CN1317367C - Method for producing lubricating oil base oil - Google Patents
Method for producing lubricating oil base oil Download PDFInfo
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- CN1317367C CN1317367C CNB2004100298680A CN200410029868A CN1317367C CN 1317367 C CN1317367 C CN 1317367C CN B2004100298680 A CNB2004100298680 A CN B2004100298680A CN 200410029868 A CN200410029868 A CN 200410029868A CN 1317367 C CN1317367 C CN 1317367C
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000002199 base oil Substances 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 52
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 42
- 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 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010457 zeolite Substances 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 239000003921 oil Substances 0.000 claims abstract description 24
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- YIFVJYNWLCNYGB-UHFFFAOYSA-N [Si]=O.[Zr] Chemical compound [Si]=O.[Zr] YIFVJYNWLCNYGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 3
- OTUXRAAQAFDEQT-UHFFFAOYSA-N magnesium oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Mg+2].[Si+2]=O.[O-2] OTUXRAAQAFDEQT-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- FMLYSTGQBVZCGN-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Si+2]=O.[O-2].[O-2] FMLYSTGQBVZCGN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- CNGGOAOYPQGTLH-UHFFFAOYSA-N [O-2].[O-2].[Mg+2].[Al+3] Chemical compound [O-2].[O-2].[Mg+2].[Al+3] CNGGOAOYPQGTLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000032798 delamination Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 238000007605 air drying Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- 125000003963 dichloro group Chemical group Cl* 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical class CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a production method of lubricating oil basic oil, which comprises: a lubricating oil fraction contacts a catalyst under the condition of hydrogenation catalytic dewaxing, the catalyst is prepared by combining a first catalyst and a second catalyst which are loaded in a delamination mode, wherein the first catalyst contains a carrier and platinum and/or palladium loaded on the carrier composed of a heat-resisting inorganic oxide and a zeolite molecular sieve in a one-dimensional elliptical pore structure, the minor axis of the zeolite molecular sieve is from 4.2 to 4.8 angstroms, and the major axis is from 5.4 to 7.0 angstroms; the second catalyst contains a carrier and platinum and/or palladium loaded on the carrier composed of a heat-resisting inorganic oxide and a non-zeolite molecular sieve in a one-dimensional elliptical pore structure, the minor axis of the non-zeolite molecular sieve is from 4.2 to 4.8 angstroms, and the major axis is from 5.4 to 7.0 angstroms. The yield of the lubricating oil basic oil is obviously improved when the lubricating oil basic oil is produced with the method provided by the present invention.
Description
Technical field
The invention relates to a kind of production method of lube base oil.
Background technology
Lubricant base generally is by crude oil process multistep treating processes, obtains as distillation, hydrocracking, hydrotreatment, dewaxing, hydrofining.Wherein, can adopt several different methods that stock oil is dewaxed, to produce the lubricant base that pour point meets the demands.
By molecule cracking of selectivity wax and/or isomerization, can effectively reduce the pour point of lubricating oil distillate.As: Re28398 (U.S.Patent No.3,700,585) has described a kind of employing ZSM-5 zeolite catalyst, by the process for dewaxing of selective splitting wax molecule.The defective one of this process for dewaxing is the reduction with pour point, generates oil viscosity raising, density increase; The 2nd, the wax destructive distillation product mainly is as C
4 -Following light ends and gas, the purpose product yield is low.
USP4,599,162 disclose a kind of series connection catalyst hydrogenation process for dewaxing, this method comprises: a) a kind of hydrocarbon feed that is selected from the normal paraffin and the normal paraffin of slight collateralization is contacted with a kind of hydroisomerisation catalysts, described hydroisomerisation catalysts comprises that a kind of ZSM-12 of having and ZSM-23 compound crystal silicate boil and the hydrogenation metal component; B) will be contacted with a kind of dewaxing catalyst by the product of partially liq at least that step a) obtains, described catalyzer contains crystalline silicate zeolite and and the hydrogenation metal component with ZSM-5 structure.
