CN106140248B

CN106140248B - A kind of preparation method of diesel oil hydrogenation modification catalyst carrier

Info

Publication number: CN106140248B
Application number: CN201510135856.4A
Authority: CN
Inventors: 于政敏; 孙晓艳; 樊宏飞; 王继锋
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: 2015-03-27
Filing date: 2015-03-27
Publication date: 2018-06-15
Anticipated expiration: 2035-03-27
Also published as: CN106140248A

Abstract

The invention discloses a kind of preparation methods of diesel oil hydrogenation modification catalyst carrier.This method includes：Beta-molecular sieve, macroporous aluminium oxide and adhesive are mixed, molding, through dry and roasting, carrier is made；Wherein beta-molecular sieve is to prepare amorphous silica-alumina predecessor using specific acid-base precipitation method, then adds in water, silicon source and template, obtains silica-alumina gel；It through two step dynamic crystallizations, then exchanges through ammonium salt and is handled with Template removal, beta-molecular sieve is made.The catalyst for hydro-upgrading prepared using the carrier has the characteristics that diesel product yield height and good product quality.

Description

A kind of preparation method of diesel oil hydrogenation modification catalyst carrier

Technical field

The present invention relates to a kind of preparation method of diesel oil hydrogenation modification catalyst carrier, more specifically one kind can be with Poor ignition quality fuel is raw material, production have the characteristics that high cetane number, low condensation point, compared with low-density diesel oil the bavin containing beta-molecular sieve The preparation method of oily catalyst for hydro-upgrading carrier.

Background technology

As crude oil heaviness, in poor quality degree are aggravated, secondary processing diesel oil fraction especially catalytic cracking diesel oil quality It is deteriorated, on the other hand, to improve yield of light oil, the processing that each refiner in countries in the world improves catalytic cracking process one after another is deep Degree, and then the quality of catalytic cracking diesel oil is caused further to be deteriorated.With environmental requirement increasingly stringent, diesel quality standard Constantly upgrading, especially discharge standard Central Europe IV, V standard of Europe to the sulphur in diesel oil and arene content, Cetane number, density, The indexs such as T95 propose more strict requirements.In addition, the people of extremely frigid zones or winter life come to the low of diesel product Warm mobile performance compares attention, and only low freezing point diesel fuel product can be met the actual needs.Winter north cold area Need a large amount of low-coagulation diesel oils, the low temperature flow of diesel oil（Condensation point, cold filter plugging point, pour point etc.）Index seems even more important.

At present, the production technology for cleaning diesel product mainly has the technologies such as hydrofinishing and Medium Pressure Hydrogenation Modification.Add hydrogen smart System can effectively reduce the sulfur content of modification diesel oil, but effect is general in terms of improving Cetane number and reducing T95 temperature.Middle pressure adds Hydrogen modification is suitably to crack diesel oil under the conditions of middle pressure, changes catalytic cracking diesel oil hydro carbons composition structure, reaches improvement diesel oil Product quality, production meet the purpose of the cleaning diesel product of harsh diesel oil standard.Institute in pressure diesel modifying catalyst in current The Cracking Component of use is mainly modified Y type molecular sieve, since Y type molecular sieve has the supercage structure of twelve-ring so that Dry large-minded, diesel product the yield of existing diesel modifying catalyst is low, the amplitude of Cetane number raising is small, the recycling of T95 points Small, the shortcomings of condensation point is high and density is big.For example, CN1184843A and CN101463271A.CN1184843A discloses a kind of bavin Oily hydrogenation conversion catalyst, the composition of the catalyst is 40 ~ 80wt% of aluminium oxide, 0 ~ 20wt% of amorphous silica-alumina, molecular sieve 5 ~ 30wt%, the molecular sieve hold 0.4 ~ 0.52mL/g, 750 ~ 900m of specific surface area for hole²/ g, lattice constant 2.420 ~ 2.500nm, silica alumina ratio are 7 ~ 15 Y type molecular sieve.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel And preparation method thereof, mainly mixed using the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y type molecular sieve, Molding and roasting introduce a effective amount of hydrogenation metal in molding species later.Above-mentioned catalyst has higher desulfurization and denitrogenation Activity, but the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is small, the shortcomings of condensation point is high and density is big.

Relative to Y type molecular sieves, beta-molecular sieve has three-dimensional twelve-ring pore structure, but without as Y type molecular sieves Supercage structure, be mainly characterized by double 6 round rings unit bug hole structures of two 4 round ringss and four 5 round ringss, main channel diameter exists 0.56-0.75nm, the duct feature of beta-molecular sieve cause it has the fracture of chain hydrocarbon-selective in cracking reaction to make well With, and with very strong isomery performance, can be used for producing low condensation point oil distillate as cracking component, industrially obtain extensively Application.

US4847055 discloses a kind of method of improved synthesis beta-molecular sieve, wherein using a kind of special silicon source, with TEABr is template, and beta-molecular sieve is prepared under the conditions of existing for crystal seed.The silicon source is in certain condition by soluble silicon solution Lower addition precipitating reagent is made.The dosage of this method template is larger, and easily generates modenite and ZSM-5 stray crystals.Only As (TEA)₂O/SiO₂>0.14, i.e. TEA⁺/SiO₂>When 0.28, the production quantity of stray crystal could be reduced.

