CN100446856C - Petroleum wax hydrofining catalyst and its prepn process - Google Patents
Petroleum wax hydrofining catalyst and its prepn process Download PDFInfo
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- CN100446856C CN100446856C CNB2006101036491A CN200610103649A CN100446856C CN 100446856 C CN100446856 C CN 100446856C CN B2006101036491 A CNB2006101036491 A CN B2006101036491A CN 200610103649 A CN200610103649 A CN 200610103649A CN 100446856 C CN100446856 C CN 100446856C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000012169 petroleum derived wax Substances 0.000 title abstract 2
- 235000019381 petroleum wax Nutrition 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 24
- 230000008569 process Effects 0.000 title description 12
- 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 58
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000012188 paraffin wax Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 206010013786 Dry skin Diseases 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- LCSNMIIKJKUSFF-UHFFFAOYSA-N [Ni].[Mo].[W] Chemical compound [Ni].[Mo].[W] LCSNMIIKJKUSFF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 13
- 230000009471 action Effects 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005984 hydrogenation reaction 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent 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
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- -1 nickel aluminate Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention is one kind of petroleum wax hydrofining catalyst and its preparation process. The catalyst consists of carrier and carrier supported active components, the carrier consists of alumina and fluorine, and the active components include Ni and Mo3 and/or WO3. The catalyst has reasonable surface property and channel structure; relative great pore size favorable to eliminating colloid, asphaltene and metal compounds from wax material; low carrier surface energy resulting in reduced mutual action between the carrier and the active components and raised utilization rate of the active components and raised hydrogenating active of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method's of Hydrobon catalyst, particularly a kind of catalyst for hydrorefining pertroleum wax preparation method.
Background technology
Pertroleum wax is the staple product of petroleum refining industry, and pertroleum wax mainly comprises paraffin, vaseline, high melting point paraffin, microwax etc., and pertroleum wax is of many uses.The oil wax material that the common solvent process for dewaxing makes in the prior art, owing to contain the impurity that some influences color and light, thermostability in the oil wax material that obtains of solvent dewaxing usually, the present hydrorefined method of industrial main employing removes.The hydrorefined purpose of oil wax material is intended to keep paraffinic components, removes with 3, and the 4-BaP is sulphur, nitrogen and the oxygen impurities of carcinogens such as the condensed-nuclei aromatics of representative and non-hydrocarbons.Because the molecule of paraffin is bigger, therefore require the pertroleum wax catalyst should have big pore volume, aperture and specific area, assorted ability is held in the diffusion, the raising that are beneficial to reactant molecule and hydrogenation products, simultaneously, also require catalyst to have to try one's best few solid acid and based on faintly acid, reason is that this process does not allow to take place cracking reaction, otherwise will cause the increase of wax material oil content and needle penetration.
At present, most catalyst for hydrorefining pertroleum wax is generally adopted Mo, W, Ni is an active component, Al
2O
3Or Al
2O
3-SiO
2Be carrier, also contain just like auxiliary agents such as silicon, phosphorus, zirconium, boron, fluorine, alkali metal and alkaline-earth metal.The sintering temperature of carrier generally is lower than 700 ℃, and average pore size has only about 6～10nm.In recent years, because heavy, the increase of crude oil with poor quality yield and the factors such as change of some oil plant production procedure cause paraffin raw material poor qualityization day by day.Pertroleum wax hydrogenation catalyst at present commonly used is when handling the high wax material inferior of colloid, asphalt content, because interior diffusion influence causes active surface area effectively not utilize, hydrogenation reaction is not thorough, poor product quality can not satisfy higher product index requirement; And the complex manufacturing of catalyst, the production cost height can not meet the needs of production, and needs further improvement badly.
Chinese patent CN1105053A discloses a kind of Hydrobon catalyst of being made by aluminium oxide and tungsten, nickel active component and fluorine auxiliary agent, this catalyst obtains the macropore alumina supporter of modification by air and the high-temperature roasting of water vapor mixture atmosphere, catalyst has hydrofinishing performance preferably, but because this pore canal structure of catalyst is still less, be unsuitable for the hydrofinishing of the bigger paraffin raw material of molecular weight, in other words the hydrogenation poor-performing.In addition, handle carrier with high-temperature water vapor, complicated operation, energy consumption are higher in industrial production.