Compare with independent employing ZSM-5 zeolite catalyst, the yield of lubricating oil of this method increases, but still lower.
U.S.Patent No.5,246,566 disclose a kind of method of producing low pour point high-quality lubricant base, this method comprises that waxy feeds is 4.2-4.8 having minor axis, major axis is isomerization on the molecular sieve catalyst of one dimension elliptical aperture structure of 5.4-7.0 , catalyzer contains at least a group VIII metal, the molecular sieve that is suitable for comprises SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 and ZSM-35, reaction pressure is the 0.1-20 MPa, catalyst system therefor also contains the porous matrix material, as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, the oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white.In addition, for improving catalyzer isomerization reaction selectivity, catalyzer contains IIA family metal in the preferred implementation method.
Employing contains the catalyzer with one dimension elliptical aperture structure molecular screen and dewaxes, and wax molecule isomerization reaction selectivity is higher.Overcome the defective that adopts ZSM-5 zeolite catalyst selective splitting wax molecule process for dewaxing to a certain extent.But, when above-mentioned catalyzer is used for the lubricating oil distillate oil dewaxing, still have pour point depression weak effect or the low shortcoming of lubricant base yield.
Summary of the invention
The deficiency that the objective of the invention is the low or pour point depression weak effect of the yield that exists at existing method provides a kind of new the have higher yields and the better method of the production lubricant base of pour point depression effect.
Method provided by the invention is included under the catalytic hydroprocessing dewaxing technique condition lubricating oil distillate is contacted with catalyzer, described catalyzer is combined by the catalyst I and the catalyst I I of layering filling, it is characterized in that described catalyst I contains a kind of by a kind of heat-resistant inorganic oxide with a kind of to have minor axis be that 4.2-4.8 , major axis are the carrier formed of the zeolite molecular sieve of the one dimension elliptical aperture structure of 5.4-7.0 and load on platinum and/or palladium on this carrier; Catalyst I I contains a kind of by a kind of heat-resistant inorganic oxide with a kind of to have minor axis be that 4.2-4.8 , major axis are the carrier formed of the non-zeolite molecular sieve of the one dimension elliptical aperture structure of 5.4-7.0 and load on platinum and/or palladium on this carrier, and the volume ratio of catalyst I wherein and catalyst I I is 0.1-10.
Compare with existing method, method yield provided by the invention and pour point depression effect obviously improve.
For example, it for a kind of pour point 61 ℃ lubricating oil distillate oil dewaxing, under the same process condition, when adopting method provided by the invention, generate in the oil＞pour point of 470 ℃ of distillates is-24 ℃, yield is 50.2 weight %, and the Comparative Examples method, generate in the oil＞pour point of 470 ℃ of distillates is-21 ℃, yield is 45.8 weight %.
Embodiment
According to method provided by the invention, it is described that to have minor axis be that 4.2-4.8 , major axis are the zeolite-type molecular sieves of the one dimension elliptical aperture structure of 5.4-7.0 , be preferably ZSM-22 (major axis 5.5 , minor axis 4.5 ), ZSM-23 (major axis 5.6 , minor axis 4.5 ), one or more among the ZSM-35 (major axis 5.4 , minor axis 4.2 ); It is described that to have minor axis be that 4.2-4.8 , major axis are that the non-zeolitic molecular sieves of the one dimension elliptical aperture structure of 5.4-7.0 is preferably SAPO-11 (major axis 6.7 , minor axis 4.4 ), SAPO-31, one or more among the SAPO-41 (major axis 7.0, minor axis 4.0 ).About the pore structure of above-mentioned zeolite-type molecular sieves and non-zeolitic molecular sieves respectively in J.M.Benett et al, Zeolites, 1,160 (1987), G.T.Kokotailo, et al, Zeolites, 5,349 (1985), W.M.Meier, and D.H.Olsen, Atlas of Zeolite Structure Types, Butterworths, (87), R.M.Kircher, and J.M.Bennett, Zeolites discloses in 14,523 (1994) in detail.
