CN106669810A

CN106669810A - Alkane isomerization catalyst and preparation method and application thereof

Info

Publication number: CN106669810A
Application number: CN201510751186.9A
Authority: CN
Inventors: 徐会青; 刘全杰; 贾立明; 王伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-11-09
Filing date: 2015-11-09
Publication date: 2017-05-17

Abstract

The invention discloses an alkane isomerization catalyst and a preparation method and an application thereof. The catalyst comprises the following components by weight percentage: a modified MCM-22/ZSM-48 molecular sieve with content of 10-90%, VIII-faminly precious metal with content of 0.05-1.0%, an auxiliary agent rhenium and/or tin with content of 0.1-10% by metering with metal, the modified MCM-22/ZSM-48 molecular sieve contains 0.1-10% of silica metering by mass, surrounding of the ZSM-48 molecular sieve is wrapped with the MCM-22 molecular sieve in the MCM-22/ZSM-48 composite molecular sieve, and the weight content of MCM-22 is 1.0-50%. The catalyst can reduce the condensation point of wax-containing raw oil, increases the yield of liquid product, and has the characteristic of high viscosity index as a lubricating oil base oil when used for a lubricating oil fraction heterogeneous de-waxing process.

Description

A kind of alkane isomerization catalyst and its preparation method and application

Technical field

The present invention relates to a kind of alkane isomerization catalyst and its preparation method and application, relates in particular to one kind and is suitable to Lube oil isodewaxing catalyst and its preparation method and application.

Background technology

The isomerization reaction of n-alkane is the different of the isomerization dewaxing process of petroleum refining process such as lubricating oil and diesel oil The important reaction of structure pour point depression process.N-alkane is the undesirable components in lube cut, so as to cause its pour point more high and low Warm poor performance.Improve these performances it is necessary to high-melting-point n-alkane therein is completely or partially removed.Conventional at present is de- Wax method mainly has solvent dewaxing, catalytic dewaxing and isomerization dewaxing.

Solvent dewaxing is exactly to be removed using wax solubility property in a solvent, and it is tired that the shortcoming of this method is that solvent is selected It is difficult, waste substantial amounts of organic solvent, harmful and pollute that environment, equipment investment and operating cost are high and product quality is received Raw material is limited.Catalytic dewaxing is exactly, using the catalyst with shape-selective cracking function, to make the wax component in fraction that selection to occur and urge Change cracking, generate the hydro carbons compared with small molecule, such as United States Patent (USP) USP.4247388 and USP.4659311 are exactly de- using catalysis The method of wax removes the wax in lubricating oil, and the shortcoming of this method is because the macromolecular compound substantial amounts of high value is converted For the small-molecule substance of low value, make that base oil yield is low, viscosity index (VI) loss is big, by-product value is low.With first two dewaxing Method is compared, and isomerization dewaxing is to make macromole wax generation isomerization reaction generation isoparaffin, and isoparaffin and same molecular The wax of amount is compared with lower condensation point and pour point and higher viscosity index (VI), and is remained in heavy distillate, from And make fraction oil yield be greatly enhanced.

It is many with regard to the report of isomerization dewaxing catalyst at present, for example, United States Patent (USP) US5990371, US5833837, US5817907、US5149421、US5135638、US5110445、US4919788、US4419420、US4601993、 US4599162, US4518485 etc. all relate to Isodewaxing Technology, wherein the acidic components for using mainly have modenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, ZSM-48 type molecular sieve etc., for the molecular sieve of different structure, Due to its unique pore passage structure and physico-chemical property, so being adapted to different purposes.ZSM-5 molecular sieve has three-dimensional ten yuan Ring structure duct, NU-87 molecular sieves have two-dimentional ten-ring structure pore, ZSN-22, EU-1, SAPO-11 structural molecule sifter device There is one-dimensional ten-ring structure pore, and MCM-22 has two kinds of independent polynary ring channel systems, one kind is two-dimentional sinusoidal wave form, The ten-ring duct of intersection, these molecular sieves in the isomerization reaction of hydrocarbon molecules, with unique effect.But, due to The nuance of pore passage structure and physico-chemical property, makes its effect for being applied to isomerization dewaxing be not quite similar again.These materials can It is enough to make paraffin hydrocarbon that isomerization reaction occurs to a certain extent, but for some reactions, such as lube cut, due to wherein containing There is very complicated component, be not that identical molecule participates in reaction, so for the molecular sieve with homogeneous structural just occurs one A little adaptive problems, are capable of the catalysis material of good match, for other component may not be managed very much to a kind of molecule Think.

