CN101173193B - Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same - Google Patents

Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same Download PDF

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CN101173193B
CN101173193B CN2006101341649A CN200610134164A CN101173193B CN 101173193 B CN101173193 B CN 101173193B CN 2006101341649 A CN2006101341649 A CN 2006101341649A CN 200610134164 A CN200610134164 A CN 200610134164A CN 101173193 B CN101173193 B CN 101173193B
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molecular sieve
catalyzer
rare earth
earth element
type molecular
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CN101173193A (en
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刘全杰
徐会青
贾立明
王刚
王伟
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a catalyst with a preparation method for wax selective isomerization, which is characterized in that the catalyst comprises a TON-type molecular sieve, a plurality of inorganic and molten resistant oxides, and a plurality of noble metals; a plurality of rare-earth elements are in the TON-type molecular sieve with oxides covering 1 to 20 percent of the total weight of the molecular sieve; the catalyst adopts the preparation process that: the rear earth elements are first put on the molecular sieve to form a molecular sieve with rear earth, and then the catalyst is prepared. The invention has the advantages of high efficiency for goal products, low pour point, and high viscosity index, and is particularly suitable for the hydrotreatment of the lube distillate.

Description

A kind of paraffinic hydrocarbon selective isomerization catalyst and preparation method thereof
Technical field
The present invention relates to a kind of paraffinic hydrocarbon selective isomerization catalyst and preparation method thereof.In particular, relate to a kind of waxy feeds oil isomerization dewaxing catalyst and preparation method thereof, be particularly suitable for the hydroisomerization dewaxing process of lubricating oil.
Background technology
Waxy feeds oil described in the present invention mainly comprises diesel oil, AGO, VGO, white oil, hydrocracking tail oil and lubricating oil distillate etc.Waxy feeds oil, especially come from the heavy distillate of paraffinic crude and contain more wax, condensation point is higher, low-temperature fluidity is poor, in storage, transportation and use, reduction with envrionment temperature can make oily retrogradation, even solidifies, thereby the fuel feeding that stops up pipe laying and interruption engine breaks down engine.It is a lot of because of the method for solidifying the variety of issue that causes to solve content of wax heavy distillate at present, and wherein main means are dewaxings, comprise 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, make the wax component generation selective catalytic cracking in the cut, generation is than the hydro carbons of small molecules, for example P.4247388 U.S. Pat removes wax in the lubricating oil with USP.4659311 with regard to the method that is to use catalytic dewaxing, 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 base oil yield is low, the viscosity index loss is big, by product value is low.Compare with preceding two kinds of process for dewaxing, isomerization dewaxing is to make macromole wax generation isomerization reaction generate isoparaffin, and isoparaffin condensation point and pour point and the higher viscosity index lower than having with the wax phase of same molecular amount, and still be retained in the heavy distillate, thereby the distillate 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 that intensity is moderate, acid amount is more 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 P5990371,5833,837,5817907,5149421,5135638,5110445,4919788,4419420,4601993,4599162,4518485 etc. all relate to the isomerization dewaxing technology, use therein acidic components mainly contain mordenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, TON type molecular sieve etc., and wherein TON type molecular sieve mainly contains ZSM-22, Nu-10, KZ-2 and ISI-1 etc.Though above-mentioned these materials can both make paraffinic hydrocarbon generation isomerization reaction to a certain extent, but, help the performance of paraffinic hydrocarbon isomerization performance because the TON structure molecular screen has special pore structure (the oval straight hole of one dimension road) and suitable acid matter (middle strong acid is main).And the at present disclosed catalyzer that contains the TON molecular sieve also can further improve its reactivity worth by the modification of molecular sieve is handled, and especially improves its isomerization selectivity.
Rare-earth element modified molecular sieve is widely used in the petroleum refining catalyst, the acid that the introducing of rare earth element can improve molecular sieve distributes, effectively improve the reactivity worth of catalyzer, that application is maximum at present is rare earth modified Y zeolite and ZSM-5, be respectively applied for hydrocracking catalyst and obtain more satisfactory result in the shape scission reaction, also have not seen reported but present rare earth modified molecular sieve is applied to paraffinic hydrocarbon isomerization aspect with selecting.