According to method provided by the invention, be benchmark with the catalyzer, described catalyst I contains the heat-resistant inorganic oxide of 5-90 weight %, the zeolite molecular sieve of 9-90 weight %, in metal, platinum and/or the palladium of 0.1-5 weight %; Described catalyst I I contains the heat-resistant inorganic oxide of 5-90 weight %, the non-zeolite molecular sieve of 9-90 weight %, and in metal, platinum and/or the palladium of 0.1-5 weight %.Preferred described catalyst I contains the heat-resistant inorganic oxide of 9-85 weight %, the zeolite molecular sieve of 14-90 weight %, and in metal, platinum and/or the palladium of 0.1-1.5 weight %; Described catalyst I I contains the heat-resistant inorganic oxide of 9-85 weight %, the non-zeolite molecular sieve of 14-90 weight %, and in metal, platinum and/or the palladium of 0.1-1.5 weight %.
Heat-resistant inorganic oxide carrier among described catalyst I and the catalyst I I is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in the optional self-alumina of described heat-resistant inorganic oxide, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more are preferably aluminum oxide.
According to method provided by the invention, the carrier of described catalyst I and catalyst I I can be with prior art customary way preparation, comprise with the porous heat-resistant oxide compound mix with molecular sieve, moulding, roasting and introducing platinum and/or metallic palladium component.
Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example when extrusion, hydrated alumina can be mixed and add an amount of extrusion aid and/or tackiness agent, extrusion moulding then with the mixture of disordering molecular sieve with suitable quantity of water.The kind of described extrusion aid, peptizing agent and consumption all can be this area routines.Described roasting condition: temperature is 350-700 ℃, is preferably 450-600 ℃, and roasting time is 2-8 hour, is preferably 3-6 hour.
The method that platinum and/or palladium or its compound are incorporated on the carrier is being known in the art, for example, flood described carrier, carry out drying and roasting afterwards with the solution impregnation of the compound of platiniferous and/or palladium, drying temperature is 60-350 ℃, be preferably 100-150 ℃, be 1-24 hour time of drying, is preferably 2-10 hour, maturing temperature is 350-550 ℃, be preferably 400-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
The compound of platiniferous or palladium is selected from one or more in platinum or the metallic palladium soluble compound, as Platinic chloride, dichloro four ammino platinum, Palladous nitrate, dichloro two ammino palladiums etc., and preferred dichloro four ammino platinum, dichloro two ammino palladiums.
According to method provided by the invention, described catalyst I and catalyst I I can be seated in the same reactor, also can fill in respectively in two or more placed in-line reactors.Described filling preferably makes the stock oil that enters reactor contact with catalyst I I with catalyst I successively.
The described hydrogen dewaxing technique condition of facing is well known in the art, and preferable reaction temperature is 200-450 ℃, and the hydrogen dividing potential drop is the 1.0-25 MPa, and the liquid volume air speed is 0.1-10 hour
-1, hydrogen to oil volume ratio is 100-3000, and further preferable reaction temperature is 250-400 ℃, and the hydrogen dividing potential drop is the 4.0-15 MPa, and the liquid volume air speed is 0.2-5 hour
-1, hydrogen to oil volume ratio is 500-1500.
Method provided by the invention is applicable to the lubricating oil distillate pour point depression that dewaxes, to produce low pour point, base oil of high viscosity index lubricant, described content of wax hydrocarbon oil crude material is selected from hydrocracking tail oil, the solvent-refined oil through hydrotreatment, deasphalted oil, slack wax, soft wax, Fischer-Tropsch synthetic wax etc.
To the present invention be described by example below.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1
The explanation of this example the invention provides method catalyst system therefor I and preparation method thereof.