For the n-alkane in lube cut and diesel oil, because its condensation point is higher, cause lubricating oil and diesel oil at low-temperature Poor mobile performance, isomerization dewaxing is to adopt the bifunctional catalyst with special pore structure making the high-melting-point long-chain in wax component just Structure alkane and polycyclic naphthene hydrocarbon are converted into the isoparaffin of the relatively low unilateral chain of fusing point and the monocyclic naphthenes of belt length side chain.But The high alkane fusing point of isomerisation degree is higher on the contrary, so must just control the isomerisation degree of wax molecule, this is just to acid group The Acidity for dividing and pore structure and hydrogenation component propose strict requirements.In general acidic components will have moderate strength Acid centre and the pore structure with space restriction effect, and active metal component has quick hydrogenation/dehydrogenation activity, prevents The only further isomery of tertiary carbonium ion, or even cracking.Due to cracking reaction so that high carbon number alkane transformations are the low of small molecule Carbon alkane should as far as possible promote the carrying out of isomerization reaction so as to reduce the yield of purpose product, while to the greatest extent may be used The generation of the suppression cracking reaction of energy.US6204426 proposes to adopt SAPO-11, SAPO- 31, SAPO-41, ZSM-48, ZSM- 23rd, the mixture of ZSM-35 etc. prepares isomerization catalyst for carrier, and US5833837 proposes to be moistened using dual catalyst system The production procedure of lubricant base oil, that is, SAPO-11, SAPO- 31, SAPO-41 catalyst series is respectively adopted carries out light lubricant The isomerization of component and the isomerization of heavy lubricating oil component is carried out using ZSM-5 catalyst.But the equal Shortcomings of both flow processs Part, the former can not effectively play the synergism of each mixed molecular sieve component, and the latter extends technological process, increased behaviour Make difficulty, considerably increase cost of investment.

The content of the invention

To overcome weak point of the prior art, the invention provides a kind of paraffin hydrocarbon that activity is high, selectivity is good is selected Shape isomerization catalyst and its preparation method and application, the catalyst can not only reduce the condensation point of waxy feeds oil, and can also The yield of fluid product is improved, in particular for lube cut isomerization dewaxing process, with lube base oil viscosity index (VI) High the characteristics of.

A kind of alkane hydroisomerization catalyst, by weight percentage, modified MC M-22/ZSM-48 composite molecular screen contains Measure as 10 ~ 90%, preferably 20% ~ 80%, the VIIIth race's bullion content is 0.05 % ~ 1.0%, preferably 0.1 % ~ 0.8%, auxiliary agent rhenium And/or Theil indices are calculated as 0.1% ~ 10%, preferably 0.5% ~ 5.0% with metal, wherein described modified MC M-22/ZSM-48 is combined Contain 0.1% ~ 10% in molecular sieve by weight, preferably 0.5% ~ 5% silicon dioxide（It is not compound including MCM-22/ZSM-48 Silicon oxide in molecular sieve）, balance of MCM-22/ZSM-48 composite molecular screens, in the MCM-22/ZSM-48 composite molecular screens MCM-22 molecular sieves are wrapped in around ZSM-48 molecular sieves, and the weight content of MCM-22 is 1.0 ~ 50%, preferably 5.0 ~ 30%。

Contain inorganic refractory oxide in catalyst of the present invention, described inorganic refractory oxide is selected from aluminium oxide, oxygen Change one or more in titanium, silicon oxide, boron oxide, magnesium oxide, Kaolin and clay, preferably aluminium oxide and/or Kaolin, More preferably aluminium oxide.