Above-mentioned hydro-thermal method synthesis β zeolites need a large amount of expensive organic formwork agent tetraethyl ammonium hydroxides, beta-molecular sieve synthesis Cost largely derived from template, typically constitute from 70% or so.Template dosage is reduced, so as to reduce β zeolite synthesis costs, one It is directly the hot spot of the area research.

Furthermore beta-molecular sieve as catalyst use it is preceding must by the organic formwork agent being blocked in zeolite cavity remove fall Catalytic activity can just be made it have.The method of conventional removing organic formwork agent is high-temperature roasting, since high-temperature roasting will destroy β The structure of molecular sieve declines its crystallinity, and thermal stability and hydrothermal stability are deteriorated, and consumption of template agent is bigger, This extent of the destruction is more serious.And use add in a small amount of template synthesizing high-silicon aluminium than beta-molecular sieve when, the crystallinity meeting of product Very low, thermal stability and hydrothermal stability are poor.

CN1351959A is related to a kind of synthetic method of molecular sieve.Al is pressed first₂O₃：(30-150)SiO₂：(5-20) (TEA)₂O：(1-8.5)Na₂O：(650-1200)H₂The mol ratio of O prepares Alusil A, by Al₂O₃：(20-80)SiO₂：(5- 15)Na₂O：(350-1000)H₂The mol ratio of O prepares Alusil B, and Alusil A and Alusil B then is pressed 1：10 weight It than mixing, is transferred in autoclave pressure after stirring evenly, after sealing at a temperature of 100-200 DEG C, is stirred under static or 10-150rpm rotating speeds Mix crystallization 15-150 hours, end product is through filtering, washing and be dried to obtain beta-molecular sieve.Although this synthetic method can will have The dosage of machine template is reduced to TEAOH/SiO₂=0.05, but beta-molecular sieve silica alumina ratio prepared by this method is relatively low, and beta-molecular sieve Characteristic peak have a small amount of miscellaneous peak, have stray crystal generation.

CN 1198404A propose a kind of method for synthesizing beta-molecular sieve, using halide, the tetraethyl by tetraethyl ammonium The composite mould plate agent that ammonium hydroxide and fluoride are formed under alkaline condition makes silicon source, silicon source and crystal seed reaction crystallization generate β points Son sieve.Although this method reduces template dosage, increase the yield of beta-molecular sieve, but need add in composite mould plate agent and Crystal seed, and silica alumina ratio be more than 30 after, crystallinity is relatively low, and thermal stability and hydrothermal stability are poor.

Invention content

For shortcoming of the prior art, the present invention provides a kind of good diesel oil hydrogenation modification catalysis of catalytic performance The preparation method of agent carrier.The catalyst for hydro-upgrading carrier is using a kind of high silica alumina ratio, high-crystallinity, bigger serface, steady Qualitative good type molecular sieve has diesel product yield as acidic components by catalyst for hydro-upgrading prepared by carrier of the present invention The features such as high and good product quality.

The preparation method of diesel oil hydrogenation modification catalyst carrier of the present invention, including：By beta-molecular sieve, macroporous aluminium oxide and glue Mixture mixes, molding, and through dry and roasting, carrier is made；On the basis of the weight of carrier, carrier composition includes：Beta-molecular sieve Content is 5~30wt%, and the content of macroporous aluminium oxide is 20~65wt%, and the content of adhesive is 15~50wt%；It is wherein described Beta-molecular sieve, including following preparation process：

（1）, amorphous silica-alumina predecessor is prepared using acid-base precipitation method, the amorphous silica-alumina predecessor is with silica On the basis of the total weight of aluminium oxide, silicon is using the content that silica is counted as 40wt%~75wt%, preferably 55wt%~70wt%； Its preparation process includes acid-base neutralization plastic, and the method that aging, wherein silicon introduce reaction system is neutralized into aluminum contained compound Introducing portion silicon-containing compound, remainder silicon-containing compound are neutralized into aluminum contained compound before glue and/or during plastic It introduces after glue and before ageing；

（2）, by Al₂O₃： SiO₂： Na₂O：H₂O=1：(62~130)：(0.5~3.0)：(100~500), TEAOH/ SiO₂For 0.010 ~ 0.095 total molar ratio, preferably SiO₂/Al₂O₃For 70 ~ 110, TEAOH/SiO₂=0.020~ 0.080, to step under conditions of 0~40 DEG C of quick stirring（1）In the amorphous silica-alumina predecessor of gained add in water, silicon source and Template, and control ph is 9.5 ~ 12.0, is stirred evenly, and obtains silica-alumina gel, TEA be quaternary amine alkali sun in template from Son；

（3）, step（2）The silica-alumina gel of gained is through two step dynamic crystallizations, and using filter, Na β type molecules are made in washing Sieve.

（4）, the Na beta molecular sieves carry out ammonium salt exchange and Template removal processing, beta-molecular sieve is made.

Preferably, step（1）Amorphous silica-alumina predecessor preparation method using conventional acid-base precipitation method, wherein wrapping Acid-base neutralization plastic is included, aging, wherein acid-base neutralization plastic process are the neutralization reaction processes of acid material and alkaline material.