Employed ZSM-22 molecular sieve is according to patent U.S.Pat.No.4 in this example, and 556,477 methods are synthetic.Take by weighing 286 gram silicon sol (silica content 25 heavy %), add 298 gram distilled water, obtain silicon sol solution.Take by weighing 10 gram Tai-Ace S 150 (Beijing Chemical Plant's product, analytical pure, alumina content 15.3 heavy %), be dissolved in the 260 gram distilled water; Take by weighing 23 gram potassium hydroxide (Beijing Chemical Plant's product, analytical pure), be dissolved in the 263 gram distilled water.Under the vigorous stirring, alum liquor slowly is added drop-wise in the potassium hydroxide solution, then silicon sol solution is added drop-wise in this solution, continue to stir 15 minutes.Under the vigorous stirring, with 50 grams 1,6-hexanediamine (Chinese Medicine main office product) is added drop-wise in the above-mentioned mixing solutions, stirs, and obtains white gels.Gel is transferred in the autoclave that has agitator, be heated to 160 ℃, crystallization 72 hours.Gained molecular sieve filtration, washing, 120 ℃ of following air dryings spend the night, 550 ℃ of roastings are 12 hours in quartz tube furnace, product ammonium nitrate (Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure) solution is 80 ℃ of exchanges 3 times, and 120 ℃ of dryings are 4 hours then, and 550 ℃ of roastings are 4 hours in the quartz tube furnace, obtain the H-ZSM-22 molecular sieve, its silica alumina ratio (in terms of oxide moles) is 60.
With 93.3 gram aluminum oxide powder (Chang Ling refinery catalyst plants, butt 75%) and 130 gram ZSM-22 molecular sieves mix, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of air dryings 4 hours, support of the catalyst Z1 is made in the roasting in following 4 hours of 560 ℃ of air atmospheres.
Get 100 gram carrier Z1, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.8 gram 4 hours, 120 ℃ of air dryings 4 hours, 450 ℃ of roastings are 4 hours in tube furnace, obtain catalyzer C1.The composition of catalyzer C1 is listed in the table 1.
Example 2
The explanation of this example the invention provides method catalyst system therefor I and preparation method thereof.
Institute's synthetic ZSM-22 molecular sieve in 173.3 gram aluminum oxide powders (with example 1) and the 70 gram examples 1 is mixed, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of air dryings 4 hours, support of the catalyst Z2 is made in the roasting in following 4 hours of 560 ℃ of air atmospheres.
Get 100 gram carrier Z2, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.3 gram 4 hours, 120 ℃ of air dryings 4 hours, 450 ℃ of roastings are 4 hours in tube furnace, obtain catalyzer C2.The composition of catalyzer C2 is listed in the table 1.
Example 3
The explanation of this example the invention provides method catalyst system therefor II and preparation method thereof.
Employed SAPO-11 molecular sieve is according to patent U.S.Pat.No.4 in this example, and example 16 methods are synthetic in 440,871.Take by weighing the phosphoric acid of 420 grams, 85 heavy %, add 880 gram distilled water, 276 gram pseudo-boehmites (alumina content 74.2 heavy %, water-content 25.8 heavy %) stir, and obtain mixture S1.Taking by weighing concentration is the hydroxyl four n-Butyl Amine 99 aqueous solution 1298.4 grams of 40 heavy %, and the silica gel of being fuming (silica content 92.8 heavy %, water-content 7.2 heavy %) 52 grams stir, and obtain mixture S2.Mixture S1 and S2 are mixed, under agitation add 204 gram di-n-propylamines, obtain reaction mixture.Reaction mixture is packed in the reactor of teflon seal, and 200 ℃ of crystallization 24 hours are filtered, the washing solid product is to neutral, and 120 ℃ of oven dry obtain SAPO-11 molecular sieve (SAPO-11 net content 85.0 heavy %).
73 gram aluminum oxide powders (with example 1) and 200 are restrained the SAP0-11 molecular sieves mix, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of air dryings 4 hours, support of the catalyst Z3 is made in the roasting in following 4 hours of 560 ℃ of air atmospheres.
Get 100 gram carrier Z3, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.7 gram 4 hours, 120 ℃ of air dryings 4 hours, 450 ℃ of roastings are 4 hours in tube furnace, obtain catalyzer C3.The composition of catalyzer C3 is listed in the table 1.
