrofining catalyst.
In the step (1), the pseudoboehmite can be prepared by a conventional method, and preferably is macroporous pseudoboehmite, so that the carrier obtained in the step (3) has the following properties: the average pore diameter is 8-25 nm, and the specific surface area is 120-450 m2The pore volume is 0.68-1.20 mL/g.
In the step (2), the Y-type molecular sieve and the water are used in a slurry state, and the mass ratio of the Y-type molecular sieve to the water is generally 0.01: 1-0.2: 1.
In the step (3), conventional forming aids, such as at least one of peptizing acid, extrusion aid and water, can be added into the kneading and forming. Wherein the peptizing acid can be inorganic acid, such as nitric acid, and the like, and can also be organic acid, such as at least one of acetic acid, citric acid, tartaric acid, and the like. The extrusion aid can be sesbania powder and the like. The water is preferably deionized water. The drying and roasting can be carried out under conventional conditions, the drying condition is drying for 2-15 hours at 80-150 ℃ in air, and the roasting condition is roasting for 3-5 hours at 350-750 ℃.
The carrier obtained in the step (3) has the following properties: the average pore diameter is 8-25 nm, and the specific surface area is 120-450 m2The pore volume is 0.68-1.20 mL/g.
In the step (4), the span surfactant is at least one of span-40, span-60 and span-80, preferably span-80. The solvent of the organic solution is at least one of ethanol, diethyl ether and methanol, preferably ethanol. The concentration of the span surfactant in the organic solution is 0.01-40.0 g/100mL, preferably 0.01-20.0 g/100 mL. The drying condition is vacuum drying for 2-24 hours at 40-100 ℃.
The carboxyl group-containing polymer in the step (5), which contains one or more carboxyl groups in the repeating unit; the carboxyl-containing polymer is a liquid compound or a soluble polymer. The carboxyl-containing polymer corresponds to the following general formula:
wherein, R1, R2 and R3 are at least one of hydrogen, aliphatic alkyl or substituted derivatives thereof, acyl or substituted derivatives thereof, hydroxyl and carboxyl independently. Further, the carbon number of the aliphatic alkyl is 1-5, the carbon number of the acyl is 1-6, and the carbon number of the carboxyl is 1-6; wherein M is at least one of H, Na and K, and n is a natural number not less than 1.
In the active metal solution containing the carboxyl-containing polymer in the step (5), the content of the carboxyl-containing polymer is 0.1-30.0 g/100mL, preferably 0.1-10.0 g/100mL, calculated by carboxylate radical.
In the method, the active metal solution in the step (5) is a molybdenum-nickel solution; or the active metal solution is a molybdenum nickel phosphorus solution.
In the method, the drying condition in the step (6) is drying for 2-15 hours at 80-150 ℃ in air, and the roasting condition is roasting for 3-5 hours at 350-650 ℃.
Compared with the prior art, the invention has the following advantages:
the paraffin hydrorefining catalyst has high surface active metal dispersion degree, high utilization rate and good activity.
The layered clay is smectite clay with a swelling single-layer mineral structure and/or regular interlayer mineral structure clay, the clay can provide more specific surface area for the catalyst carrier, and the larger specific surface area is beneficial to forming more active metal sites in the subsequent active metal impregnation process of the carboxyl-containing polymer, so that the paraffin component is contacted and reacted with more active metal centers.
The Y-type molecular sieve is added into the catalyst, has the function of peptizing acid, can adjust the acid property of the carrier, and is matched with the property of high dispersion degree of the active metal of the catalyst, so that the catalyst has better aromatic hydrocarbon hydrogenation saturation capacity.
The organic solution containing span surfactant is sprayed and soaked on the carrier, so that the polarity and free energy of the surface of the carrier can be reduced, the capillary pressure in the soaking process is weakened, the active metal entering small pores is reduced, the utilization rate of the active metal is improved, and the uniform distribution of the active metal solution of the soaked carboxyl-containing polymer is facilitated.
Due to the action of carboxylate anions on a macromolecular chain, strong electrostatic force exists near the macromolecular chain, so that the electrostatic attraction between the carboxylate and cations on the macromolecular chain is far larger than that between the corresponding monomer carboxylate and the same cations, and the constraint action of the carboxylate on the cations is increased along with the increase of the dissociation degree of the polymer, the increase of the cation valence and the decrease of the ion radius. Thus, the carboxyl group-containing polymer binds divalent metal ions more strongly than monovalent metal ions. After the carboxyl-containing polymer is added into the active metal impregnation liquid, the dissociated macromolecular anions are combined with divalent nickel ions to play a role in fixing the nickel ions, and meanwhile, the macromolecular ions combined with the nickel ions still have negative charges and are mutually and electrostatically repelled with phosphomolybdic acid radicals in the impregnation liquid to play a role in dispersing the active metal molybdenum.
