CN100457869C - Dewaxing catalyst for lubricant oil distillate and its uses - Google Patents
Dewaxing catalyst for lubricant oil distillate and its uses Download PDFInfo
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Abstract
The invention disclosed a kind of lubricating oil deparaffinage catalyst as well as its application during the deparaffinage process. The mentioned catalyst contains TON and/or MTT molecular sieve, at least one VIII group precious metal and zinc, the ratio of zinc and VIII group precious metal is 0.1-50. According to the invention, the zinc can regulate the catalyst's acidifying function and hydrogenating function so as to improve the activity and selectivity of the catalyst. If the catalyst is used in the deparaffinage process of lubricating oil to get the base oil of the same pour point, it can increase the liquid yield and base oil yield by 1.5wt%-5wt% and 2wt%-10wt% respectively.
Description
Technical field
The present invention relates to a kind of hydrogen dewaxing catalyst that faces, particularly a kind of lube oil hydrogenation dewaxing catalyst and face application in the hydrogen dewaxing process at lubricating oil.
Background technology
Contain the higher macromole straight chain of a large amount of fusing points or few branched paraffin (being commonly referred to wax) in the lubricating oil, so its pour point is higher, viscosity index is low and poor performance at low temperatures.Improve these performances, will remove high melting-point wax wherein is all or part of.Process for dewaxing commonly used at present mainly contains solvent dewaxing, catalytic dewaxing and isomerization dewaxing.
Solvent dewaxing is exactly to utilize the solubility property of wax in solvent to remove, and the shortcoming of this method is that solvent selects a large amount of organic solvent of difficulty, waste, harmful and contaminate environment, facility investment and process cost height and quality product limited by raw material.Catalytic dewaxing just is to use has the catalyzer of selecting shape cracking function, makes wax component generation selective catalytic cracking, generates the hydro carbons than small molecules, thereby makes the base oil depression of pour point.For example P.4247388 U.S. Pat just is to use the method for catalytic dewaxing with USP.4659311, the shortcoming of this method is because the macromolecular cpd of a large amount of high values is converted into the small-molecule substance of low value, makes that the purpose product yield is low, by product value is low.In lubricant base hydrogenation process, isomerization dewaxing can make macromole wax generation isomerization reaction generate isoparaffin, and isoparaffin pour point and the higher viscosity index lower than having with the wax phase of same molecular amount, and still be retained in the lubricating oil distillate, thereby base oil yield is greatly enhanced.
The purpose of isomerization dewaxing is exactly to make high melting-point wax be converted into the lower isoparaffin of fusing point, but the alkane fusing point that isomerisation degree is high is higher on the contrary, so isomerisation degree that just must control wax molecule, this has just proposed strict requirement to the acid matter of acidic components and pore structure and hydrogenation component.Acidic components will have the moderate acid sites of intensity and have the pore structure of space constraint effect in general, and active metal component has hydrogenation/dehydrogenation activity fast, prevent the further isomery and even the cracking of uncle's carbonium ion.
At present a lot of about the report of isomerization dewaxing catalyst, for example, U.S. Pat P5990371,5833837,5817907,5149421,5135638,5110445,4919788,4419420,4601993,4599162,4518485 etc. is that report relates to the isomerization dewaxing technology and produces lubricant base, and use therein acidic components mainly contain mordenite, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, SSZ-32, Nu-10, KZ-2 and ISI-1 etc.Because isomerization reaction requires very strict to the pore structure and the acid matter of material, special requirement hydrogenating function and acid function balance, the acid function deficiency causes selectivity to descend easily, and the hydrogenating function deficiency causes active the reduction, even small difference all may cause the serious difference of catalytic performance of catalyzer in preparation process, particularly for the isomerization reaction of macromole hydrocarbon.Though prior art can make macromole alkane selective isomerization reactive behavior be improved to a certain extent, selectivity improves not fairly obvious, and it is very satisfied that the result can not make us.
CN 1552822A discloses a kind of lube oil hydrogenation and has handled Catalysts and its preparation method.This catalyzer adopts a kind of NEW TYPE OF COMPOSITE molecular sieve with TON and two kinds of constitutional featuress of MFI, its process is as follows: composite molecular screen, additive, other inorganic refractory oxide, extrusion aid, water, peptizing agent etc. are fully mixed together pinch into plastic paste, extruded moulding obtains support of the catalyst through last handling processes such as super-dry, roastings; Supported active metal component and auxiliary agent on the carrier obtain this catalyzer by dry, activation then.But the acid function of this catalyzer and hydrogenating function coupling are improper, and side reactions such as cracking take place easily, and it is low to cause liquid to be incorporated.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of active lubricating oil high, that selectivity is good and face hydrogen dewaxing catalyst and preparation method thereof.This catalyzer is specially adapted to the lubricating oil dewaxing process, not only can reduce the pour point of base oil, improve viscosity index, and base oil yield is improved significantly also.