Summary of the invention
For overcoming weak point of the prior art, the invention provides paraffinic hydrocarbon selective isomerization catalyst that a kind of activity is high, selectivity is good and preparation method thereof, this catalyzer not only can reduce the condensation point of waxy feeds oil, and can also improve the yield of liquid product, in particular for lubricating oil distillate isomerization dewaxing process, have the high characteristics of lubricant base viscosity index.
Paraffinic hydrocarbon selective isomerization catalyst of the present invention contains TON type molecular sieve, inorganic refractory oxide and hydrogenation metal component, contains rare earth element in the wherein said TON type molecular sieve, in oxide compound (RE 2O 3), the weight in catalyzer consists of 1%~20%, is preferably 2%~15%.
Catalyzer of the present invention, in the weight of catalyzer, composed as follows:
Contain rare earth element TON type molecular sieve: 10%~90%;
Hydrogenation metal is in metal: 0.1%~5.0%;
Inorganic refractory oxide: surplus.
Described TON type molecular sieve is one or more among ZSM-22, Nu-10, KZ-2 and the ISI-1, is preferably the ZSM-22 molecular sieve.The silica alumina ratio of described TON type molecular sieve is 50~200, is preferably 70~150.
Described rare earth element is that those of ordinary skills are known, comprises one or more mixtures such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, lutetium, is preferably lanthanum or/and cerium.Its precursor is the salt that is dissolvable in water water, and for example muriate, nitrate and acetate etc. are preferably nitrate.
The kind of described hydrogenation metal is that those of ordinary skills are known, the preferred noble metal hydrogenation component of the present invention, more preferably platinum and/or palladium.In metal, its weight in catalyzer consists of 0.1%~5.0%, is preferably 0.2%~3.0%.
Described inorganic refractory oxide is to be selected from aluminum oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium white and the clay one or more, is preferably aluminum oxide and/or silicon oxide, more preferably aluminum oxide.Its precursor can be selected from boehmite, pseudo-boehmite, diaspore, gibbsite and visit in the aluminium stone one or more, is preferably pseudo-boehmite.
Catalyst property of the present invention is as follows: specific surface is 200~350m 2/ g, pore volume are 0.3~0.5ml/g.The specific surface of catalyzer and pore volume are to adopt ASAP2400 among the present invention, and the low temperature liquid nitrogen absorption method calculates through BET.
Preparation of catalysts method disclosed in this invention comprises:
(1), rare earth element is loaded on the TON type molecular sieve, through super-dry, roasting, obtain containing the TON type molecular sieve of rare earth element.
(2), the TON type molecular sieve that contains rare earth element, inorganic refractory oxide, extrusion aid, water, peptizing agent that step (1) is obtained fully mix together and pinch into plastic paste, extruded moulding through super-dry, roasting, obtains support of the catalyst;
(3), load hydrogenation component on the carrier that obtains of step (2), drying and roasting obtain catalyzer of the present invention.
The described rare earth element mode of loading of step (1) can adopt the method for mixing or flooding, and preferably adopts pickling process.The blended method is directly mixed rare-earth compound with molecular sieve exactly, adds an amount of water then and mixes, and such benefit is once the content of molecular sieve middle-weight rare earths element once to be adjusted to the content that needs; The method of dipping is exactly to be prepared into the solution that contains rare earth element with rare-earth compound earlier, then with molecular sieve and its thorough mixing, pass through normal temperature~300 ℃ dry 1h~48h again, 400 ℃~800 ℃ roasting 0.5h~10h, obtain containing the TON type molecular sieve of rare earth element, the weight percent content of prepared solution middle-weight rare earths element can be a conventional content, is generally 2%~50%.Supported rare earth element preferable methods of the present invention can make rare earth element be more evenly distributed on the molecular sieve surface like this, and help the modification to the molecular sieve aperture for the method for dipping.The described rare-earth compound that contains is the salt that is dissolvable in water water, and for example muriate, nitrate and acetate etc. are preferably nitrate.
The described extrusion aid of step (2) is the additive that helps smooth extrusion, and as sesbania powder, starch, graphite etc., add-on is a conventional amount used, is generally 2%~10% of carrier (butt) weight.Described peptizing agent is the material that can make the mixture peptization, and for example silicon sol, basic cpd or acidic cpd are preferably acidic cpd, mineral acid more preferably, for example hydrochloric acid, nitric acid etc., its add-on is a conventional amount used, is generally 1%~5% of carrier (butt) weight.Described support shapes (cross-sectional shape) can also can be the distortion of these shapes for circle, tetragon, trilateral, cloverleaf pattern or Herba Galii Bungei shape etc.