Chinese patent CN1044816C has introduced a kind of catalyst for hydrorefining pertroleum wax of being made up of magnesia, nickel oxide, tungsten oxide and aluminium oxide, this catalyst adopts roasting under air atmosphere, obtain modified aluminium oxide supports through the water vapour high-temperature process again, soak magnesium, drying, roasting then earlier, soak tungsten-nickel, drying, roasting again and obtain catalyst, catalyst is used for routine paraffin wax hydrofinishing, better performances, but Catalyst Production complex procedures, cost is higher, and is also relatively poor to the adaptability and the contamination resistance of inferior raw material.
Chinese patent CN1393528A discloses a kind of catalyst for hydrogen refining of paraffin wax and its production and use.Its carrier characteristics are, contain titanium dioxide through chemical treatment on alumina surface, have improved the characteristic of carrier; The catalyst activity component adopts W-Mo-Ni solution single-steeping method, and metal component reaches common competitive Adsorption, to make the special-purpose catalyst for hydrogen refining of paraffin wax with greater activity.Its modified additive is the Ti element, but also relatively poor to the adaptability and the contamination resistance of raw material.
Chinese patent CN1085594A discloses a kind of Wax hydrofining catalyst and method for making thereof.This Preparation of catalysts process: use in the ammoniacal liquor and the silicon behind low temperature aging-aluminium mixed sols, after filtering, washing, with phosphoric acid and nitric acid peptization, by the oil ammonia column moulding, drying and roasting get P more then
2O
5-SiO
2-Al
2O
3Carrier with the aqueous solution dipping that contains molybdenum and nickel, makes catalyst then.Catalyst preparation process complexity, environmental pollution weigh, product yield is low, preparation cost is high.
Summary of the invention
The objective of the invention is to overcome that prior art catalyst preparation process complexity, environmental pollution are heavy, product yield is low, preparation cost is high, the catalyst aperture is little, active surface area can not effectively be utilized, hydrogenation reaction is not thorough, poor product quality, can not satisfy higher product index requirement, to the adaptability of raw material and the shortcoming of contamination resistance difference, provide that a kind of preparation technology of having is simple and easy to control, average pore size is big, catalyst activity is high, contamination resistance is strong, be applicable to the hydrogenation catalyst of the pertroleum wax raw material inferior of handling high impurity content.
Catalyst for hydrogen refining of paraffin wax of the present invention is made up of carrier and the active component that is carried on the carrier, in this catalyst by weight percentage composition represent: carrier 60～80%, active component 20～40%; Carrier is made up of aluminium oxide and fluorine, and by the weight ratio of carrier, aluminium oxide: fluorine is 90～99: 1～10; Active component comprises the Ni element and is selected from Mo
3, WO
3In two kinds or any one material, the weight ratio of each component is: Mo
3: WO
3: NiO is 0～30: 0～40: 1～10.
Catalyst for hydrogen refining of paraffin wax, percentage composition is represented by weight, optimization formula is: carrier 65-75%, active component 25-35%.
Catalyst for hydrogen refining of paraffin wax, percentage composition is represented by weight, optimization formula is: carrier 70%, active component 30%.
Described activity component weight ratio is preferably: Mo
3: NiO is 20～25: 5～10 or WO
3: NiO is 25～35: 3～8 or Mo
3: WO
3: NiO is 10～15: 10～20: 3～8.
Described activity component weight ratio is preferably: Mo
3: NiO is 22: 8 or WO
3: NiO is 30: 5 or Mo
3: WO
3: NiO is 12: 15: 5.
The preparation method of catalyst for hydrogen refining of paraffin wax, step is as follows:
(1) with the alumina precursor extrusion modling, then 100～120 ℃ of dryings 2～14 hours, 400～600 ℃ of roastings 2～6 hours, be warmed up to 750～1000 ℃ of roastings 1～4 hour then, obtain macropore alumina supporter;
(2) with the above-mentioned carrier that obtains, through the fluorinated water solution impregnation, 100～120 ℃ of dryings 2～14 hours, 200～500 ℃ of air were handled 2～8 hours down, obtained fluorine-containing carrier;
(3) the fluorine-containing carrier that will obtain, through the water-soluble co-impregnated solution of the active constituent that contains tungsten-nickel or tungsten-molybdenum-nickel or molybdenum nickel dipping, 100～120 ℃ of dryings 2～14 hours, 400～600 ℃ of air were handled 2～8 hours down, obtained catalyst.