Catalyst property of the present invention is as follows：BET specific surfaces are 200～350m2/g, and pore volume is 0.3～0.5ml/g.This The specific surface and pore volume of bright middle catalyst is that, using ASAP 2400, low temperature liquid nitrogen absorption method is calculated through BET.

A kind of preparation method of alkane hydroisomerization catalyst, its step is：

1）Prepare MCM-22/ZSM-48 composite molecular screens；

2）Tetraethyl orthosilicate is loaded on above-mentioned molecular sieve, then Jing high-temperature vapors are processed, and through dry and roasting, are changed The MCM-22/ZSM-48 composite molecular screens of property；

3）By step（2）The modified composite molecular screen and inorganic refractory oxide for preparing is mixed and made into catalyst carrier；

4）ByRace's element and auxiliary agent load to step（3）In obtained catalyst carrier, through dry and roasting, obtain To catalyst of the present invention.

The inventive method, step（1）The preparation of middle MCM-22/ZSM-48 composite molecular screens includes following content, by ZSM- 48 molecular sieves are added in silica-alumina gel, and described silica-alumina gel mole is consisted of：Al₂O₃/SiO₂=0.01 ~ 0.05, OH^-/SiO₂ =0.02 ~ 0.35, R/SiO₂=0.15 ~ 1.0, H₂O/SiO₂=5 ~ 50, halogen compounds and SiO₂Mol ratio be 0.03 ~ 0.5, R For organic formwork agent.Preferably：Al₂O₃/SiO₂=0.02 ~ 0.04, OH^-/SiO₂=0.01 ~ 0.10, R/SiO₂=0.25 ~ 0.7, H₂O/SiO₂=10 ~ 40, halogen compounds and SiO₂Mol ratio be 0.05 ~ 0.3.Wherein organic formwork agent R can be two methylenes Base imines, may also be the hybrid template of one or more composition in dimethylene imines and hydro carbons, organic amine, alcohols, ketone Agent.Described halogen compounds are CH₃I、CH₃CHCl₂、CHCl₃Deng in the organohalogen compound containing 1 ~ 3 carbon atom Plant or several.Involved silicon source, silicon source and alkali source are the compound commonly used in Zeolite synthesis, and such as silicon source is that silica gel, silicon are molten Glue or waterglass etc., silicon source is hydrochlorate of sodium metaaluminate, aluminium hydroxide, activated alumina or aluminum etc., and described alkali source is hydrogen-oxygen Change sodium or potassium hydroxide etc..The addition of described ZSM-48 molecular sieves is silicon dioxide（In terms of the silicone content in silica-alumina gel） The 0.5 ~ 20 of weight, preferably 1.0 ~ 15.The crystallization under self-generated pressure hydrothermal condition, wherein crystallization temperature are 100 DEG C ~ 200 DEG C, Preferably 110 DEG C ~ 150 DEG C, crystallization time is 16 hours ~ 120 hours, preferably 20 hours ~ 70 hours.Obtain compound molecule Sieve.

Step 2）Described MCM-22/ZSM-48 composite molecular screens will be through modification, and the modifying agent for being used is for just Silester, mode of loading be able to can be selected using infusion process and kneading method, preferably infusion process, preparation containing teos solution Select organic alkoxide or ether, preferably methanol or ethanol.On the basis of modified composite molecular screen, the load capacity of tetraethyl orthosilicate （With SiO₂Meter）For 0.1% ~ 10%, preferably 0.5% ~ 5%, dip time 1 hour ~ 10 hours, preferably 3 hours ~ 6 hours, Jing Again the high-temperature vapors of Jing 100% are processed composite molecular screen after tetraethyl orthosilicate dipping, and actual conditions is as follows：Processing pressure 0.1MPa ~ 5.0MPa, preferred 0.5MPa ~ 3.0MPa, 100 DEG C ~ 500 DEG C for the treatment of temperature, preferably 150 DEG C ~ 350 DEG C, during process Between 0.5 hour ~ 5 hours, preferably 1.0 hours ~ 3.0 hours.