The load of the described hydrogenation component of step (3) can be adopted metal load method at present commonly used, and for example dipping or ion-exchange etc. are preferably the method for dipping, more preferably the method for saturated dipping.The method of saturated dipping is exactly the solution that is mixed with the carrier saturated extent of adsorption with a certain amount of hydrogenation component compound, then solution is mixed with carrier.The hydrogenation component compound be for adopting this area salt that is dissolved in water commonly used, for example Platinic chloride, Palladous chloride, Palladous nitrate or contain the ammonia complex aqueous solution etc. of precious metal.
The drying of support of the catalyst and catalyzer and roasting condition can be same as the prior art described in step (2) and (3), 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.
The present invention adopts the TON structure molecular screen, because this molecular sieve analog has the oval straight hole road that the aperture is 0.53nm * 0.57nm, and its acid matter is based on middle strong acid, can produce tangible restriction to highly-branched chain isomerous body, help long-chain n-praaffin and carry out isomerization reaction according to the key reaction mechanism, isomerization has special effect to long-chain n-praaffin.But because unmodified molecular sieve pore passage structure and the reaction of acid confrontation isomerization of long-chain normal paraffin also are not very desirable, cause its reactivity worth to decrease, especially the selectivity of isomerization reaction is lower, after passing through among the present invention to introduce rare earth element, an aspect can combine with some strongly-acid centers on molecular sieve surface, form more stable title complex, produce more weak acid center, and strong acid center is the major cause that causes side reactions such as cracking.The another one aspect is the duct that the rare earth element of introducing can enter into molecular sieve, the size in aperture is reduced, so just further increased constraint, improved the selectivity of few branched chain isomer, thereby improved the isomery selectivity of catalyzer highly-branched chain isomerous body.
The present invention preferably adopts precious metal as hydrogenation component, be because isomerization reaction and cracking reaction all are consecutive reactions, isomerization process is generally all passed through in cracking for long chain alkane, when the isomer that produces can not be in time from the acid sites desorption, just further isomerization generates highly-branched chain isomerous body, and then generation scission reaction, improve the isomerization selectivity, the isomer that just need make the reaction generation is timely from the acid sites desorption, avoid side reaction generations such as cracking, this just requires catalyzer can have higher hydrogenation activity, and precious metal element obviously is best selection.
Catalyzer of the present invention can be handled various waxy feeds, and these raw materials can be the waxy feeds of initial boiling point more than 140 ℃ for example diesel oil, white oil, AGO, VGO, hydrocracking tail oil, lubricating oil or paraffin etc., is particularly suitable for the treating processes of lubricating oil.Paraffin selective isomerization reaction conditions is in the lube stock: hydrogen pressure 2MPa~20MPa, 260 ℃~400 ℃ of temperature, volume space velocity 0.5h -1~4.0h -1, hydrogen to oil volume ratio 200~1000, optimum condition is: hydrogen pressure 5MPa~10MPa, 320 ℃~380 ℃ of temperature, volume space velocity 1.0h -1~3.0h -1, hydrogen to oil volume ratio 300~500.
Catalyzer of the present invention needs to reduce processing before charging, reductive condition is as follows: in the presence of hydrogen, and 300 ℃~500 ℃ of temperature, pressure 0.5MPa~10MPa, 1 hour~12 hours time.
Catalyzer of the present invention is applied to have purpose product yield height in the lubricating oil isomerization dewaxing process, the low and high characteristics of viscosity index of pour point (condensation point).
Embodiment
Further specify Preparation of catalysts process of the present invention below by embodiment, but invention should not be deemed limited among the following embodiment.
Catalyzer of the present invention is to adopt the medium-sized fixed-bed reactor of 200ml to estimate, and loaded catalyst is 200ml, before the charging catalyzer is carried out prereduction, precious metal on the catalyzer is changed into go back ortho states, reductive condition is: 400 ℃ of temperature, pressure 6.0MPa, 8 hours time.Estimate employed stock oil main character and see Table 1.