Detailed Description
The following examples are given to further illustrate the effects and effects of the method of the present invention, but are not limited thereto.
Example 1
(1) Weighing 500g of pseudo-boehmite and 30g of montmorillonite, and uniformly mixing;
(2) weighing 5g of hydrogen type Y-shaped molecular Sieve (SiO)2/Al2O3The molar ratio is 4.7), adding into 400g of deionized water, mixing and pulping;
(3) and (3) adding the slurry obtained in the step (2) into the mixture obtained in the step (1), adding 10g of sesbania powder, 20g of methyl cellulose and 15g of acetic acid, supplementing a proper amount of deionized water, and then kneading and molding at room temperature. After molding, the mixture was dried at 120 ℃ for 4 hours and calcined at 600 ℃ for 4 hours. The specific surface area of the calcined carrier was 365 m2The pore volume is 0.90 mL/g, and the average pore diameter is 12 nm;
(4) weighing 100g of the catalyst carrier prepared in the step (3), spraying and soaking the catalyst carrier by using 100mL of span-80 ethanol solution with the concentration of 0.3g/100mL, and then drying the catalyst carrier for 5 hours in vacuum at the temperature of 60 ℃;
(5) ammonium molybdate, nickel nitrate and phosphoric acid are added into water to be dissolved, and then sodium polymethacrylate is added to obtain an impregnation solution, wherein the content of molybdenum oxide is 51.4/100mL, the content of nickel oxide is 11.0g/100mL, the content of phosphorus is 2.1g/100mL, and the content of sodium polymethacrylate is 0.6g/100mL calculated by carboxylate radical.
(6) And (3) dipping the catalyst carrier dried in the step (4) by using the dipping solution prepared in the step (5), wherein the dipping time is 2 hours, drying is carried out for 5 hours at the temperature of 120 ℃, and then roasting is carried out for 4 hours at the temperature of 500 ℃, so as to obtain the paraffin hydrofining catalyst A.
Example 2
The other steps are the same as example 1 except that 50g of montmorillonite is weighed and mixed with pseudo-boehmite in the step (1) to obtain a paraffin hydrofining catalyst B.
Example 3
Otherwise, the same as example 1 except that 10g of the hydrogen-type Y molecular sieve was weighed in the step (2) and added to 400g of deionized water, and mixed and beaten to obtain a paraffin hydrorefining catalyst C.
Example 4
The rest is the same as the example 1, except that span is used in the step (4) and the ethanol solution with the span-80 concentration of 0.6g/100mL is used. Obtaining the paraffin hydrofining catalyst D.
Example 5
The same procedure as in example 1 was repeated, except that the impregnation solution prepared in step (5) contained 0.8g/100mL of sodium polymethacrylate in terms of carboxylate group and the impregnation time was 3 hours. Thus obtaining the paraffin hydrofining catalyst E.
Comparative example 1
The rest is the same as the example 1, except that the process of adding montmorillonite in the step (1) and spraying and soaking the ethanol solution containing span-80 in the step (4) is not carried out, and the carrier is soaked in the soaking solution prepared in the step (5) to obtain the paraffin hydrofining catalyst F.
Comparative example 2
The rest of the process was the same as example 1 except that the step (4) was not included, and the carrier obtained in the step (3) was directly added to the step (5) to be treated. To obtain the paraffin hydrofining catalyst G.
Comparative example 3
The procedure is otherwise the same as in example 1, except that the impregnation solution in step (5) does not contain sodium polymethacrylate. Obtaining the paraffin hydrofining catalyst H.
Comparative example 4
The other steps are the same as example 1 except that no montmorillonite is added in the step (1), and no sodium polymethacrylate is added in the impregnation liquid in the steps (2), (4) and (5). Obtaining the paraffin hydrofining catalyst I.
The properties of the catalysts prepared in the above examples and comparative examples are shown in Table 1.