Step 3）Described inorganic refractory oxide is selected from aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, oxygen Change one or more in zirconium and clay, preferably aluminium oxide and/or silicon oxide, more preferably aluminium oxide.Its precursor can be with Selected from boehmite, boehmite, diaspore, gibbsite and one or more in aluminum stone is visitd, preferably intend thin Diaspore.

Step 4）The preferred platinum of VIIIth race's element and/or palladium.Most preferably platinum.Described noble metal and auxiliary agent is added to urges Mode in agent can be using infusion process or ion exchange, preferably infusion process.Step impregnation can be adopted, it would however also be possible to employ Impregnate simultaneously.Conventional activity component impregnation solution is the aqueous solution containing active metal soluble compound, such as chloroplatinic acid Solution, platinum ammonium complex solution, palladium ammonium complex solution, palladium nitrate solution, palladium chloride solution and its organic coordination compound solution, institute The rhenium-containing auxiliary agent stated is perrhenic acid, and stanniferous auxiliary agent is butter of tin or stannous chloride solution.

Catalyst of the present invention can apply to various waxy feeds isomery processing procedures, and waxy feeds can be initial boiling point More than 140 DEG C of waxy feeds such as diesel oil, white oil, atmospheric heavy distillate（AGO）, vacuum distillate（VGO）, be hydrocracked tail Oil, lubricating oil or paraffin etc., are particularly suitable for the processing procedure of lubricating oil.The waxy feeds higher for sulfur-bearing, nitrogen impurity content Typically need to carry out carrying out isomery process after hydrofinishing again.Paraffin selective isomerization reaction condition is in crude lube stock：Hydrogen Pressure 2MPa ~ 20MPa, 260 DEG C ~ 400 DEG C of temperature, the h of volume space velocity 0.5^-1~4.0h^-1, hydrogen to oil volume ratio 200 ~ 1000, preferably Condition is：Hydrogen Vapor Pressure 5MPa ~ 10MPa, 320 DEG C ~ 380 DEG C of temperature, volume space velocity 1.0h^-1~3.0h^-1, hydrogen to oil volume ratio 300 ~ 500。

Compared with prior art, a kind of alkane hydroisomerization catalyst of the invention and its preparation method and application has such as Lower advantage：

（1）The MCM-22/ZSM-48 composite molecular screens that the present invention is provided are different from MCM-22 and ZSM-48 molecular sieve simple physicals The composite molecular sieve of mixing, composite molecular screen has the pore passage structure feature of two kinds of molecular sieves of MCM-22 and ZSM-48 concurrently and acidity is special Levy, that is, ZSM-48 molecular sieve surfaces " absorption " MCM-22 molecular sieves, because the section of MCM-22 zeolites is twelve-ring Column type supercage, supercage free internal space 0.71*0.71*0.91nm can be formed in crystal outer surface and be had larger energy of adsorption The pocket of power, for reactant two subchannels are provided, prevention has the reactant contact active center of side chain, it is to avoid highly branched chain is different The generation of structure body, while while making catalyst that there is preferable long chain alkane isomerization function, cracking reaction etc. can be reduced The generation of side reaction, improves isomerisation selectivity；

（2）The present invention adds organohalogen compound in the preparation process of composite molecular screen, can make MCM-22 molecular sieves more Easily, and equably it is grown in around ZSM-48, it is to avoid aggregation occurs and MCM-22 molecules are generated in ZSM-48 ducts Sieve；

（3）The present invention selects kinetic diameter than larger tetraethyl orthosilicate（Molecular diameter>0.8nm）As modifying agent, because of it Molecular volume, can be with the hydroxy combining of molecular sieve surface than larger, can be with autotelic covering " outer layer " molecular sieve catalyst Acid centre, it is to avoid here occurs the cracking reaction of non-selectivity；Make reactant contact more likely that there is the ZSM- of type of selecting At 48 molecular sieve apertures, isomerisation selectivity is improved；

（4）Catalyst of the present invention adds auxiliary agent rhenium and stannum again, and by introducing auxiliary agent the dispersion of noble metal component can be improved Degree, this is likely due to auxiliary agent and can form alloy phase with noble metal, so as to avoid the aggregation of metal.Catalyst can not only be made More active sites are provided, and the load capacity of active metal component can be reduced, reduce the production cost of catalyst.