Lubricating oil of the present invention faces the hydrogen dewaxing catalyst, comprises at least a molecular sieve and at least a group VIII noble metals, also contains zinc in the described catalyzer, and wherein said molecular sieve is the molecular sieve of TON and/or MTT structure; Weight with catalyzer is benchmark, molecular sieve content is 10%～90%, be preferably 30～80%, more preferably 40～70%, group VIII noble metals content counts 0.01～10% with metal, is preferably 0.1～5.0%, be preferably 0.2～2.0%, zinc (in metal) content is 0.01%～20%, is preferably 0.1%～10%, more preferably 0.2%～5.0%; Wherein the weight ratio of zinc (in metal) and group VIII noble metals is 0.1～50 in the catalyzer, is preferably 1～30, more preferably 5～20.
The physico-chemical property of catalyzer of the present invention is as follows: specific surface is 160～287m
2/ g, pore volume are 0.25～0.60ml/g (adopting ASAP2400 low temperature n2 absorption apparatus to record specific surface and pore volume).
Said group VIII noble metals is preferably platinum and/or palladium, most preferably is platinum.
Said molecular sieve preferably adopts TON and MTT molecular sieve.Described TON and MTT molecular sieve can be the mixtures of two kinds of structure molecular screens, also can be the composite molecular screens with two kinds of structures.Described TON type molecular sieve is one or more among theta, ISI-1, NU-10, KZ-2 and the ZSM-22, and described MTT type molecular sieve is one or more among ZSM-23, EU-13, ISI-4, KZ-1 and the SSZ-32.Molecular sieve described in the catalyzer of the present invention is preferably among NU-10, ZSM-22, ZSM-23 and the SSZ-32 one or more, and the structure of molecular sieve is determined by the XRD characterization result.In catalyzer, the weight ratio of TON molecular sieve and MTT molecular sieve is 1: 5～5: 1, and the silica alumina ratio of TON molecular sieve is 40～150, and the silica alumina ratio of MTT molecular sieve is 50～200.
In order to improve catalyst performance, can add proper assistant as required, be generally in phosphorus, silicon, the boron one or more, be preferably phosphorus; Auxiliary agent is 0～20wt% in the content of oxide compound in catalyzer, is preferably 0.1wt%～10wt%, more preferably 0.2wt%～5.0wt%.
Also can contain other porous, inorganic refractory oxide in the catalyzer of the present invention,, be preferably aluminum oxide and/or silicon oxide, more preferably aluminum oxide such as in aluminum oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium white and the clay one or more.
Catalyzer of the present invention can adopt conventional method preparation, and wherein the mode that is added in the catalyzer of noble metal component and zinc can adopt pickling process or ion exchange method, is preferably pickling process.Activity component impregnation solution commonly used is the aqueous solution that contains the reactive metal soluble compound, for example platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof.Zinciferous soluble compound is one or more in zinc nitrate, zinc chloride and the zinc sulfate etc.
The mode that described auxiliary agent is added in the catalyzer is generally pickling process, contain the auxiliary compound that needs add in the employed steeping fluid, for example phosphoric acid, boric acid or silicofluoric acid amine etc., the order of dipping can be the reactive metal load before, later on or adding simultaneously, be preferably before the reactive metal load and join in the carrier.
Described catalyzer is suitable for lubricating oil and faces the hydrogen dewaxing process, and sulphur content preferably less than 50 μ g/g, is more preferably less than 10 μ g/g less than 100 μ g/g in the lube stock; Nitrogen content preferably less than 10 μ g/g, is more preferably less than 1 μ g/g less than 50 μ g/g.Reaction conditions is: pressure 0.1～20MPa, 280～400 ℃ of temperature, volume space velocity 0.1～5h during liquid
-1, hydrogen to oil volume ratio is 100～2000.This catalyzer also can be used for the pour point depression process of VGO, white oil, diesel oil and other heavy distillates of high pour point.