Table 1 stock oil main character
Density (20 ℃), kg/m 3 861.1
Sulphur, μ g/g 4.0
Nitrogen, μ g/g 1.2
Viscosity (40 ℃), mm/s 2 29.69
Pour point, ℃ 21
Wax content, wt% 9.8
Boiling range, ℃ (D1160)
IBP/10% 227/399
30%/50% 428/441
70%/90% 455/469
95%/EBP 477/500
Embodiment 1
The preparation method of catalyzer of the present invention (E-1) is as follows:
(1) the used ZSM-22 of the present invention is the method preparation according to Chinese patent CN1565969A embodiment 1, and the molecular sieve silica alumina ratio that obtains is 92, specific surface area 223m 2/ g, pore volume 0.21mL/g.
(2) with La (NO 3) 36H 2O (Beijing Chemical Plant produces, analytical pure) and water are mixed with La 2O 3Weight percent concentration is 10% the aqueous solution, molecular sieve 4500 grams that step (1) is obtained and the above-mentioned lanthanum aqueous solution thorough mixing that contains of 5000 grams, and in 110 ℃ of following constant temperature 6 hours, 450 ℃ of following constant temperature 6 hours obtained La 2O 3Weight percent content be 10% contain lanthanum ZSM-22.
(3) contain lanthanum molecular sieve (dry basis with what 1500 gram steps (2) obtained, together following) and 500 gram (dry basises, down together) (Germany produces the SB aluminum oxide powder, trade names are SB) thorough mixing, adding 100 gram weight concentration then is 40% rare nitric acid and an amount of water, mix and pinch into plastic paste, it is the cylindrical bar of 1.2mm that extrusion becomes diameter, with this forming composition in 110 ℃ of constant temperature 8 hours, again 550 ℃ of following constant temperature 4 hours, obtain support of the catalyst, it consists of: 75wt% modified ZSM-5-22 and 25wt% aluminum oxide.
(4) with containing H 2PtCl 6The aqueous solution, the method that adopts saturated dipping loads to platinum on the carrier that step (3) obtains, in 150 ℃ of following constant temperature 4 hours, 500 ℃ of following constant temperature 6 hours obtained catalyzer of the present invention, is numbered E-1, the content of platinum is 0.38wt% in the catalyzer.
Embodiment 2
The preparation method of catalyzer of the present invention (E-2) is as follows:
The Preparation of catalysts method is with embodiment 1, what difference was support of the catalyst consists of 20wt% modified ZSM-5-22 and 80wt% aluminum oxide, the content of platinum is 0.74wt% in the catalyzer, dry and the roasting condition of catalyzer is: 110 ℃ of following constant temperature 4 hours, 420 ℃ of following constant temperature 6 hours, obtain catalyzer of the present invention and be numbered E-2, its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Embodiment 3
The preparation method of catalyzer of the present invention (E-3) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that used rare-earth compound is (NH 4) 2Ce (NO3) 6(Beijing Chemical Plant produce, analytical pure) usedly contains Ce in the cerium solution 2O 3Content is 2.0wt%, and hydrogenation component is a palladium, and the used palladium compound that contains is a Palladous nitrate, and wherein palladium is in metal, and strength of solution is 3wt%, obtains catalyzer E-3 of the present invention, and its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Embodiment 4
The preparation method of catalyzer of the present invention (E-4) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that rare-earth compound is La (NO 3) 36H 2O and (NH 4) 2Ce (NO 3) 6Mixture, La in the solution 2O 3And Ce 2O 3Concentration be respectively 4wt% and 8wt%, the modified molecular screen weight content is 90% in the support of the catalyst, hydrogenation component is a platinum, obtains catalyzer E-4 of the present invention, its composition and physico-chemical property see Table 2, evaluation result sees Table 3.
Embodiment 5
The preparation method of catalyzer of the present invention (E-5) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that rare earth element is that (Inner Mongol rare earth element chemical industry company limited produces mixeding acid rare-earth, and in oxide compound, the weight of each composition consists of in the total amount of rare earth: Ce 2O 3Be 63%, La 2O 3Be 25%, Pr 2O 3Be 2.1%, Nd 2O 3Be 5.0%, Sm 2O 3Be 0.5%, other is 4.4%), Re in the solution 2O 3Content be 8.3wt%, the modified molecular screen weight content is 50% in the support of the catalyst, hydrogenation component is a platinum, obtains catalyzer E-5 of the present invention, its composition and physico-chemical property see Table 2, evaluation result sees Table 3.