（5）The paraffin hydro isocatalysis prepared using the MCM-22/ZSM-48 composite molecular screens with appropriate mass ratio Agent, for the hydro-isomerization dealkylation reaction of lube cut in, pour point high with purpose product yield（Condensation point）Low and viscosity index (VI) High the characteristics of.

Specific embodiment

The preparation process of catalyst of the present invention, but it is not considered that the present invention only office are further illustrated below by embodiment In being limited to below example, the content in following examples or comparative example is if no special instructions weight percentage.

Embodiment 1

First by 4.26g NaAlO₂Mix homogeneously in 500 milliliters of stainless steel cauldrons with 19.08g sodium hydroxide solutions, stirring Mix lower by 33g silica gel, 408.2g deionized waters, 18.96g hexamethylene imines（HMI）In sequentially adding kettle, 1.65g is added CH₃I, finally adds 55g ZSM-48.After continuing to stir 10 minutes, reactor is sealed, crystallization 15h at 120 DEG C.Crystallization After end, solid product (MCM-22/ZSM-48) is isolated, numbering is S-1, and the weight content of MCM-22 is 25.4%.

Tetraethyl orthosilicate 5.5g is taken, the methanol solution of 150g tetraethyl orthosilicates is configured to, above-mentioned MCM-22/ZSM-48 is taken Molecular sieve 100g, in being impregnated into above-mentioned solution, impregnates 6.5 hours, and then again the high-temperature vapors of Jing 100% are processed, and actual conditions is such as Under：Processing pressure 1.0MPa, 350 DEG C for the treatment of temperature, process time 3.5 hours.Obtain SiO₂Load capacity be 1.5% it is modified MCM-22/ZSM-48 composite molecular screens, numbering is S-1.

Embodiment 2

First by 1.488g NaAlO₂Mix homogeneously in 500 milliliters of stainless steel cauldrons with 36.06g sodium hydroxide solutions, stirring Mix lower by 23g silica gel, 3.3gCHCl_3、359.3g deionized water, 3.00gHMI are sequentially added in kettle, 100g is finally added ZSM-48.After continuing to stir 10 minutes, reactor is sealed, crystallization 20h at 130 DEG C.After crystallization terminates, solid product is isolated Thing (MCM-22/ZSM-48), it is 11.1% that numbering is the weight content of S-2 MCM-22.Tetraethyl orthosilicate 16.8g is taken, is configured to The methanol solution of 150g tetraethyl orthosilicates, takes above-mentioned MCM-22/ZSM-48 molecular sieve 100g, in being impregnated into above-mentioned solution, leaching Stain 2.5 hours, then again the high-temperature vapors of Jing 100% are processed, and actual conditions is as follows：Processing pressure 1.5MPa, treatment temperature 350 DEG C, process time 2.0 hours.Obtain SiO₂Load capacity is 4.8% modified MC M-22/ZSM-48 composite molecular screen, and numbering is S- 2。

Embodiment 3

First by 1.136g NaAlO₂Mix homogeneously in 500 milliliters of stainless steel cauldrons with 24.04g sodium hydroxide solutions, stirring Mix it is lower 22g silica gel, 237g deionized waters, 12g HMI and 6g hexamethylene are sequentially added in kettle, finally add 120g ZSM- 48.After continuing to stir 10 minutes, reactor is sealed, crystallization 15h at 120 DEG C.After crystallization terminates, solid product is isolated (MCM-22/ZSM-48), numbering be S-3 MCM-22 weight content be 7.5%.Tetraethyl orthosilicate 10.8g is taken, 150g is configured to The methanol solution of tetraethyl orthosilicate, takes above-mentioned MCM-22/ZSM-48 molecular sieve 100g, in being impregnated into above-mentioned solution, dipping 6.5 Hour, then again the high-temperature vapors of Jing 100% are processed, and actual conditions is as follows：Processing pressure 1.5MPa, 350 DEG C for the treatment of temperature, place 4.0 hours reason time.Obtain SiO₂Load capacity is 3.1% modified MC M-22/ZSM-48 composite molecular screen, and numbering is S-3.