Further say, the preparation method of catalyst for hydrogen refining of paraffin wax, step is as follows:
(1) with alumina precursor extrusion modling according to a conventional method, then 100～120 ℃ of dry 6-10 hours, at 450-550 ℃ of roasting 3-5 hour, be rapidly heated then 800-900 ℃ of roasting 2-3 hour, obtain macropore alumina supporter.
(2) with the above-mentioned carrier that obtains, through the fluorinated water solution impregnation, at 100～120 ℃ of dry 6-10 hours, 200～500 ℃ of air were handled 4-6 hour down, obtained fluorine-containing carrier.
(3) the fluorine-containing carrier that will obtain, through the water-soluble co-impregnated solution dipping of the active constituent that contains tungsten-nickel or tungsten-molybdenum-nickel or molybdenum nickel, at 100～120 ℃ of dry 6-10 hours, 450-550 ℃ of air handled 4-6 hour down, obtained catalyst.
The presoma of described aluminium oxide is selected from unformed aluminium hydroxide, boehmite, boehmite, gibbsite, surge aluminium stone or promise diaspore.Preferably with the purity of acid system preparation boehmite, boehmite greater than 65% (weight).
Described forming method is meant methods such as compressing tablet, balling-up or extrusion commonly used in the supported catalyst preparation process, preferred extrusion method.The material that will contain alumina precursor, sesbania powder, rare nitric acid and citric acid places kneading machine to mix and pinches, mixed material is put into the hopper of banded extruder, make material just can obtain the catalyst carrier bar of required form by orifice plate by squeezing action, drying, roasting then just can obtain the catalyst carrier of modification.
Described fluorinated water solution is meant the aqueous solution that contains inorganic fluorine compound, as (wherein F content are 10～15g/ milliliter) such as ammonium fluoride, the hydrofluoric aqueous solution;
Tungsten-nickel, tungsten-molybdenum-nickel, the molybdenum-nickel aqueous solution that described dipping is used, the normally mixed solution of making by ammonium metatungstate, ammonium tungstate, ethyl metatungstic acid, metatungstic acid nickel and nickel nitrate, nickel acetate, basic nickel carbonate and molybdenum trioxide, ammonium heptamolybdate etc. and water or ammoniacal liquor (MoO wherein
3Concentration 0～70g/100ml; WO
3Concentration is 0～70g/100ml; NiO concentration is 10～40g/100ml; ).
Prepare the carrier process as stated above, wherein conventional sintering temperature is preferably 450～550 ℃, and the high-temperature roasting temperature is preferably 800～950 ℃.
The present invention adopts conventional temperature-high-temperature roasting (＞750 ℃) and fluorine additive modification to handle the aluminium hydroxide carrier.High-temperature roasting has guaranteed that not only the phase inversion of aluminium hydroxide is complete, and its surface nature and pore passage structure are tending towards rationally, and average pore size reaches 12～18nm, and bigger aperture helps removing gum asphalt and the metallic compound in the wax material inferior; Owing to adopt high-temperature roasting, carrier surface is the weak acid center of remaining low-surface-energy only, has weakened the interaction of carrier and active component, helps improving the utilization rate of active component and the hydrogenation activity of catalyst.Adopt the fluorine auxiliary agent that aluminum oxide modification treatments is helped suppressing the generation of nickel aluminate simultaneously, improve the dispersity and the interaction of metal active constituent, improve the utilization ratio of active component, further improve activity of such catalysts.
The specific embodiment
Following embodiment helps further to understand the present invention, rather than limits content of the present invention.
Embodiment 1
(1) preparation of carrier
Take by weighing the boehmite (Sanju Environment Protection New Material Co., Ltd., Beijing's production), 30g sesbania powder, 30g citric acid of 1000g, rare nitric acid of 3～5% mixes for 800 milliliters, use the banded extruder extrusion modling, 110 ℃ of oven dry, after the following 550 ℃ of calcination process of air, with 100 ℃ of/hour 750 ℃ of high-temperature process 4 hours of being rapidly heated, obtain macropore alumina supporter again.
(2) Preparation of catalysts
Take by weighing the alumina support of 500g, with saturated the spraying 30 minutes of ammonium fluoride aqueous solution (wherein F content is 10～15g/ milliliter), 110 ℃ of dryings, roasting then obtains the fluoro-containing alumina carrier.