Embodiment 6
The preparation method of catalyzer of the present invention (E-6) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that hydrogenation component is platinum and palladium bimetal, obtains catalyzer E-6 of the present invention, and its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Embodiment 7
The preparation method of catalyzer of the present invention (E-7) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that the preparation process of modified molecular screen is:
Get 400 gram La (NO 3) 36H 2O (La 2O 3Content is 37.6wt%) mixes the back with 4500 gram ZSM-22 molecular sieves and add 2600 and restrain water, after said mixture fully stirred, in 110 ℃ of following constant temperature 6 hours, 450 ℃ of following constant temperature 6 hours obtained La 2O 3Weight percent content be 10% contain lanthanum ZSM-22.
Other preparation process of catalyzer obtains catalyzer E-7 of the present invention with embodiment 1, and its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Comparative Examples 1
Comparative catalyst's (C-1) preparation method is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that used molecular sieve without containing the rare earth element solution processing, obtains comparative catalyst C-1, and its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Comparative Examples 2
Comparative catalyst's (C-2) preparation method is as follows:
The Preparation of catalysts method is with embodiment 6, and difference is that used molecular sieve without containing the rare earth element solution processing, obtains comparative catalyst C-2, and its composition and physico-chemical property see Table 2, and evaluation result sees Table 3.
Each implements the main physico-chemical property of (comparison) example preparation catalyzer table 2
Catalyzer Pt,wt%① Pd,wt%① RE 2O 3,wt%② Modified ZSM-5-22, % are 1. S,m 2/g V,ml/g
E-1 0.38 - 10.0 75 244 0.33
E-2 0.74 - 6.7 20 261 0.41
E-3 - 2.0 1.6 75 248 0.34
E-4 1.05 - 12.0 90 232 0.30
E-5 0.52 - 8.3 50 230 0.35
E-6 0.21 0.40 10.0 75 240 0.35
E-7 0.38 - 10.0 75 239 0.32
C-1 0.38 - - 75 246 0.36
C-2 0.20 0.40 - 75 282 0.35
Annotate: 1. be benchmark with the catalyzer; 2. with the molecular sieve benchmark; S is the specific surface of catalyzer, and V is the pore volume of catalyzer.
Table 3 evaluating catalyst condition and result
Figure S061D4164920061129D000111
The evaluation result of table 3 shows, compares with the comparative catalyst, adopts catalyzer provided by the invention, is used for the hydrotreatment process of lubricating oil distillate, when the lubricant base pour point is close, and C 5 +Liquid receive to improve 3wt%~8wt%, and the lubricant base yield improves 3wt%~10wt%, and the viscosity index of product improves 10~20 units, catalyzer of the present invention be described in processing lube stock process, and effect has and significantly improves.
In addition, the reaction result of embodiment 1 and embodiment 7 as can be seen from last table, the Preparation of catalysts method also influences its reactivity worth, method with the lanthanum nitrate hexahydrate dipping is better than the effect that lanthanum loads on the molecular sieve molecular sieve to be handled with the blended method, catalyzer is formed when identical, under the approaching condition of product property, the lubricant base yield that the catalyzer for preparing with the method for flooding obtains improves 3.8wt%.
Catalyzer of the present invention can also be applied to the treating processes of waxy feeds such as paraffin, white oil, VGO, AGO, is particularly suitable for the production of white oil.

Claims (13)

1. a paraffinic hydrocarbon selective isomerization catalyst contains TON type molecular sieve, inorganic refractory oxide and hydrogenation component, it is characterized in that described TON type molecular sieve contains rare earth element, and in oxide compound, its weight content in molecular sieve is 1%~20%.
2. according to the described catalyzer of claim 1, it is characterized in that in the described TON type molecular sieve, rare earth element is 2%~15% in the weight content of oxide compound.
3. according to the described catalyzer of claim 1, it is characterized in that described rare earth element is to be selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, the lutetium one or more.
4. according to the described catalyzer of claim 1, it is characterized in that described rare earth element is that lanthanum is or/and cerium.