Embodiment 4

With embodiment 1, the ZSM-48 that difference is added divides the preparation process of composite molecular screen MCM-22/ZSM-48 of the present invention Son sieve is 150g, SiO₂Load capacity is 1.1% modified MC M-22/ZSM-48 composite molecular screen, and numbering is S-4, MCM-22's Weight content is 8.32%.

Embodiment 5

With embodiment 1, difference adds ZSM-48 molecules to the preparation process of composite molecular screen MCM-22/ZSM-48 of the present invention Sieve as 90g, SiO₂Load capacity is 2.8% modified MC M-22/ZSM-48 composite molecular screen, and numbering is S-5, the weight of MCM-22 Content is 14.1%.

Embodiment 6

The preparation of catalyst E-1 of the present invention

Example 1 prepare MCM-22/ZSM-48 molecular sieves 100g and 100 grams（In terms of aluminium oxide）Aluminium hydroxide（Germany The SB of Condean companies production）It is sufficiently mixed and 10 grams of sesbania powder mix homogeneously, is subsequently adding 230ml water and 14ml is dense Nitric acid（Mass concentration is 66.5%）, abundant kneading makes paste plastic, extrudes a diameter of 1.5mm's on banded extruder Cylindrical bars, cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalysis of the present invention in 4 hours in air atmosphere Agent carrier, using the dipping method in common filling hole with containing perrhenic acid and H₂PtCl₆Solution saturation impregnates, then again 100 DEG C It is dried 8 hours, 500 DEG C of roasting 3h in air atmosphere, catalyst of the present invention is obtained, numbering is E-1, and its physico-chemical property is shown in Table 1, Reaction result is shown in Table 3.

Embodiment 7

The preparation of catalyst E-2 of the present invention

With embodiment 7, difference is the MCM-22/ZSM- prepared with embodiment 2 to the preparation process of catalyst E-2 of the present invention 48 composite molecular screens, the catalyst of the present invention prepared, numbering is E-2, and its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.

Embodiment 8～10

The preparation of catalyst E-3 ~ E-5 of the present invention

With embodiment 1, the molecular sieve used by difference respectively is reality to the preparation process of catalyst E-3 ~ E-5 of the present invention The molecular sieve of the preparation of example 3 to 5 is applied, aluminium hydroxide is different with the amount of the amount of the noble metal of load, the catalyst of the present invention prepared E-3 ~ E-5, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.

Comparative example 1

The preparation of comparative catalyst C-1 of the present invention

The preparation method of comparative catalyst of the present invention is a difference in that used molecular sieve is same with embodiment 6 Method synthesis ZSM-48 molecular sieves provided in CN200510066975, molecular sieve numbering is Z-1, and that what is prepared is of the invention right Than catalyst C-1, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.

Comparative example 2

The preparation method of comparative catalyst of the present invention is a difference in that the same United States Patent (USP) of used molecular sieve with embodiment 6 （USP 4,954,325）Provided in method synthesis MCM-22 molecular sieves, molecular sieve numbering be M-1, the present invention for preparing Comparative catalyst C-2, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.

Comparative example 3

The preparation of comparative catalyst C-3 of the present invention

With embodiment 1, the molecular sieve used by difference is ZSM-48 and MCM- to the preparation process of comparative catalyst C-3 of the present invention 22 two kinds of molecular sieves press 4:1（Mass ratio）Mechanical mixture, the comparative catalyst C-3 of the present invention for preparing, its physico-chemical property is shown in Table 1, reaction result is shown in Table 3.

Table 1 is respectively implemented（Relatively）Example prepares the main physico-chemical property of catalyst

Note：（1）1. on the basis of catalyst quality, ZSM-48 and MCM-22 mixed molecular sieves, mass ratio 4 are 2. represented:1,3. help Agent rhenium, 4. auxiliary agent stannum（2）S represents specific surface area, and V represents pore volume.