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst numbering | A | B | C | D | E |
| Specific surface area, m2/g | 196 | 211 | 195 | 194 | 206 |
| Pore volume, mL/g | 0.60 | 0.68 | 0.58 | 0.59 | 0.62 |
| Several pore diameters, nm | 9.8 | 10.7 | 9.7 | 9.8 | 9.9 |
| MoO3，w% | 22.7 | 22.8 | 22.6 | 22.5 | 23.0 |
| NiO，w% | 6.7 | 6.8 | 6.7 | 6.6 | 6.9 |
| P，w% | 1.9 | 1.9 | 1.9 | 1.8 | 1.9 |
| Degree of dispersion of active metal | |||||
| IMo/IAl | 0.2178 | 0.2236 | 0.2153 | 0.2172 | 0.2245 |
| INi/IAl | 0.0816 | 0.0887 | 0.0809 | 0.0830 | 0.0913 |
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst numbering | F | G | H | I |
| Specific surface area, m2/g | 183 | 193 | 194 | 179 |
| Pore volume, mL/g | 0.50 | 0.56 | 0.57 | 0.48 |
| Several pore diameters, nm | 9.2 | 9.4 | 9.5 | 9.0 |
| MoO3，w% | 22.3 | 22.5 | 22.6 | 22.0 |
| NiO，w% | 6.4 | 6.6 | 6.7 | 6.4 |
| P，w% | 1.7 | 1.7 | 1.9 | 1.7 |
| Degree of dispersion of active metal | ||||
| IMo/IAl | 0.1364 | 0.1490 | 0.1472 | 0.0907 |
| INi/IAl | 0.0676 | 0.0549 | 0.0621 | 0.0459 |
Note: i isMo/IAl、INi/IAlRespectively represent the number ratio of active metal atoms and aluminum atoms on the surface of the catalyst. The degree of dispersion of the active metal in the catalysts obtained in the above examples and comparative examples was measured by using a u.s.multilab 2000 photoelectron spectrometer.
As can be seen from table 1, the paraffin hydrofinishing catalyst prepared by the method of the present invention has higher active metal dispersion degree compared to the comparative example.
The catalysts in the above examples were evaluated by a small paraffin hydrofining evaluation device under the following reaction conditions: the reaction pressure is 6.0MPa, the reaction temperature is 260 ℃, and the LHSV is 1.0h-1The hydrogen wax ratio was 300. The feed wax and corresponding hydrofinished product properties are shown in table 2.
TABLE 2 raw wax and hydrofinished product Properties
| Catalyst numbering | Raw material wax | A | B | C | D | E |
| Melting point of | 59.35 | 59.45 | 59.45 | 59.45 | 59.45 | 59.45 |
| Oil content, wt% | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
| Color (Sai's), number | -15 | +30 | +30 | +30 | +30 | +30 |
| Penetration (25 deg.C)/10-1mm | 15 | 15 | 15 | 15 | 15 | 15 |
| Light stability No. | 6 | 3 | 2～3 | 3 | 3 | 2～3 |
| Heat stability No. 1 | -17 | 28 | 29 | 28 | 28 | 29 |
| Easily carbonized substance | Fail to be qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
TABLE 2 Properties of the raw wax and the hydrorefined products
| Catalyst numbering | Raw material wax | F | G | H | I |
| Melting point of | 59.35 | 59.40 | 59.40 | 59.30 | 59.30 |
| Oil content, wt% | 0.20 | 0.23 | 0.24 | 0.23 | 0.25 |
| Color (Sai's), number | -15 | +28 | +27 | +28 | +25 |
| Penetration (25 deg.C)/10-1mm | 15 | 15 | 15 | 16 | 16 |
| Light stability No. | 6 | 3 | 3 | 3～4 | 4 |
| Heat stability No. 1 | -17 | 23 | 24 | 24 | 21 |
| Easily carbonized substance | Fail to be qualified | Qualified | Qualified | Qualified | Qualified |
As can be seen from Table 2, the catalyst of the present invention has excellent effect on hydrogenation of petroleum wax. Compared with the comparative example, the refined wax obtained by adopting the paraffin hydrofining catalyst prepared by the invention has less oil content, all colors reach No. 30, and the light stability and the heat stability are better than those of the comparative example.
Claims (18)
1. A catalyst for hydrorefining paraffin wax, which is characterized in that: the carrier of the catalyst comprises alumina, layered clay and a Y-type molecular sieve, wherein nickel and molybdenum are used as active metal components, the mass of the catalyst is taken as a reference, the content of the molybdenum oxide is 2.0-35.0%, preferably 12.0-25.0%, more preferably 15.0-25.0%, the content of the nickel oxide is 0.5-20.0%, preferably 4.0-10.0%, more preferably 4.0-9.0%, and the dispersity of the active metal components is IMo/IAl0.15 to 0.30, preferably 0.20 to 0.25, INi/IAlIs 0.07 to 0.15, preferably 0.08 to 0.10.
2. The catalyst of claim 1, wherein: the paraffin hydrofining catalyst contains phosphorus, and the content of the phosphorus is 0.1-8.0 percent, preferably 0.1-5.0 percent by mass of the catalyst.
3. The catalyst of claim 1, wherein: the carrier of the catalyst takes the mass of the carrier as a reference, the content of alumina is 50-95%, the content of layered clay is 3-40%, and the content of Y-type molecular sieve is 1-10%.
4. The catalyst of claim 1, wherein: the layered clay is smectite clay with a single-layer mineral structure and/or clay with a regular interlayer mineral structure, and has expansibility; the smectite clay with a single-layer mineral structure with expansibility is preferably one or more of montmorillonite, bentonite, hank montmorillonite and beidellite; the regular interstratified mineral structure clay is preferably one or more of rectorite, mica-smectite, glauconite-smectite and chlorite-smectite.