Example 4
The explanation of this example the invention provides method catalyst system therefor II and preparation method thereof.
Institute's synthetic SAPO-11 molecular sieve in 195 gram aluminum oxide powders (with example 1) and the 70 gram examples 3 is mixed, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of air dryings 4 hours, support of the catalyst Z4 is made in the roasting in following 4 hours of 560 ℃ of air atmospheres.
Get 100 gram carrier Z4, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.3 gram 4 hours, 120 ℃ of air dryings 4 hours, 450 ℃ of roastings are 4 hours in tube furnace, obtain catalyzer C4.The composition of catalyzer C4 is listed in the table 1.
Comparative Examples 1
Contain ZSM-5 zeolite catalyst and preparation method thereof.
With 93.3 gram aluminum oxide powder (Chang Ling refinery catalyst plants, butt 75%) and 139.0 gram ZSM-5 molecular sieve (dying of Shanghai seven factory's products, butt 94.5%) mixes, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of air dryings 4 hours, support of the catalyst DZ1 is made in the roasting in following 4 hours of 560 ℃ of air atmospheres.
Get 100 gram carrier DZ1, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.3 gram 4 hours, 120 ℃ of air dryings 4 hours, 450 ℃ of roastings are 4 hours in tube furnace, obtain catalyzer D1, and catalyst property sees Table 1.
Table 1
| The catalyzer numbering | C1 | C2 | C3 | C4 | D1 |
| Catalyzer is formed, % Pt ZSM-22 molecular sieve SAPO-11 molecular sieve ZSM-5 molecular sieve-4 A l 2O 3 | 0.79 65.0 surpluses | 0.30 35.0 surpluses | 0.69 75.4 surpluses | 0.29 28.8 surpluses | 0.29 65.2 surpluses |
Example 5
The explanation of this example the invention provides the lubricating oil pour point depression effect of method.
At 175 milliliters of catalyzer C3, upper stratas 25 milliliters of catalyzer C1 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 1 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 3.
Example 6
The explanation of this example the invention provides the lubricating oil pour point depression effect of method.
At 50 milliliters of catalyzer C3, upper stratas 150 milliliters of catalyzer C1 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 1 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 3.
Example 7
The explanation of this example the invention provides the lubricating oil pour point depression effect of method.
At 20 milliliters of catalyzer C3, upper stratas 180 milliliters of catalyzer C1 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 1 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 3.
Comparative Examples 2
The lubricating oil pour point depression effect of the catalyzer that contains the SAPO-11 molecular sieve is used in the explanation of this Comparative Examples separately.
The 200 milliliters of catalyzer C3 that pack in 200 milliliters of down-flow fixed bed hydrogenators are warming up to 450 ℃, and hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 1 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 3.
Comparative Examples 3
The lubricating oil pour point depression effect of the catalyzer that contains the ZSM-22 molecular sieve is used in the explanation of this Comparative Examples separately.
The 200 milliliters of catalyzer C1 that pack in 200 milliliters of down-flow fixed bed hydrogenators are warming up to 450 ℃, and hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 1 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 3.
Table 2 stock oil character
| Numbering | Raw material 1 | Raw material 2 | Raw material 3 |
| Density, kg/m 3Viscosity, mm 240 ℃ of 100 ℃ of viscosity index condensation points of/s, ℃ S, μ g/g N, μ g/g boiling range, ℃ (ASTM D1160) IBP/5% 10%/30% 50%/70% 90%/95% FBP | 862.8 36.48 6.229 119 18 6.0 1.0 364/396 411/440 459/475 503/517 541 | 880.4 8.01 43 8.0 1.5 419/430 441/450 464/475 501/510 | 893.1 27.26 61 7.0 1.2 470/487 504/527 544/549 572/575 |
Table 3
| Example 5 | Example 6 | Example 7 | Comparative Examples 2 | Comparative Examples 3 | |
| Catalyst reaction temperatures, ℃ reaction pressure, MPa hydrogen-oil ratio LHSV, h -1 | C1/C3＝0.14 350 12.0 1000 1.0 | C1/C3＝3 350 12.0 1000 1.0 | C1/C3＝9 345 12.0 1000 1.0 | C3 370 12.0 1000 1.0 | C1 340 12.0 1000 1.0 |
| Product characteristics＞370 ℃ cut yield, the % pour point, ℃ viscosity index | 78.6 -18 112 | 77.1 -21 112 | 75.4 -21 110 | 72.5 -18 110 | 72.0 -18 99 |
Example 8
The explanation of this example the invention provides the lubricating oil pour point depression effect of method.