Before charging, catalyzer is carried out reduction activation, active noble metals is existed with simple substance form, reductive condition is as follows: in the presence of hydrogen, 100 ℃～500 ℃ kept 1～12 hour, and pressure is 0.5MPa～10MPa.
Catalyzer of the present invention preferably adopts two kinds of molecular sieves, separately characteristics of performance, and, regulate the acid function and the hydrogenating function of catalyzer by adding zinc, make activity of such catalysts and selectivity be improved significantly.Compare with the correlation technique document, be used for the treating processes of lubricating oil distillate, when obtaining same pour point base oil, adopt catalyzer of the present invention, liquid is received and is improved 1.5wt%～5wt%, and base oil yield improves 2wt%～10wt%.
Embodiment
A kind of concrete preparation method of catalyzer of the present invention is provided below, but is not limited thereto method, concrete steps are:
(1) molecular sieve, inorganic refractory oxide, extrusion aid, water and peptizing agent are fully mixed together pinch into plastic paste, extruded moulding through super-dry, calcination process, obtains support of the catalyst;
(2) with the aqueous solution that contains active metal component, selectivity adds the water-soluble cpds that contains auxiliary agent, by dry, calcination process, obtains catalyzer of the present invention;
Wherein zinc can be in step (2) before, and with containing the support of the catalyst that zinc aqueous solution impregnation steps (1) obtains, drying, roasting obtain containing the zinc catalyst carrier; Also can be dipped on the support of the catalyst together with active metal component; Also can soak reactive metal earlier, soak zinc again; Preferred one of the preceding two kinds of methods that adopt.
The drying of support of the catalyst of the present invention and catalyzer, the operational condition of roasting process can be same as the prior art, for example drying conditions is normal temperature～300 ℃ maintenance 1h～48h, the carrier roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that the catalyzer roasting condition is 350 ℃～600 ℃ and keeps 1h～8h.
Give further instruction below by embodiment to technology of the present invention but be not limited to this scope.
The experiment feedstock property that uses sees Table 1, and experiment is to finish on pilot plant, and catalyst volume 100ml is packed into reactor after diluting with the 100ml quartz sand, and catalyzer reduces 4h in the presence of 653K hydrogen before charging.
Table 1 stock oil character
| Density (20 ℃), kg/m 3 | 835 |
| Viscosity, mm 2/s，100℃ | 4.255 |
| Pour point, ℃ | 31 |
| Sulphur, μ gg -1 | 12.3 |
| Nitrogen, μ gg -1 | 1.0 |
| Wax content, wt% | 23.5 |
| Boiling range, ℃ | |
| IBP/10％ | 330/384 |
| 30％/50％ | 409/426 |
| 70％/90％ | 446/474 |
| 95％/EBP | 483/504 |
Comparative Examples 1
A kind of preparation method of comparative catalyst of the present invention
(1) preparation of NU-10 molecular sieve: the method according to United States Patent (USP) 4900528 embodiment 1 prepares the NU-10 molecular sieve, being about to 1.04 gram alumina trihydrates is dissolved in the solution that is formed by 8.03 gram one water rubidium hydroxides and 10 gram water, add 24 gram silicon sol, 15.5 grams 1 then successively, 6-hexanediamine and 348 gram water, fully stir, form the homogeneous gel phase.With gel 180 ℃ of crystallization 49 hours in autoclave, product filters, drying, and the silica alumina ratio that obtains molecular sieve is 44.
(2) with NU-10 molecular sieve, the aluminum oxide powder thorough mixing of step (1) gained, the nitric acid that adds 66wt% mixes pinches into mouldable paste, being extruded into diameter is the cylinder bar of 1.5mm, through 110 ℃ of dryings 8 hours, 550 ℃ of roastings 6 hours in air atmosphere then, the carrier note that makes diameter and be 1.35mm is S-1, and wherein the content of molecular sieve is 60wt% in the carrier, and surplus is an aluminum oxide.
(3) get the carrier that 200 gram steps (2) obtain, use and contain Pt (NH
3)
4Cl
2And Pd (NH
3)
4(NO
3)
2Solution carry out saturated dipping, then 110 ℃ dry 6 hours down, 380 ℃ of roastings are 6 hours in air atmosphere, make the comparative catalyst of the present invention who contains 0.4wt%Pt, 0.8wt%Pd, are numbered C-1, its physico-chemical property sees Table 3, reaction result sees Table 4.