Preferably, neutralize plastic process may be used acid material or the continuous acid-base titration of alkaline material mode or In a manner that acid material and alkaline material cocurrent neutralize.

Preferably, it is described aluminum contained compound with introducing portion is siliceous in precipitating reagent and before plastic and/or during plastic The mode of compound is：Part silicon-containing compound is pre-mixed with the aluminum contained compound and/or precipitating reagent, can also will be contained Silicon compound is individually added into reaction system in aluminum contained compound and during plastic or the combination of the above method.

When being pre-mixed, can first be mixed according to the property of different silicon-containing compounds with acid material or alkaline material It closes, then carries out acid-base neutralization plastic（For example during containing silicon materials using sodium metasilicate, sodium metasilicate can be mixed with alkaline material；It is siliceous When material uses Ludox, add in acid aluminiferous material）.

Silicon-containing compound is individually added into the mode of reaction system in aluminum contained compound and during plastic is：It is described to contain Aluminium compound and precipitating reagent are first mixed, and are then individually added into silicon-containing compound or by the part silicon-containing compound, institute It states aluminum contained compound and precipitating reagent is separately added into reaction kettle simultaneously；Or by the part silicon-containing compound and aluminum contained compound It is added separately in the precipitating reagent simultaneously；Or the part silicon-containing compound and precipitating reagent are added separately to simultaneously described In aluminum contained compound.Be individually added into the mode of reaction system is not influenced by the property containing silicon materials, and silicon-containing compound can be direct It adds in.

Preferably, in step（1）In, in the aluminum contained compound and after plastic and the siliceous chemical combination that introduces before ageing Object accounted in terms of silica silicon 5wt% ~ 85wt% in terms of silica, preferably 30wt% in amorphous silica-alumina predecessor ~ 70wt%。

Preferably, the aluminum contained compound is selected from Al₂(SO₄)₃、AlCl₃、Al(NO₃)₃It is one or more in solution, institute State a concentration of 30~150g A1 of aluminum contained compound solution₂O₃/L；It is molten that precipitating reagent is selected from sodium hydroxide solution, ammonium hydroxide, sodium carbonate It is one or more in liquid, sodium bicarbonate solution, sodium aluminate solution.

Preferably, the aluminum contained compound be sodium aluminate solution, a concentration of the 40~100 of the sodium aluminate solution g A1₂O₃/ L, the acidic precipitation agent are nitric acid.

The silicon-containing compound can be described to be one or more in waterglass, Ludox and organo-silicon compound etc. Organo-silicon compound are preferably one or more in silanol, silicon ether and siloxanes, with SiO₂Quality meter, the silicon-containing compound A concentration of 40~200 g SiO₂/L。

In step（2）In, the silicon source is routinely using silicon source during beta molecular sieve is prepared, and the silicon source is white It is one or more in carbon black, silica gel, Ludox, waterglass.The template is preferably tetraethyl ammonium hydroxide.

In the step（1）In, the condition of the plastic is：Temperature is 20~85 DEG C, and pH value is 7.0~10.0, preferably For temperature is 40~80 DEG C, and pH value is 7.5~9.0；

The condition of the aging is：Temperature is 20~85 DEG C, and pH is 7.0~10.0,0.2~8.0 hour time, preferably For temperature is 40~80 DEG C, and pH is 7.0~9.5, and the time is 0.5~5.0 hour.

In step（2）In, 0~40 DEG C of the reaction temperature of the silica-alumina gel is generated, pH value is 9.5~12.0, preferably, The reaction temperature for generating the silica-alumina gel is 10~30 DEG C, and pH value is 10~11.

In the step（3）In, step（2）Specific steps of the silica-alumina gel of gained through two step dynamic crystallizations include：The The condition of one step dynamic crystallization is：Crystallization is carried out under agitation, and temperature is 50~90 DEG C, and the time is 0.5~18 hour；The The condition of two step dynamic crystallizations is：Crystallization is carried out under agitation, and temperature is 100~200 DEG C, and the time is 40~120 hours.

In the step（3）In, the condition of the first step dynamic crystallization is：Crystallization, temperature are carried out under agitation It it is 60~80 DEG C, the time is 1~10 hour；The condition of the second step dynamic crystallization is：Crystallization is carried out under agitation, temperature It is 120~170 DEG C to spend, and the time is 50~100 hours.

In the step（3）In, in step（2）The silica-alumina gel of gained, using filter, washs it through two step dynamic crystallizations Afterwards, drying can be passed through or be not dried to obtain Na beta molecular sieves.

Preferably, step（4）In, ammonium salt is exchanged to be carried out using conventional method, and such as one or many ammonium salts exchange, and ammonium salt is handed over Na in beta-molecular sieve after changing₂O weight contents are less than 0.3%；Ammonium salt can pass through washing and dry step after exchanging, wherein Dry condition is as follows：In 80 DEG C ~ 150 DEG C dryings 3~6 hours.

Preferably, step（4）In, Template removal processing uses aerobic high-temperature process, treatment temperature for 400~ 800 DEG C, processing time is 5~20 hours, and preferably, treatment temperature is 500~700 DEG C, and processing time is 10~15 hours.