With above-mentioned fluoro-containing alumina carrier, with the aqueous solution of a certain amount of ammonium metatungstate and nickel nitrate (WO wherein
3Concentration is 70g/100ml; NiO concentration is 20g/100ml) saturated spraying 1 hour, 110 ℃ of dryings 450 ℃ of following roastings, obtain catalyst then.
Embodiment 2
(1) preparation of carrier
The preparation process of carrier is identical with embodiment 1, but the temperature of high-temperature process is 800 ℃.
(2) Preparation of catalysts
Take by weighing the alumina support of 500g, with saturated the spraying 30 minutes of ammonium fluoride aqueous solution (wherein F content is 10～15g/ milliliter), 110 ℃ of dryings, roasting then obtains the fluoro-containing alumina carrier.
With above-mentioned fluoro-containing alumina carrier, with the aqueous solution of a certain amount of ammonium molybdate and nickel nitrate (MoO wherein
3Concentration is 50g/100ml; NiO concentration is 10g/100ml) saturated spraying 1 hour, 110 ℃ of dryings 450 ℃ of following roastings, obtain catalyst then.Preparation of catalysts step and embodiment 1 are identical.
Embodiment 3
(1) preparation of carrier
The preparation process of carrier is identical with embodiment 1, but the temperature of high-temperature process is 900 ℃.
(2) Preparation of catalysts
Take by weighing the alumina support of 500g, with saturated the spraying 30 minutes of ammonium fluoride aqueous solution (wherein F content is 10～15g/ milliliter), 110 ℃ of dryings, roasting then obtains the fluoro-containing alumina carrier.
With above-mentioned fluoro-containing alumina carrier, with the aqueous solution of a certain amount of ammonium metatungstate, molybdenum trioxide and nickel nitrate (WO wherein
3Concentration is 60g/100ml; MoO
3Concentration is 30g/100ml; NiO concentration is 10g/100ml) saturated spraying 1 hour, 110 ℃ of dryings 450 ℃ of following roastings, obtain catalyst then.
Comparative example 1
(1) preparation of carrier
Take by weighing the boehmite (Sanju Environment Protection New Material Co., Ltd., Beijing's production), 50g sesbania powder, 30g citric acid of 1000g, rare nitric acid of 3～5% mixes for 800 milliliters, use the banded extruder extrusion modling, 110 ℃ of oven dry, the following 550 ℃ of roastings of air obtain alumina support.
(2) Preparation of catalysts step and embodiment 1 are identical.
Comparative example 2
The present embodiment introduction prepares the process of catalyst by CN1044816C.
Take by weighing 200 gram aluminium hydrate powders and mix, use the banded extruder extrusion modling, 110 ℃ of oven dry with a small amount of shaping assistant and deionized water, after the following 550 ℃ of calcination process of air, be under the condition of 2.0 (weight) in 550 ℃, water/agent ratio again, steam treatment 4 hours obtains alumina support.
Get 5 gram magnesium nitrates and add the dissolving of water 80 gram, the dissolving back adds 100 gram alumina supports, 120 ℃ of dryings of soaked carrier, and 570 ℃ of roastings 4 hours obtain magnesium-containing carrier.With this contain the magnesium aluminium oxide join soak 4 hours in the 80 ml water solution that contain 60 gram ammonium metatungstates and 30 gram nickel nitrates after, 120 ℃ of dryings, 450 ℃ of following roastings 4 hours obtain the comparative catalyst, its composition (weight %) is WO
328.2%, NiO 5.0%, and MgO 0.4%, and all the other are aluminium oxide.
More than the physico-chemical property of the made carrier of each example list in table one, the physico-chemical property of catalyst is listed in table two, catalyst activity appreciation condition, feedstock property and 100ml hydrogenation evaluation result see Table three, table four.