Comparative Examples 2
A kind of preparation method of comparative catalyst of the present invention
The preparation of carrier is with comparative example 1, difference is that wherein molecular sieve is ZSM-23, this molecular sieve prepares according to United States Patent (USP) 5332566 embodiment 3 methods, the silica alumina ratio that obtains molecular sieve is 68, be pure ZSM-23 crystallization, its content in support of the catalyst is 40wt%, obtains the carrier note and makes S-2.
Get 200 gram carrier S-2, use and contain H
2PtCl
6Carry out saturated dipping with the solution of phosphoric acid, then 120 ℃ dry 12 hours down, 480 ℃ of roastings are 8 hours in air atmosphere, make the comparative catalyst who contains 1.0wt%Pt, 1.4wt%P, are numbered C-2, its physico-chemical property sees Table 3, reaction result sees Table 4.
Comparative Examples 3
A kind of preparation method of comparative catalyst of the present invention
The preparation of carrier is with comparative example 1, and difference is wherein to contain two kinds of molecular sieves, and ZSM-22 content is 25wt%, and SSZ-32 content is 45wt%.Wherein ZSM-22 is the method preparation according to United States Patent (USP) 4481177 embodiment 5, and obtaining the molecular sieve silica alumina ratio is 82; SSZ-32 is according to the preparation of United States Patent (USP) 5053373 embodiment 2 methods, and the molecular sieve silica alumina ratio is 39; Gained carrier note is made S-3.
Get 200 gram carrier S-3, use and contain PdCl
2Solution carried out ion-exchange 48 hours at 45 ℃, then 80 ℃ dry 24 hours down, 550 ℃ of roastings are 2 hours in air atmosphere, make the comparative catalyst who contains 1.2wt%Pd, are numbered C-3, its physico-chemical property sees Table 3, reaction result sees Table 4.
Embodiment 1
A kind of preparation method of catalyzer of the present invention
Get 200 gram S-1 carriers, use and contain Pt (NH
3)
4Cl
2With the saturated dipping of solution of zinc acetate, then 100 ℃ of dryings 8 hours, 500 ℃ of roastings are 3 hours in air atmosphere, make the catalyzer of the present invention that contains 0.6wt%Pt and 2.4wt%Zn, are numbered E-1, and its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 2
A kind of preparation method of catalyzer of the present invention
Get 200 gram S-2 carriers, the solution that use contains Palladous nitrate and zinc chloride carried out ion-exchange 12 hours at 60 ℃, then 110 ℃ of dryings 6 hours, 480 ℃ of roastings are 4 hours in air atmosphere, make the catalyzer of the present invention that contains 0.8wt%Pd and 0.6wt%Zn, be numbered E-2, its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 3
A kind of preparation method of catalyzer of the present invention
The catalyzer used carrier is with Comparative Examples 3, with the saturated impregnation catalyst agent carrier of the solution that contains Platinic chloride, zinc nitrate and phosphoric acid, then 150 ℃ of dryings 4 hours, 540 ℃ of roastings are 2 hours in air atmosphere, obtain catalyzer of the present invention and be numbered E-3, its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 4
Preparation of catalysts method of the present invention
The preparation method of catalyzer used carrier is with Comparative Examples 3, and difference is that wherein ZSM-22 content is 40wt%, and SSZ-32 content is 40wt%.With the saturated impregnation catalyst agent carrier of the solution that contains zinc chloride,, obtain containing the zinc catalyst carrier through 250 ℃ of dryings 4 hours.Contain the zinc catalyst carrier with the saturated dipping of the aqueous solution that contains Platinic chloride and Palladous chloride again, 120 ℃ of dryings 6 hours, 400 ℃ of roastings were 8 hours in the air atmosphere, obtain catalyzer of the present invention and are numbered E-4, and its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 5
Preparation of catalysts method of the present invention
Used carrier and method for preparing catalyst are with embodiment 4, and difference is that zinc is different with active metallic content in the catalyzer, obtain catalyzer of the present invention and are numbered E-5, and its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 6
Preparation of catalysts method of the present invention
The preparation method of catalyzer used carrier is with Comparative Examples 3, and difference is that wherein ZSM-22 content is 60wt%, and SSZ-32 content is 15wt%.With the saturated impregnation catalyst agent carrier of the solution that contains zinc nitrate and boric acid,, obtain containing the support of the catalyst of zinc and boron through 100 ℃ of dryings 4 hours and 400 ℃ of roastings 2 hours.The support of the catalyst that contains zinc and boron again with the saturated dipping of the aqueous solution that contains platinous chloride amine complex and ammonum chloropalladate title complex, 120 ℃ of dryings 4 hours, 500 ℃ of roastings were 4 hours in the air atmosphere, obtain catalyzer of the present invention and are numbered E-6, its physico-chemical property sees Table 3, and reaction result sees Table 4.