The property of beta-molecular sieve used is as follows in catalyst for hydro-upgrading carrier of the present invention：SiO₂/Al₂O₃Molar ratio for 60~ 120, specific surface area is 505~850m²0.35~0.60mL/g of/g, Kong Rongwei, relative crystallinity are 100%~135%；The β Relative crystallinity of the molecular sieve after water vapour hydro-thermal process is more than 95%.

Beta-molecular sieve preferred property used is SiO₂/Al₂O₃Molar ratio is 65~100, specific surface area for 550~ 800m²0.40~0.60mL/g of/g, Kong Rongwei, relative crystallinity be 110%~130%, the beta-molecular sieve through water vapour hydro-thermal at Relative crystallinity after reason is 95%~125%.

Beta-molecular sieve property used is more preferably：SiO₂/Al₂O₃Molar ratio is 65~100, specific surface area 600 ~750 m²/ g, hole hold 0.45~0.55mL/g, and relative crystallinity is 115%~130%；The beta-molecular sieve is through water vapour hydro-thermal Treated, and relative crystallinity is 110%~125%.

In the present invention, condition of the beta-molecular sieve through water vapour hydro-thermal process is as follows：Through 750 DEG C of water vapour hydro-thermal process 2 Hour.

In the preparation method of catalyst for hydro-upgrading carrier of the present invention, adhesive therefor is preferably used in small porous aluminum oxide 0.3~0.5 mL/g of Kong Rongwei of small porous aluminum oxide, specific surface area are 200~400m²/g。

In catalyst carrier of the present invention, 0.7 ~ 1.0 mL/g of Kong Rongwei of macroporous aluminium oxide used, specific surface area 200 ~ 500 m²/g。

Catalyst carrier of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..It is being catalyzed In agent carrier forming process, shaping assistant, such as peptization acid, extrusion aid can also be added in, peptizing agent generally may be used inorganic Acid and/or organic acid, extrusion aid such as sesbania powder.Catalyst carrier of the present invention is dried and is roasted using conventional method, is had Body is as follows：It is 3~10 hours dry at a temperature of 80~150 DEG C, it is roasted 3~12 hours at 400~800 DEG C.

When catalyst carrier of the present invention is used to prepare hydrocracking catalyst, load side conventional in the prior art can be used Method, preferably infusion process can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component Final hydrocracking catalyst is made after drying, roasting in agent carrier, the carrier after dipping.

Diesel oil hydrogenation modification catalyst support properties of the present invention are as follows：Specific surface area is 400~600 m²/ g, Kong Rong are 0.50~1.0 mL/g.

The present invention is in the preparation process of beta-molecular sieve, first by part silicon-containing compound before plastic and/or during plastic It adds in reaction system, forms stable colloidal state and sial integrated structure.Since this colloid surface has many hydroxyls Structure can be combined with the remainder silicon-containing compound added in below well, so as to which amorphous silica-alumina predecessor be made to have more Add stable structure.Later, amorphous silica-alumina predecessor, template and another part silicon source etc. are mixed and made into silica-alumina gel, More nucleus can be formed in synthetic system in this way, are evenly dispersed in synthetic system, there is good crystallization to be oriented to and make With, then through two step dynamic crystallizations, easily form complete skeleton structure, the high beta-molecular sieve of crystallinity.The method of the present invention not only may be used To reduce the usage amount of organic formwork agent, the beta-molecular sieve of high-crystallinity, high silica alumina ratio can also be synthesized, and with better Thermal stability and hydrothermal stability, and the beta-molecular sieve purity of the present invention is high, without stray crystal.Moreover, the beta-molecular sieve of the present invention is By Na beta molecular sieves by the exchange of simple ammonium salt and Template removal, can obtain, without carrying out dealuminzation or dealumination complement silicon again Wait dual-spectrum process.

When being modified as the catalyst prepared by diesel oil hydrogenation modification catalyst carrier of the present invention for poor ignition quality fuel, particularly In middle press strip part（4~12MPa）With very high catalytic activity and diesel yield when handling poor ignition quality fuel, and diesel oil distillate Condensation point reduction amplitude is big, improves the Cetane number of modification diesel oil by a relatively large margin, and the density of diesel product is also effectively reduced, Can meet refinery's increase operating flexibility, increase device processing capacity, the diesel oil that further raises productivity and improves the quality needs.

Specific embodiment

In order to which the present invention is better described, further illustrated the present invention with reference to embodiment and comparative example.But this hair Bright range is not limited solely to the range of these embodiments.Analysis method of the present invention：Specific surface area, Kong Rong use low temperature liquid nitrogen physics Absorption method, relative crystallinity use x-ray diffraction method, and silica alumina ratio uses chemical method.In the present invention, wt% is mass fraction.