Catalyst prepared by above example and comparative example is evaluated using the medium-sized fixed bed reactors of 200ml, is catalyzed Agent loadings are 200ml, and prereduction is carried out to catalyst before charging, make the noble metal on catalyst be changed into reduction-state, are reduced Condition is as follows：In presence of hydrogen, 300 DEG C ~ 500 DEG C of temperature, pressure 0.5MPa ~ 10MPa, 1 hour ~ 12 hours time,

Evaluate used raw oil main character and be shown in Table 2.

The raw oil main character of table 2

Catalyst of the present invention is applied to during lubricating oil isomerization dewaxing, high with purpose product yield, pour point（Condensation point）It is low and The characteristics of viscosity index (VI) is high.

The evaluating catalyst condition of table 3 and result

The evaluation result of table 3 shows, compared with comparative catalyst, the catalyst provided using the present invention, for lube cut Hydroprocessing processes in, when lube base oil pour point is close, C₅ ⁺Liquid is received and improves more than 5wt%, lube base oil yield More than 10wt% is improved, the viscosity index (VI) of product improves 10 ~ 24 units, illustrate that catalyst of the present invention is processing crude lube stock During, effect have significantly improve.

Claims

1. a kind of alkane hydroisomerization catalyst, it is characterised in that：By weight percentage, modified MC M-22/ZSM-48 is answered It is 10 ~ 90% to close molecular sieve content, and the VIIIth race's bullion content is 0.05 % ~ 1.0%, and auxiliary agent rhenium and/or Theil indices are in terms of metal For 0.1% ~ 10%, wherein by weight containing 0.1% ~ 10% dioxy in described modified MC M-22/ZSM-48 composite molecular screen SiClx, balance of MCM-22/ZSM-48 composite molecular screens, MCM-22 molecular sieves in the MCM-22/ZSM-48 composite molecular screens It is wrapped in around ZSM-48 molecular sieves, the weight content of MCM-22 is 1.0 ~ 50%.

2. catalyst according to claim 1, it is characterised in that：By weight percentage, modified MC M-22/ZSM-48 is answered It is 20% ~ 80% to close molecular sieve content, and the VIIIth race's bullion content is 0.1 % ~ 0.8%, and auxiliary agent rhenium and/or Theil indices are in terms of metal For 0.5% ~ 5.0%, wherein by weight containing 0.5% ~ 5% dioxy in described modified MC M-22/ZSM-48 composite molecular screen SiClx, MCM-22 molecular sieves are wrapped in around ZSM-48 molecular sieves in the MCM-22/ZSM-48 composite molecular screens, MCM- 22 weight content is 5.0 ~ 30%.

3. catalyst according to claim 1, it is characterised in that：Contain inorganic refractory oxide in catalyst, it is described Inorganic refractory oxide be the one kind in aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, Kaolin and clay or It is several.

4. catalyst according to claim 1, it is characterised in that：Catalyst property is as follows：Specific surface is 200～350m²/ G, pore volume is 0.3～0.5ml/g.

5. the preparation method of the arbitrary catalyst of Claims 1-4, it is characterised in that：Comprise the steps：

Prepare MCM-22/ZSM-48 composite molecular screens；

Tetraethyl orthosilicate is loaded on above-mentioned molecular sieve, then Jing high-temperature vapors are processed, and through dry and roasting, are modified MCM-22/ZSM-48 composite molecular screens；

By step（2）The modified composite molecular screen and inorganic refractory oxide for preparing is mixed and made into catalyst carrier；

ByRace's element and auxiliary agent load to step（3）In obtained catalyst carrier, through dry and roasting, this is obtained Invention catalyst.

6. method according to claim 5, it is characterised in that：Step（1）The system of middle MCM-22/ZSM-48 composite molecular screens It is standby to include following content, ZSM-48 molecular sieves are added in silica-alumina gel, described silica-alumina gel mole is consisted of：Al₂O₃/ SiO₂=0.01 ~ 0.05, OH^-/SiO₂=0.02 ~ 0.35, R/SiO₂=0.15 ~ 1.0, H₂O/SiO₂=5 ~ 50, halogen compounds with SiO₂Mol ratio be organic formwork agent for 0.03 ~ 0.5, R.