Embodiment 7
Preparation of catalysts method of the present invention
The catalyzer used carrier is with embodiment 6.With the saturated impregnation catalyst agent carrier of the solution that contains primary ammonium phosphate,, obtain the phosphorated support of the catalyst through 200 ℃ of dryings 2 hours.Again with containing the saturated dipping phosphorated of the aqueous solution support of the catalyst of Palladous chloride and zinc chloride, 110 ℃ of dryings 4 hours, 450 ℃ of roastings were 3 hours in the air atmosphere, obtain catalyzer of the present invention and are numbered E-7, and its physico-chemical property sees Table 3, and reaction result sees Table 4.
The main physico-chemical property of table 3 catalyzer
| Catalyzer | Pt，wt％ | Pd，wt％ | Zn，wt％ | P 2O 5(B 2O 3)，wt％ | S，m 2/g | V，ml/g | d，nm |
| C-1 | 0.4 | 0.8 | - | - | 223 | 0.41 | 8.7 |
| C-2 | 1.0 | - | - | 1.4 | 261 | 0.53 | 8.4 |
| C-3 | - | 1.2 | - | - | 287 | 0.60 | 8.6 |
| E-1 | 0.6 | - | 2.4 | - | 218 | 0.38 | 7.7 |
| E-2 | - | 0.8 | 0.6 | - | 252 | 0.43 | 7.2 |
| E-3 | 0.3 | - | 4.7 | 2.2 | 201 | 0.32 | 6.9 |
| E-4 | 0.2 | 0.4 | 1.2 | - | 246 | 0.45 | 7.9 |
| E-5 | 0.5 | - | 6.8 | - | 160 | 0.25 | 6.6 |
| E-6 | 1.4 | 0.1 | 3.1 | (0.5) | 223 | 0.40 | 7.4 |
| E-7 | - | 1.8 | 0.2 | 1.0 | 217 | 0.39 | 7.6 |
Wherein, S represents specific surface, and V represents pore volume, and d represents average pore diameter
Table 4 catalyst runs condition and result
| The catalyzer numbering | C-1 | C-2 | C-3 | E-1 | E-2 | E-3 | E-4 | E-5 | E-6 | E-7 |
| Reaction pressure, MPa | 9.0 | 16.0 | 4.0 | 9.0 | 16.0 | 4.0 | 8.0 | 9.0 | 9.0 | 9.0 |
| Volume space velocity, h -1 | 0.8 | 1.0 | 0.9 | 0.8 | 1.0 | 0.9 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 | 800 | 800 | 800 | 400 | 1200 | 1200 | 2000 |
| Temperature of reaction, ℃ | 340 | 345 | 340 | 345 | 350 | 340 | 330 | 340 | 350 | 325 |
| C 5 +Liquid is received, wt% | 93.1 | 93.8 | 94.4 | 96.7 | 97.9 | 98.2 | 97.1 | 98.3 | 97.2 | 97.3 |
| 350℃ +Yield, wt% | 71.4 | 73.5 | 74.4 | 79.2 | 77.8 | 81.3 | 80.1 | 81.6 | 80.3 | 80.8. |
| Pour point, ℃ | -18 | -21 | -15 | -24 | -21 | -27 | -21 | -23 | -20 | -21 |
Table 4 result shows that catalyzer of the present invention is compared with the comparative catalyst, has the base oil yield of better pour point depressing effect and Geng Gao.
Claims (13)
1, a kind of lubricating oil faces the hydrogen dewaxing catalyst, comprise at least a molecular sieve and at least a group VIII noble metals, it is characterized in that containing zinc in the described catalyzer, wherein said molecular sieve is the molecular sieve of TON and/or MTT structure, zinc is 0.01%～20% in the weight content of metal in catalyzer, and the weight ratio of zinc and group VIII noble metals is 0.1～50 in the catalyzer.
2, according to the described catalyzer of claim 1, it is characterized in that zinc is 0.1%～10% in the weight content of metal in catalyzer, the weight ratio of zinc and group VIII noble metals is 1～30 in the catalyzer.