Embodiment 1

（1）The preparation of amorphous silica-alumina predecessor

Solid aluminum sulfate is configured to a concentration of 80g A1 of 100mL₂O₃/ L aluminum sulfate working solutions（a）.Concentrated ammonia liquor is added in Appropriate distilled water is diluted to about 10wt% weak aqua ammonias（b）.It takes with SiO₂The sodium silicate solution of quality meter 28wt%, then be diluted to A concentration of 150g SiO of 80mL₂/ L sodium metasilicate working solutions（c）.One 5 liters of steel retort is taken, 0.2 is added in retort After rising distilled water and being heated with stirring to 70 DEG C, open simultaneously and have respectively（a）、（b）With（c）The valve of container, control（a）With （c）Flow so that the neutralization reaction time at 40 minutes, and adjust rapidly（b）Flow the pH value of system is made to be maintained at 7~8, And the temperature of control system is at 60 DEG C or so.After the completion of reacting aluminum sulfate, stop adding in（b）,（c）Addition for 40mL, it is raw Into silicon-aluminum sol stablize after twenty minutes, continuously add（c）40mL is added in 10 minutes, starts the ageing process of system, is kept PH value is 8.0, and temperature 60 C, aging 30 minutes obtains amorphous silica-alumina predecessor, and amorphous silica-alumina predecessor is with silica On the basis of the wgt dry basis by total of aluminium oxide, using the content that silica is counted as 60wt%.

（2）The preparation of gel

According to Al₂O₃：SiO₂：Na₂O：H₂O=1：80 ：1.6 : 240、TEAOH/SiO₂=0.075 total molar ratio Each material is mixed, to step（1）Water, sodium silicate solution and tetraethyl hydroxide are added in the amorphous silica-alumina predecessor of gained Ammonium, and control ph is 11, reaction temperature is 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.

（3）Crystallization

By step（2）Obtained silica-alumina gel is poured into stainless steel cauldron, stirs crystallization 5 hours at 80 DEG C, then 150 DEG C are warming up to, then stirring crystallization 30 hours filters, dry at 120 DEG C after washing to neutrality, obtains Na beta-molecular sieve products N β -1, measures relative crystallinity；N β -1 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；Nβ-1 After 750 DEG C of water vapour hydro-thermal process 2 hours, then the relative crystallinity after hydro-thermal process is measured, specific N β -1 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Suitable water purification is added, and add a certain amount of ammonium nitrate in Na beta-molecular sieve N β -1, make liquid-solid ratio（Weight）For 10：1, a concentration of 2mol/L of ammonium nitrate, stirring are warming up to 95~100 DEG C, and constant temperature stirs 2 hours, then filters, filter cake is again Secondary progress ammonium salt exchange, the condition of exchange is identical with first time, until finally washing molecule is sieved to pH value neutrality, is put into dry It is dry in dry band, it is 8 hours dry at 100~120 DEG C.Dried beta-molecular sieve is taken to carry out abjection template processing, is used Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and beta-molecular sieve S β -1, XRD determining S β -1 relative crystallinities is made；S β -1 is after 750 DEG C of water vapour hydro-thermal process 2 hours, then measures the relative crystallinity after hydro-thermal process, the results are shown in Table 2.

Embodiment 2

（1）The preparation of amorphous silica-alumina predecessor

Solid aluminum chloride is configured to a concentration of 100g A1 of 100mL₂O₃/ L aluminium chloride working solutions（a）.By concentrated ammonia liquor plus Enter appropriate distilled water and be diluted to about 10wt% weak aqua ammonias（b）.It takes with SiO₂The sodium silicate solution of quality meter 28wt%, then be diluted to A concentration of 100g SiO of 100mL₂/ L sodium metasilicate working solutions（c）.2 liters of steel retort is taken, 0.3 liter is added in retort Distilled water and after being heated with stirring to 70 DEG C, opens simultaneously and has respectively（a）、（b）With（c）The valve of container, control（a）With（c） Flow so that the neutralization reaction time at 40 minutes, and adjust rapidly（b）Flow the pH value of system is made to be maintained at 7~8, and control The temperature of system processed is at 60 DEG C or so.After the completion of aluminium reaction, stop adding in（b）,（c）Addition for 60mL, generation Silicon-aluminum sol is stablized after twenty minutes, continuously adds（c）40mL is added in 10 minutes, starts the ageing process of system, keeps pH value 8.0, temperature 60 C, aging 30 minutes obtains amorphous silica-alumina predecessor, and amorphous silica-alumina predecessor is with silica and oxygen On the basis of the wgt dry basis by total for changing aluminium, using the content that silica is counted as 50wt%.

（2）The preparation of gel

According to Al₂O₃：SiO₂：Na₂O：H₂O=1：90 ：1.8 : 260、TEAOH/SiO₂=0.062 total molar ratio Each material is mixed, to step（1）Water, sodium silicate solution and tetraethyl hydroxide are added in the amorphous silica-alumina predecessor of gained Ammonium, and control ph is 11, reaction temperature is 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.