At 150 milliliters of catalyzer C4, upper stratas 50 milliliters of catalyzer C2 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 2 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 4.
Comparative Examples 4
The lubricating oil pour point depression effect of the catalyzer that contains the SAPO-11 molecular sieve is used in the explanation of this Comparative Examples separately.
The 200 milliliters of catalyzer C4 that pack in 200 milliliters of down-flow fixed bed hydrogenators are warming up to 450 ℃, and hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 2 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 4.
Table 4
| Example 8 | Comparative Examples 4 | |
| Catalyst reaction temperatures, ℃ reaction pressure, MPa hydrogen-oil ratio LHSV, h -1 | C2/C4＝0.33 340 12.0 1000 1.0 | C4 370 12.0 1000 1.0 |
| Product characteristics liquid is received, %＞370 ℃ cut yield, the % pour point, ℃ viscosity index | 92.0 60.3 -39 110 | 92.4 51.3 -24 110 |
Example 9
The explanation of this example the invention provides the lubricating oil pour point depression effect of method.
At 120 milliliters of catalyzer C3, upper stratas 80 milliliters of catalyzer C1 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 3 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 5.
Comparative Examples 5
The lubricating oil pour point depression effect of the catalyzer that contains the SAPO-11 molecular sieve is used in the explanation of this Comparative Examples separately.
The 200 milliliters of catalyzer C3 that pack in 200 milliliters of down-flow fixed bed hydrogenators are warming up to 450 ℃, and hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 3 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 5.
Comparative Examples 6
The explanation of this Comparative Examples is used and is contained ZSM-22 zeolite catalyst and the lubricating oil pour point depression effect that contains the combination of ZSM-5 zeolite catalyst.
At 120 milliliters of catalyzer C3, upper stratas 80 milliliters of catalyzer D1 that pack into that pack into of the lower floor of 200 milliliters of down-flow fixed bed hydrogenators, be warming up to 450 ℃, hydrogen reducing 4 hours is cooled to desired reaction temperature then, switches to raw material 3 (character sees Table 2) and reacts.Reaction conditions and product characteristics are listed in table 5.
Table 5
| Example 9 | Comparative Examples 5 | Comparative Examples 6 | |
| Catalyst reaction temperatures, ℃ reaction pressure, MPa hydrogen-oil ratio LHSV, h -1 | C1/C3＝0.67 340 12.0 1000 1.0 | C3 370 12.0 1000 0.7 | C1/D1＝0.67 340 12.0 1000 1.0 |
| Product characteristics liquid is received, %＞470 ℃ cut yield, the % pour point, ℃ viscosity index | 89.2 50.2 -24 105 | 89.0 40.6 -24 105 | 84.2 45.8 -21 98 |
The result who is provided by table 3,4,5 can illustrate, adopts when the invention provides method different material oil being dewaxed pour point depression, and its pour point depression effect and yield obviously improve.