3, according to claim 1 or 2 described catalyzer, it is characterized in that zinc is 0.2%～5% in the weight content of metal in catalyzer, the weight ratio of zinc and group VIII noble metals is 5～20 in the catalyzer.
4, according to claim 1 or 2 described catalyzer, it is characterized in that the weight with catalyzer is benchmark, molecular sieve content is 10%～90%, group VIII noble metals content counts 0.01%～10% with metal.
5, according to claim 1 or 2 described catalyzer, it is characterized in that the weight with catalyzer is benchmark, molecular sieve content is 30%～80%, group VIII noble metals content counts 0.1%～5.0% with metal.
6, according to claim 1 or 2 described catalyzer, it is characterized in that the weight with catalyzer is benchmark, molecular sieve content is 40～70%, group VIII noble metals content counts 0.2%～2.0% with metal.
7, according to the described catalyzer of claim 1, it is characterized in that said group VIII noble metals is platinum and/or palladium, said molecular sieve is TON and MTT molecular sieve; The silica alumina ratio of TON molecular sieve is 40～150, and the silica alumina ratio of MTT molecular sieve is 50～200; In catalyzer, the weight ratio of TON molecular sieve and MTT molecular sieve is 1: 5～5: 1.
8, according to claim 1 or 7 described catalyzer, it is characterized in that described TON type molecular sieve is one or more among theta, ISI-1, NU-10, KZ-2 and the ZSM-22, described MTT type molecular sieve is one or more among ZSM-23, EU-13, ISI-4, KZ-1 and the SSZ-32.
9, according to claim 1 or 7 described catalyzer, it is characterized in that described group VIII noble metals is a platinum, described molecular sieve be among NU-10, ZSM-22, ZSM-23 and the SSZ-32 one or more.
10, according to the described catalyzer of claim 1, it is characterized in that containing auxiliary agent in the described catalyzer, described auxiliary agent is one or more in phosphorus, silicon and the boron; In oxide compound, its content in catalyzer is 0.1wt%～20wt%.
11,, it is characterized in that described auxiliary agent is a phosphorus according to the described catalyzer of claim 10.
12, according to the described catalyzer of claim 1, the specific surface that it is characterized in that described catalyzer is 160～287m
2/ g, pore volume are 0.25～0.60ml/g.
13, the arbitrary described catalyzer of claim 1～12 faces application in the hydrogen dewaxing process at lubricating oil, it is characterized in that the described reaction conditions that faces the hydrogen dewaxing is: pressure 0.1MPa～20MPa, 280 ℃～400 ℃ of temperature, volume space velocity 0.1h during liquid
-1～5h
-1, hydrogen to oil volume ratio is 100～2000.
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| CN101942321B (en) * | 2009-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by isomerization dewaxing |
| CN101942320B (en) * | 2009-07-09 | 2014-12-10 | 中国石油化工股份有限公司 | Method for producing base oil by isodewaxing |
| CN102443416B (en) * | 2010-10-13 | 2015-05-13 | 中国石油化工股份有限公司 | Lubricating oil basic oil production method |
| CN105214717B (en) * | 2015-10-22 | 2017-07-28 | 中国海洋石油总公司 | A kind of preparation method of lube base oil isomerization dewaxing catalyst |
| CN107876084B (en) * | 2017-10-23 | 2021-02-23 | 中海油天津化工研究设计院有限公司 | Preparation method of integral nano heteroatom ZSM-22 molecular sieve catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128858C (en) * | 2001-09-26 | 2003-11-26 | 中国石油化工集团公司 | Hydrocatalyst and its preparing process |
| DE10257239B3 (en) * | 2002-12-04 | 2004-07-01 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Continuous partial photooxidation of liquid or dissolved olefin, used for preparing organic intermediate or fine chemical, e.g. allyl hydroperoxides, 1,2-dioxetanes or endo-peroxides, uses falling film microreactor then immediate reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128858C (en) * | 2001-09-26 | 2003-11-26 | 中国石油化工集团公司 | Hydrocatalyst and its preparing process |
| DE10257239B3 (en) * | 2002-12-04 | 2004-07-01 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Continuous partial photooxidation of liquid or dissolved olefin, used for preparing organic intermediate or fine chemical, e.g. allyl hydroperoxides, 1,2-dioxetanes or endo-peroxides, uses falling film microreactor then immediate reduction |
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