（3）Crystallization

By step（2）Obtained silica-alumina gel is poured into stainless steel cauldron, stirs crystallization 5 hours at 90 DEG C, then 160 DEG C are warming up to, then stirring crystallization 30 hours filters, dry at 120 DEG C after washing to neutrality, obtains Na beta-molecular sieve products N β -2, measure relative crystallinity；N β -2 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；Nβ-2 After 750 DEG C of water vapour hydro-thermal process 2 hours, then the relative crystallinity after hydro-thermal process is measured, specific N β -2 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Suitable water purification is added, and add a certain amount of ammonium nitrate in Na beta-molecular sieve N β -2, make liquid-solid ratio（Weight）For 10：1, a concentration of 2mol/L of ammonium nitrate, stirring are warming up to 95~100 DEG C, and constant temperature stirs 2 hours, then filters, filter cake is again Secondary progress ammonium salt exchange, the condition of exchange is identical with first time, until finally washing molecule is sieved to pH value neutrality, is put into dry It is dry in dry band, it is 8 hours dry at 100~120 DEG C.Dried beta-molecular sieve is taken to carry out abjection template processing, is used Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and beta-molecular sieve S β -2, XRD determining S β -2 relative crystallinities is made；S β -2 is after 750 DEG C of water vapour hydro-thermal process 2 hours, then measures the relative crystallinity after hydro-thermal process, the results are shown in Table 2.

Embodiment 3

（1）The preparation of amorphous silica-alumina predecessor.

Solid aluminum chloride is configured to a concentration of 100g A1 of 120mL₂O₃/ L aluminium chloride working solutions（a）.By concentrated ammonia liquor plus Enter appropriate distilled water and be diluted to about 10wt% weak aqua ammonias（b）.It takes with SiO₂The sodium silicate solution of quality meter 28wt%, then be diluted to A concentration of 80g SiO of 100mL₂/ L sodium metasilicate working solutions（c）.One 2 liters of steel retort is taken, 0.3 is added in retort Distilled water is risen, opening has（a）The valve of container, will（a）It is added in retort and stirs, then open and have（c）Container Valve, 30 minutes or so by 40ml（c）It is added in retort, after being heated to 70 DEG C, opening has（b）The valve of container, Control（b）Flow so that the neutralization reaction time at 40 minutes, when system pH reaches 7 ~ 8 or so, close valve, generation Silicon-aluminum sol stablize after twenty minutes, continuously add（c）50ml is added in 10 minutes, starts the ageing process of system, keeps pH Value is 8.5, temperature 60 C, aging 30 minutes, obtains amorphous silica-alumina predecessor, amorphous silica-alumina predecessor with silica and On the basis of the wgt dry basis by total of aluminium oxide, using the content that silica is counted as 40wt%.

（2）The preparation method of gel is substantially identical with embodiment 1.Difference is：According to Al₂O₃：SiO₂：Na₂O：H₂O =1：70 ：1.8 : 260、TEAOH/SiO₂=0.064 total molar ratio mixes each material.

（3）Crystallization obtains Na beta-molecular sieve product N β -3, measures relative crystallinity with embodiment 1；N β -3 are through in 550 DEG C of air After roasting 3 hours, the relative crystallinity after roasting is measured；N β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure water Relative crystallinity after heat treatment, specific N β -3 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Ammonium salt exchanges and the method for Template removal is with embodiment 1, and Na beta-molecular sieve N β -3 are made beta-molecular sieve S β -3, XRD Measure S β -3 relative crystallinities；S β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure the opposite knot after hydro-thermal process Brilliant degree, the results are shown in Table 2.

Embodiment 4

By 20 grams of S β -1 molecular sieves, (hole holds 0.9mLg, specific surface area 350m to 105 grams of macroporous aluminium oxides²/ g), 90 grams it is viscous The small porous aluminum oxide of mixture, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, Add water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT- 1, property is shown in Table 3.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Embodiment 5

By 40 grams of S β -2 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), 90 grams it is viscous The small porous aluminum oxide of mixture, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, Add water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT- 2。

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Embodiment 6

By 40 grams of S β -3 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), 90 grams it is viscous The small porous aluminum oxide of mixture, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, Add water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT- 3。

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Comparative example 1（With reference to CN1351959A）

By 20.5g White Carbon blacks, 2mL sodium aluminate solutions, 59g tetraethyl ammonium hydroxides and 0.9g sodium hydroxides, in room temperature With mixed under mechanical agitation, and continue stirring and be uniformly mixed to raw material：Mixture is transferred in autoclave pressure, at 130 DEG C after sealing At a temperature of after static ageing 5 hours, take out and be quickly cooled down autoclave pressure, obtain Alusil A.By 120g Ludox, the inclined aluminium of 6.3mL Sour sodium, 6g sodium hydroxides and 17mL distilled water mix under room temperature and mechanical agitation, and stir and be uniformly mixed to raw material, obtain silicon Aluminium glue B.5g Alusils A and 50g Alusil B under room temperature and mechanical agitation is mixed, and stirs and turns after mixing to raw material Enter in autoclave pressure, after sealing at a temperature of 130 DEG C, to stir crystallization under 60rpm rotating speeds 48 hours, take out and be quickly cooled down pressure Kettle.Product is dry at 120 DEG C after washing to neutrality through filtering, washing, and obtains Na beta-molecular sieve products C N β -1, characterization result table Bright, product is the characteristic peak for having beta-molecular sieve, but has a small amount of miscellaneous peak, that is, has a small amount of stray crystal.And measure the opposite crystallization of CN β -1 Degree；CN β -1 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；CN β -1 are through 750 DEG C of water vapour water After heat treatment 2 hours, then the relative crystallinity after hydro-thermal process is measured, specific CN β -1 properties are shown in Table 1.