5. according to the described catalyzer of claim 1, it is characterized in that the composition of described catalyzer is as follows by weight:
The TON type molecular sieve that contains rare earth element: 10%~90%;
Hydrogenation component is in metal: 0.1%~5.0%;
Inorganic refractory oxide: surplus.
6. according to the described catalyzer of claim 1, it is characterized in that described TON type molecular sieve is the ZSM-22 molecular sieve, its silica alumina ratio is 50~200.
7. according to the described catalyzer of claim 1, it is characterized in that described hydrogenation metal is to be selected from palladium, platinum, ruthenium and the rhodium one or more; Described inorganic refractory oxide is to be selected from aluminum oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium white and the clay one or more.
8. according to the described catalyzer of claim 1, it is characterized in that described hydrogenation metal is platinum and/or palladium; Described inorganic refractory oxide is an aluminum oxide, and its precursor can be selected from boehmite, pseudo-boehmite, diaspore, gibbsite and visit in the aluminium stone one or more.
9. according to the described catalyzer of claim 1, it is characterized in that described catalyst property is as follows: specific surface is 200~350m 2/ g, pore volume are 0.3~0.5ml/g.
10. the arbitrary described Preparation of catalysts method of claim 1~9 is characterized in that comprising the steps:
(1), rare earth element is loaded on the TON type molecular sieve, through super-dry, roasting, obtain containing the TON type molecular sieve of rare earth element, the mode of loading of described rare earth element adopts the method for mixing or flooding, drying conditions is as follows: normal temperature~300 ℃ dry 1h~48h, 400 ℃~800 ℃ roasting 0.5h~10h;
(2), the TON type molecular sieve that contains rare earth element, inorganic refractory oxide, extrusion aid, water, peptizing agent that step (1) is obtained fully mix together and pinch into plastic paste, extruded moulding through super-dry, roasting, obtains support of the catalyst;
(3), load hydrogenation component on the carrier that obtains of step (2), drying and roasting obtain catalyzer of the present invention;
The drying conditions of support of the catalyst and catalyzer described in described step (2) and (3) is normal temperature~300 ℃ maintenance 1h~48h, and the carrier roasting condition is 400 ℃~800 ℃ roasting 0.5h~10h, and the catalyzer roasting condition is 350 ℃~600 ℃ and keeps 1h~8h.
11. in accordance with the method for claim 10, it is characterized in that it is pickling process that the described rare earth element of step (1) is responsible for method, be about to contain the solution and the TON type molecular sieve thorough mixing of rare earth element, the weight percent that wherein contains the solution middle-weight rare earths element of rare earth element is 2%~50%.
12. the application of the arbitrary described catalyzer of claim 1~9 in lube stock isomerization dewaxing process, its reaction conditions is: hydrogen pressure 2MPa~20MPa, 260 ℃~400 ℃ of temperature, volume space velocity 0.5h -1~4.0h -1, hydrogen to oil volume ratio 200~1000.
13., it is characterized in that the reaction conditions of lube stock isomerization dewaxing is: hydrogen pressure 5MPa~10MPa, 320 ℃~380 ℃ of temperature, volume space velocity 1.0h according to the described application of claim 12 -1~3.0h -1, hydrogen to oil volume ratio 300~500.
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CN102441416B (en) * 2010-10-13 2013-10-09 中国石油化工股份有限公司 Paraffin hydrocarbon shape selective isomerization catalyst, preparation method and application thereof
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
CN107303505B (en) * 2016-04-21 2020-04-14 中国石油化工股份有限公司 Composite molecular sieve catalyst and preparation method thereof
CN108102698B (en) * 2016-11-25 2020-07-03 中国石油化工股份有限公司 Method for producing lubricating oil base oil
CN106964398B (en) * 2017-03-09 2019-07-02 武汉凯迪工程技术研究总院有限公司 Hydroisomerizing dewaxing catalyst and preparation method thereof
CN109201110B (en) * 2017-07-06 2021-07-23 中国科学院上海高等研究院 Rare earth element modified hydroisomerization catalyst and synthesis method and application thereof
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CN113694962B (en) * 2021-09-30 2023-06-13 中化泉州石化有限公司 Isomerization dewaxing catalyst for hydrocracking tail oil and preparation method thereof

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