5. The catalyst of claim 1, wherein: the properties of the Y-type molecular sieve are as follows: SiO 22/Al2O3The molar ratio is 3.0-10.0; the Y-type molecular sieve is preferably a hydrogen Y-type molecular sieve.
6. A preparation method of a paraffin hydrofining catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing pseudo-boehmite and layered clay;
(2) mixing and pulping the Y-shaped molecular sieve and water to obtain uniformly dispersed slurry;
(3) adding the slurry obtained in the step (2) into the mixture obtained in the step (1), kneading and molding, and drying and roasting to obtain a carrier;
(4) spraying and soaking the carrier obtained in the step (3) by using an organic solution containing span surfactant, and then drying;
(5) preparing an active metal solution impregnation liquid containing a carboxyl polymer;
(6) and (4) dipping the carrier obtained in the step (4) by using the dipping solution prepared in the step (5), and then drying and roasting to prepare the paraffin hydrofining catalyst.
7. The method of claim 6, wherein: in the step (2), the mass ratio of the Y-type molecular sieve to water is 0.01: 1-0.2: 1.
8. The method of claim 6, wherein: in the step (3), a forming aid is added in the kneading and forming process, wherein the forming aid is at least one of peptization acid, extrusion aid and water.
9. The method of claim 6, wherein: in the step (3), the drying condition is drying in air at 80-150 ℃ for 2-15 hours, and the roasting condition is roasting at 350-750 ℃ for 3-5 hours.
10. The method of claim 6, wherein: the carrier obtained in the step (3) has the following properties: the average pore diameter is 8-25 nm, and the specific surface area is 120-450 m2The pore volume is 0.68-1.20 mL/g.
11. The method of claim 6, wherein: the span surfactant in the step (4) is at least one of span-40, span-60 and span-80, preferably span-80; the solvent of the organic solution is at least one of ethanol, diethyl ether and methanol, preferably ethanol.
12. The method of claim 6, wherein: the concentration of the span surfactant in the organic solution in the step (4) is 0.01-40.0 g/100mL, preferably 0.01-20.0 g/100 mL.
13. The method of claim 6, wherein: and (4) drying for 2-24 hours in vacuum at 40-100 ℃.
14. The method of claim 6, wherein: the carboxyl group-containing polymer in the step (5), which contains one or more carboxyl groups in the repeating unit; the carboxyl-containing polymer is a liquid compound or a soluble polymer.
15. A method according to claim 6 or 14, characterized by: the carboxyl-containing polymer corresponds to the following general formula:
wherein, R1, R2 and R3 are at least one of hydrogen, aliphatic alkyl or substituted derivatives thereof, acyl or substituted derivatives thereof, hydroxyl and carboxyl independently; the carbon number of the aliphatic alkyl is 1-5, the carbon number of the acyl is 1-6, and the carbon number of the carboxyl is 1-6; wherein M is at least one of H, Na and K, and n is a natural number not less than 1.
16. The method of claim 6, wherein: in the active metal solution containing the carboxyl-containing polymer in the step (5), the content of the carboxyl-containing polymer is 0.1-30.0 g/100mL, preferably 0.1-10.0 g/100mL, calculated by carboxylate radical.
17. The method of claim 6, wherein: in the step (5), the active metal solution is a molybdenum-nickel solution or a molybdenum-nickel-phosphorus solution.
18. The method of claim 6, wherein: and (3) drying for 2-15 hours at 80-150 ℃ in air under the drying condition, and roasting for 3-5 hours at 350-650 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425361A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN116060087A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
| CN116060085A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Aromatic hydrocarbon hydrogenation saturation catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090858A (en) * | 1998-03-18 | 2000-07-18 | Georgia Tech Reseach Corporation | Shape control method for nanoparticles for making better and new catalysts |
| CN104549430A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst as well as preparation method and application thereof |
| CN105665027A (en) * | 2015-12-29 | 2016-06-15 | 四川大学 | Preparation method of high-dispersing supported metal nano catalyst |
| CN106140310A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
-
2018
- 2018-10-26 CN CN201811257297.4A patent/CN111097489A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090858A (en) * | 1998-03-18 | 2000-07-18 | Georgia Tech Reseach Corporation | Shape control method for nanoparticles for making better and new catalysts |
| CN104549430A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst as well as preparation method and application thereof |
| CN106140310A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN105665027A (en) * | 2015-12-29 | 2016-06-15 | 四川大学 | Preparation method of high-dispersing supported metal nano catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425361A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN114425361B (en) * | 2020-10-29 | 2023-07-28 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN116060087A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
| CN116060085A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Aromatic hydrocarbon hydrogenation saturation catalyst and preparation method and application thereof |
| CN116060087B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
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