Claims (9)
1, a kind of production method of lube base oil, this method is included under the catalytic hydroprocessing dewaxing condition lubricating oil distillate is contacted with catalyzer, described catalyzer is combined by the catalyst I and the catalyst I I of layering filling, it is characterized in that described catalyst I contains a kind of by a kind of heat-resistant inorganic oxide with a kind of to have minor axis be that 4.2-4.8 , major axis are the carrier formed of the zeolite molecular sieve of the one dimension elliptical aperture structure of 5.4-7.0 and load on platinum and/or palladium on this carrier; Catalyst I I contains a kind of by a kind of heat-resistant inorganic oxide with a kind of to have minor axis be that 4.2-4.8 , major axis are the carrier formed of the non-zeolite molecular sieve of the one dimension elliptical aperture structure of 5.4-7.0 and load on platinum and/or palladium on this carrier, with the catalyzer is benchmark, described catalyst I contains the heat-resistant inorganic oxide of 5-90 weight %, the zeolite molecular sieve of 9-90 weight %, in metal, platinum and/or the palladium of 0.1-5 weight %; Described catalyst I I contains the heat-resistant inorganic oxide of 5-90 weight %, the non-zeolite molecular sieve of 9-90 weight %, and in metal, platinum and/or the palladium of 0.1-5 weight %, the volume ratio of catalyst I wherein and catalyst I I is 0.1-10.
2, method according to claim 1 is characterized in that, described layering filling contacts the stock oil that enters reactor successively with catalyst I I with catalyst I.
3, method according to claim 1, it is characterized in that the heat-resistant inorganic oxide among described catalyst I and the catalyst I I is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, the oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, in the clay one or more.
4, method according to claim 3 is characterized in that, described heat-resistant inorganic oxide is an aluminum oxide.
5, method according to claim 1 is characterized in that, described zeolite molecular sieve is selected from one or more among ZSM-22, ZSM-23 and the ZSM-35.
6, method according to claim 1 is characterized in that, described non-zeolite molecular sieve is selected from one or more among SAPO-11, SAPO-31, the SAPO-41.
7, method according to claim 1 is characterized in that, is benchmark with the catalyzer, and described catalyst I contains the heat-resistant inorganic oxide of 9-85 weight %, the zeolite molecular sieve of 14-90 weight %, and in metal, platinum and/or the palladium of 0.1-1.5 weight %; Described catalyst I I contains the heat-resistant inorganic oxide of 9-85 weight %, the non-zeolite molecular sieve of 14-90 weight %, and in metal, platinum and/or the palladium of 0.1-1.5 weight %.
8, method according to claim 1 is characterized in that, described catalytic hydroprocessing dewaxing technique condition is, temperature of reaction is that 200-450 ℃, hydrogen dividing potential drop are that 1-25 MPa, liquid volume air speed are that 0.1-10 hour-1, hydrogen to oil volume ratio are 100-3000.
9, method according to claim 8 is characterized in that, described catalytic hydroprocessing dewaxing technique condition is, temperature of reaction is that 250-400 ℃, hydrogen dividing potential drop are that 4-15 MPa, liquid volume air speed are that 0.2-5 hour-1, hydrogen to oil volume ratio are 500-1500.
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| CN107790176B (en) * | 2016-08-30 | 2021-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodewaxing catalyst, catalyst prepared by method and application of catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0134682A1 (en) * | 1983-08-08 | 1985-03-20 | Mobil Oil Corporation | Improvement of overnight cloud and color in lube dewaxing |
| US5246566A (en) * | 1989-02-17 | 1993-09-21 | Chevron Research And Technology Company | Wax isomerization using catalyst of specific pore geometry |
| CN1257104A (en) * | 1998-12-16 | 2000-06-21 | 中国石油化工集团公司 | Method for producing base oil of high viscosity index lubricant |
-
2004
- 2004-03-31 CN CNB2004100298680A patent/CN1317367C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0134682A1 (en) * | 1983-08-08 | 1985-03-20 | Mobil Oil Corporation | Improvement of overnight cloud and color in lube dewaxing |
| US5246566A (en) * | 1989-02-17 | 1993-09-21 | Chevron Research And Technology Company | Wax isomerization using catalyst of specific pore geometry |
| CN1257104A (en) * | 1998-12-16 | 2000-06-21 | 中国石油化工集团公司 | Method for producing base oil of high viscosity index lubricant |
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