Ammonium salt exchange and Template removal are carried out according to the method for embodiment 1, H β type molecules are made in Na beta-molecular sieve CN β -1 Sieve products C S β -1, XRD determining CS β -1 relative crystallinities；CS β -1 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure water Relative crystallinity after heat treatment, the results are shown in Table 2.

By 40 grams of CS β -1 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), it is 90 grams small Porous aluminum oxide is put into mixed grind in roller with dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, be rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCCAT-1.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Comparative example 2（With reference to CN1198404A）

16g tetraethylammonium bromides and 1.6g sodium fluorides D are dissolved in 30g deionized waters, are sequentially added under stirring by 1.67g aluminic acids Sodium B is dissolved in 20g deionized waters acquired solution, 53.7g Ludox and 0.72g crystal seeds, continues stirring 60 minutes, is transferred to stainless steel In reaction kettle, crystallization 4 days at 160 DEG C.Then it is filtered, washed, dries to obtain Na beta-molecular sieve products C N β -2, measure CN β's -2 Relative crystallinity；CN β -2 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；CN β -2 are through 750 DEG C After water vapour hydro-thermal process 2 hours, then the relative crystallinity after hydro-thermal process is measured, specific CN β -2 properties are shown in Table 1.

Ammonium salt exchange and Template removal are carried out according to the method for embodiment 1, H β type molecules are made in Na beta-molecular sieve CN β -2 Sieve products C S β -2, XRD determining CS β -2 relative crystallinities；CS β -2 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure water Relative crystallinity after heat treatment, the results are shown in Table 2.

By 40 grams of CS β -2 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), it is 90 grams small Porous aluminum oxide is put into mixed grind in roller with dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, be rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-2.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Comparative example 3

（1）The preparation of amorphous silica-alumina predecessor

Solid aluminum sulfate is configured to a concentration of 80g A1 of 100mL₂O₃/ L aluminum sulfate working solutions（a）.Concentrated ammonia liquor is added in Appropriate distilled water is diluted to about 10wt% weak aqua ammonias（b）.It takes with SiO₂The sodium silicate solution of quality meter 28wt%, then be diluted to A concentration of 150g SiO of 80mL₂/ L sodium metasilicate working solutions（c）.One 5 liters of steel retort is taken, 0.2 is added in retort After rising distilled water and being heated with stirring to 70 DEG C, open simultaneously and have respectively（a）、（b）With（c）The valve of container, control（a）With （c）Flow so that the neutralization reaction time at 40 minutes, and adjust rapidly（b）Flow the pH value of system is made to be maintained at 7~8, And the temperature of control system is at 60 DEG C or so.After the completion of reaction, stop adding in（b）, the silicon-aluminum sol of generation stablizes 20 minutes.It opens The ageing process of initial body system keeps pH value 8.0, and temperature 60 C, aging 30 minutes obtains amorphous silica-alumina predecessor, without fixed Shape sial predecessor is on the basis of the wgt dry basis by total of silica and aluminium oxide, using the content that silica is counted as 60wt%.

（2）The preparation of gel is the same as embodiment 1.

（3）Crystallization measures relative crystallinity with embodiment 1 after obtaining Na beta-molecular sieve products C N β -3；CN β -3 are through 550 DEG C After being roasted 3 hours in air, the relative crystallinity after roasting is measured；CN β -3 after 750 DEG C of water vapour hydro-thermal process 2 hours, then The relative crystallinity after hydro-thermal process is measured, specific CN β -3 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Ammonium salt exchanges and the method for Template removal is with embodiment 1, by Na beta-molecular sieve CN β -3 be made H beta molecular sieve CS β - 3, XRD determining CS β -3 relative crystallinities；CS β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then after measuring hydro-thermal process Relative crystallinity the results are shown in Table 2.

By 40 grams of CS β -3 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), it is 90 grams small Porous aluminum oxide is put into mixed grind in roller with dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, be rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-3.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Comparative example 4

（1）The preparation of amorphous silica-alumina predecessor

Solid aluminum sulfate is configured to a concentration of 80g A1 of 100mL₂O₃/ L aluminum sulfate working solutions（a）.By concentrated ammonia liquor plus Enter appropriate distilled water and be diluted to about 10wt% weak aqua ammonias（b）.It takes with SiO₂The sodium silicate solution of quality meter 28wt%, then be diluted to A concentration of 150g SiO of 80mL₂/ L sodium metasilicate working solutions（c）.One 5 liters of steel retort is taken, 0.2 liter of distillation is added in tank Water and after being heated with stirring to 70 DEG C, opens simultaneously and has respectively（a）With（b）The valve of container, control（a）Flow so that neutralize Reaction time adjusted rapidly at 40 minutes（b）Flow the pH value of system is made to be maintained at 7~8, and the temperature of control system exists 60 DEG C or so.After the completion of reacting aluminum sulfate, stop adding in（b）, stablize after twenty minutes, add in（c）80mL is added in 10 minutes, The ageing process of beginning system, keeping pH value, temperature 60 C, aging 30 minutes obtains amorphous silica-alumina predecessor, nothing 8.0 Amorphous silicon-alumina predecessor is on the basis of the wgt dry basis by total of silica and aluminium oxide, using the content that silica is counted as 60wt%.

（2）The preparation of gel is the same as embodiment 1.