7. method according to claim 6, it is characterised in that： Al₂O₃/SiO₂=0.02 ~ 0.04, OH^-/SiO₂=0.01~ 0.10, R/SiO₂=0.25 ~ 0.7, H₂O/SiO₂=10 ~ 40, halogen compounds and SiO₂Mol ratio be 0.05 ~ 0.3.

8. method according to claim 6, it is characterised in that：Organic formwork agent R is dimethylene imines, or sub- for two The mixed templates of one or more composition in methylene imine and hydro carbons, organic amine, alcohols, ketone.

9. method according to claim 6, it is characterised in that：Described halogen compounds are CH₃I、CH₃CHCl₂、CHCl₃ One or more in organohalogen compound.

10. method according to claim 6, it is characterised in that：Involved silicon source is silica gel, Ludox or water in gel Glass, silicon source is the hydrochlorate of sodium metaaluminate, aluminium hydroxide, activated alumina or aluminum, and alkali source is sodium hydroxide or potassium hydroxide.

11. methods according to claim 6, it is characterised in that：The addition of described ZSM-48 molecular sieves is in gel The 0.5 ~ 20 of silica weight, the wherein crystallization under self-generated pressure hydrothermal condition, crystallization temperature are 100 DEG C ~ 200 DEG C, crystallization Time obtained composite molecular screen for 16 hours ~ 120 hours.

12. methods according to claim 11, it is characterised in that：The addition of described ZSM-48 molecular sieves is in gel The 1.0 ~ 15 of silica weight, crystallization temperature is 110 DEG C ~ 150 DEG C, and crystallization time is 20 hours ~ 70 hours.

13. methods according to claim 5, it is characterised in that：Step 2）Tetraethyl orthosilicate, dipping are loaded using infusion process 1 hour ~ 10 hours time, again the high-temperature vapors of Jing 100% are processed the composite molecular screen Jing after tetraethyl orthosilicate dipping, concrete bar Part is as follows：Processing pressure 0.1MPa ~ 5.0MPa, 100 DEG C ~ 500 DEG C for the treatment of temperature, process time 0.5 hour ~ 5 hours.

14. methods according to claim 13, it is characterised in that：Dip time 3 hours ~ 6 hours, processing pressure 0.5MPa ~ 3.0MPa, 150 DEG C ~ 350 DEG C for the treatment of temperature, process time is 1.0 hours ~ 3.0 hours.

15. methods according to claim 5, it is characterised in that：Step 3）Described inorganic refractory oxide is selected from oxygen Change one or more in aluminum, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium oxide and clay.

16. methods according to claim 15, it is characterised in that：Inorganic refractory oxide is aluminium oxide, its precursor choosing From boehmite, boehmite, diaspore, gibbsite and visit one or more in aluminum stone.

17. methods according to claim 5, it is characterised in that：Step 4）VIIIth race's element is platinum and/or palladium.

18. methods according to claim 5, it is characterised in that：Step 4）Noble metal and auxiliary agent are added in catalyst to be adopted Use infusion process.

Application of the arbitrary catalyst of 19. Claims 1-4 in alkane isomerization, it is characterised in that：The raw material be diesel oil, One or more in white oil, atmospheric heavy distillate, vacuum distillate, hydrocracking tail oil, lubricating oil or paraffin.

20. applications according to claim 19, it is characterised in that：Raw material is lubricating oil, and operating condition is as follows：Hydrogen pressure Power 2MPa ~ 20MPa, 260 DEG C ~ 400 DEG C of temperature, the h of volume space velocity 0.5^-1~4.0h^-1, hydrogen to oil volume ratio 200 ~ 1000.

21. applications according to claim 20, it is characterised in that：Operating condition is as follows：Hydrogen Vapor Pressure 5MPa ~ 10MPa, temperature Degree 320 DEG C ~ 380 DEG C, volume space velocity 1.0h^-1~3.0h^-1, hydrogen to oil volume ratio 300 ~ 500.