The data of table one show, the relatively disperse of the alumina support pore-size distribution of comparative example 1 gained, and the aperture is less than normal, though the macropore of some 10nm～20nm is still more less than the micropore of 6nm; The alumina support of comparative example 2 and comparative example 1 alumina support pore structure are similar, and the big pore size distribution that the method that adopts hydrothermal treatment consists can not obviously improve alumina support is described.The pore volume of the alumina support of embodiment does not almost change, and pore size distribution is then obviously moved to the macropore aspect, mainly is distributed in 6nm～30nm, wherein concentrates on mostly in 8nm～20nm scope.Though the specific area of the alumina support of embodiment is starkly lower than the alumina support of comparative example 1,2, the shared effective active surface area of its macropore does not reduce.This has just determined catalyst of the present invention, because its macropore is more and concentrated, is more suitable for macromolecular hydrogenation process in the heavy charge wax.Adopt catalyst that the present invention makes than the catalyst that adopts comparative example 1,2 carriers to make as can be seen from the data of table two, have bigger aperture, more help the hydrogenation and removing of macromolecular gum asphalt.
From the result of table three as can be seen: when handling the lower wax material of conventional impurity content, adopt the light stability of the resulting purified product of catalyst of the method for the invention preparation slightly to be better than comparative example.
From the result of table four as can be seen: with No. 58 inverted sequence waxes without furfural treatment is raw material, its color is dark, poor, the tenor height of stability, belong to typical wax material inferior, adopt the color and the stability of the resulting purified product of catalyst of the method for the invention preparation obviously to be better than comparative example, illustrate that the catalyst that adopts the inventive method preparation is more suitable for handling the wax material inferior of high impurity content.
The physico-chemical property of each routine carrier of table 1
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Pore volume, mL.g 1 | 0.63 | 0.65 | 0.64 | 0.65 | 0.61 |
| Specific area, m 2.g 1 | 195 | 183 | 175 | 220 | 248 |
| Average pore size, nm | 14.6 | 16.4 | 18.4 | 9.2 | 9.9 |
| Pore-size distribution (nm), % | |||||
| ＜6.0 6.0～8.0 8.0～10.0 10.0～15.0 15.0～20.0 20.0～30.0 ＞30.0 | 1.3 4.3 10.1 54.4 23.4 4.9 1.6 | 0.8 3.3 10.0 53.2 24.4 5.9 2.4 | 0.5 2.0 9.1 52.4 26.4 6.9 2.7 | 11.6 29.8 34.1 11.6 12.0 0.9 -- | 12.6 21.9 31.2 25.7 4.2 2.6 1.8 |
The composition of each routine catalyst of table 2
The conventional wax material activity rating result of each routine catalyst of table 3
| Project | Paraffin | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Fusing point, ℃ | 60.2 | 60.3 | 62.4 | 60.4 | 60.3 | 60.3 |
| Oil content, wt% | 0.37 | 0.35 | 0.37 | 0.36 | 0.38 | 0.37 |
| Color, number | 14 | 30 | 30 | 30 | 30 | 30 |
| Light stability, number | 6 | 2 | 2 | 2 | 3 | 3 |
| Thermostability, number | 8 | 30 | 30 | 30 | 30 | 30 |
| Fe，ppm | 1 | 0 | 0 | 0 | 0 | 0 |
The wax material activity rating result inferior of each routine catalyst of table 4
| Project | Paraffin | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Fusing point, ℃ | 58.6 | 58.5 | 58.7 | 58.5 | 58.6 | 58.6 |
| Oil content, wt% | 1.17 | 1.15 | 1.17 | 1.16 | 1.18 | 1.18 |
| Color, number | ＜-16 | 30 | 30 | 30 | 25 | 26 |
| Light stability, number | ＞9 | 4 | 4 | 4 | 5 | 5 |
| Thermostability, number | ＜-16 | 26 | 24 | 25 | 19 | 20 |
| Fe，ppm | 4 | 0 | 0 | 0 | 1 | 2 |
Annotate: (1) conditions of vulcanization: catalyst is at first used the CS that contains 2 (volume) % under 290 ℃ of hydrogen atmospheres
2Grand celebration hydrocracking kerosene carried out presulfurization 20 hours, advance raw material then.
(2) reaction condition: 250 ℃ of reaction temperatures, pressure 7.0MPa, air speed (volume) 1.0h
-1, hydrogen oil (volume) is than 300.
Embodiment 4-22
Prepare catalyst for hydrogen refining of paraffin wax according to embodiment 1 described method, raw material is with embodiment 1 raw materials used unanimity, but proportion of raw materials is adjusted to some extent, and such adjustment can calculate out that each component content is as shown in the table in the catalyst for hydrogen refining of paraffin wax of preparing by the content of composition:
Claims (2)
1. the preparation method of a catalyst for hydrogen refining of paraffin wax is characterized in that, step is as follows:
(1) with the alumina precursor extrusion modling, then 100～120 ℃ of dryings 2～14 hours, 400～600 ℃ of roastings 2～6 hours, be warmed up to 750～1000 ℃ of roastings 1～4 hour then, obtain macropore alumina supporter;
(2) with the above-mentioned carrier that obtains, through the fluorinated water solution impregnation, 100～120 ℃ of dryings 2～14 hours, 200～500 ℃ of air were handled 2～8 hours down, obtained fluorine-containing carrier;
(3) the fluorine-containing carrier that will obtain, through the water-soluble co-impregnated solution of the active constituent that contains tungsten-molybdenum-nickel or molybdenum nickel dipping, 100～120 ℃ of dryings 2～14 hours, 400～600 ℃ of air were handled 2～8 hours down, obtained catalyst;
Described alumina precursor is selected from unformed aluminium hydroxide, boehmite, boehmite, gibbsite, surge aluminium stone or promise diaspore;
Described catalyst is made up of carrier and the active component that is carried on the carrier, in the described catalyst by weight percentage composition represent: carrier 60～80%, active component 20～40%; Carrier is made up of aluminium oxide and fluorine, and by the weight ratio of carrier, aluminium oxide: fluorine is 90～99: 1～10; Active component comprises NiO and MoO
3Or MoO
3, WO
3And NiO, by the weight ratio of active component, wherein MoO
3: NiO is 20～25: 5～10, MoO
3: WO
3: NiO is 10～15: 10～20: 3～8.
2. according to the preparation method of the described catalyst for hydrogen refining of paraffin wax of claim 1, it is characterized in that step is as follows:
(1) with alumina precursor extrusion modling according to a conventional method, then 100～120 ℃ of dry 6-10 hours, at 450-550 ℃ of roasting 3-5 hour, be rapidly heated then 800-900 ℃ of roasting 2-3 hour, obtain macropore alumina supporter;
(2) with the above-mentioned carrier that obtains, through the fluorinated water solution impregnation, at 100～120 ℃ of dry 6-10 hours, 200～500 ℃ of air were handled 4-6 hour down, obtained fluorine-containing carrier;
(3) the fluorine-containing carrier that will obtain, through the water-soluble co-impregnated solution dipping of the active constituent that contains tungsten-molybdenum-nickel or molybdenum nickel, at 100～120 ℃ of dry 6-10 hours, 450-550 ℃ of air handled 4-6 hour down, obtained catalyst.
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| CN102039148B (en) * | 2009-10-22 | 2012-08-08 | 中国石油天然气股份有限公司 | Preparation method of petroleum wax hydrofining catalyst |
| CN102485847B (en) * | 2010-12-03 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
| CN102909038A (en) * | 2012-10-25 | 2013-02-06 | 南通扬子催化剂有限公司 | Preparation process of catalyst containing tungsten nickel molybdenum fluoride components |
| FR2999453B1 (en) | 2012-12-18 | 2015-02-06 | IFP Energies Nouvelles | RESIDUAL HYDROTREATMENT CATALYST COMPRISING VANADIUM AND USE THEREOF IN A RESIDUAL HYDROCONVERSION PROCESS |
| CN109833880A (en) * | 2017-11-29 | 2019-06-04 | 中国石油天然气股份有限公司 | Poly α olefin synthetic oil hydrofining catalyst and preparation method thereof |
| CN111097434A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111097462A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111821988B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN113546638A (en) * | 2020-04-26 | 2021-10-26 | 中国石油天然气股份有限公司 | Paraffin hydrogenation catalyst and preparation method thereof |
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Effective date of registration: 20201109 Address after: 100007 Dongcheng District, Dongzhimen, China, North Street, No. 9 Oil Mansion, No. Patentee after: PetroChina Company Limited Address before: 163714 Daqing, Heilongjiang, Longfeng District, No. 2 Patentee before: PetroChina Company Limited Effective date of registration: 20201109 Address after: 163714 Daqing, Heilongjiang, Longfeng District, No. 2 Patentee after: PetroChina Company Limited Address before: 163714, Heilongjiang, Daqing Province, Longfeng District, Xinghua Village Road No. 18 friendship Patentee before: Institute of daqing Petrochemical Corp., Petrochina Co.,Ltd. Patentee before: PetroChina Company Limited |