（3）Crystallization measures relative crystallinity with embodiment 1 after obtaining Na beta-molecular sieve products C N β -4；CN β -4 are through 550 DEG C After being roasted 3 hours in air, the relative crystallinity after roasting is measured；CN β -4 after 750 DEG C of water vapour hydro-thermal process 2 hours, then The relative crystallinity after hydro-thermal process is measured, specific CN β -4 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Ammonium salt exchanges and the method for Template removal is with embodiment 1, by Na beta-molecular sieve CN β -4 be made H beta molecular sieve CS β - 4, XRD determining CS β -4 relative crystallinities；CS β -4 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then after measuring hydro-thermal process Relative crystallinity the results are shown in Table 2.

By 40 grams of CS β -4 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), it is 90 grams small Porous aluminum oxide is put into mixed grind in roller with dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, be rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-4.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-4 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Comparative example 5

（1）The preparation of amorphous silica-alumina predecessor is the same as embodiment 1；

（2）The preparation of gel is substantially same as Example 1, and difference is：Amorphous silica-alumina predecessor, sodium metasilicate, four Ethyl ammonium hydroxide and water are according to Al₂O₃： SiO₂： Na₂O：H₂O=1：80 ：1.6 : 240、TEAOH/SiO₂=0.2 total throwing Expect molar ratio.

（3）Crystallization is with embodiment 1, and finally obtained Na beta-molecular sieve CN β -5, measure relative crystallinity；CN β -5 are through 550 DEG C of skies After being roasted 3 hours in gas, the relative crystallinity after roasting is measured；CN β -5 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then survey The relative crystallinity after hydro-thermal process is obtained, specific CN β -5 properties are shown in Table 1.

（4）Ammonium salt exchanges and Template removal

Ammonium salt exchanges and the method for Template removal is with embodiment 1, by Na beta-molecular sieve CN β -5 be made H beta molecular sieve CS β - 5, XRD determining CS β -5 relative crystallinities；CS β -5 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then after measuring hydro-thermal process Relative crystallinity the results are shown in Table 2.

By 40 grams of CS β -5 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 90 grams of macroporous aluminium oxides²/ g), it is 90 grams small Porous aluminum oxide is put into mixed grind in roller with dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, be rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-5.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst CCAT-5 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Table 1

	Feed intake SiO₂/Al₂O₃Molar ratio	Specific surface area, m²/g	Kong Rong, mL/g	SiO₂/Al₂O₃Molar ratio	Relative crystallinity, %	Opposite crystallization reservation degree after hydro-thermal process, %
							Nβ-1	80	659	0.52	72	121	118
Nβ-2	90	675	0.54	80	120	110
							Nβ-3	70	625	0.50	63	126	118
CNβ-1	86	581	0.46	28	102	93
							CNβ-2	43	570	0.44	33	98	78
CNβ-3	80	601	0.48	60	103	94
							CNβ-4	80	590	0.47	54	105	97
CNβ-5	80	603	0.49	63	105	96

Table 2

	Relative crystallinity, %	Opposite crystallization reservation degree after hydro-thermal process, %
			Sβ-1	120	115
Sβ-2	115	108
			Sβ-3	120	115
CSβ-1	94	83
			CSβ-2	80	57
CSβ-3	93	86
			CSβ-4	98	87
CSβ-5	97	88

The physico-chemical property of 3 carrier of table and catalyst

Bearer number	TCAT-1	TCAT-2	TCAT-3	CTCAT-1	CTCAT-2	CTCAT-3	CTCAT-4	CTCAT-5
									Beta-molecular sieve, wt%	10	20	20	20	20	20	20	20
Macroporous aluminium oxide, wt%	70	60	60	60	60	60	60	60
									Adhesive, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
Specific surface area, m²/g	481	477	469	452	440	458	451	553
									Kong Rong, mL/g	0.74	0.73	0.72	0.66	0.67	0.67	0.67	0.68
Catalyst is numbered	CAT-1	CAT-2	CAT-3	CCAT-1	CCAT-2	CCAT-3	CCAT-4	CCAT-5
									WO₃, wt%	22.0	21.9	22.2	22.0	22.1	22.1	22.0	22.1
NiO, wt%	5.9	5.8	6.0	6.0	5.9	6.2	6.1	6.0
									Specific surface area, m²/g	411	406	403	379	373	388	378	393
Kong Rong, mL/g	0.57	0.57	0.56	0.48	0.48	0.50	0.49	0.51

By the invention described above catalyst CAT-1, CAT-2, CAT-3 and comparative example catalyst CCAT-1, CCAT-2, CCAT- 3rd, CCAT-4, CCAT-5 carry out active evaluation test.Evaluation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 800, during liquid Volume space velocity 1.5h^-1, using catalytic diesel oil as feedstock oil, raw material oil nature is shown in Table 4.Catalyst Activating Test the results are shown in Table 5.

4 raw material oil nature of table

Feedstock oil	Iranian VGO
		Density (20 DEG C), g/cm³	0.9080
IBP/10%	150/226
		30%/50%	268/301
70%/90%	325/352
		95%/EBP	370/387
Condensation point, DEG C	7
		S, wt%	0.92
N, wt%	0.1178
		C, wt%	85.91
H, wt%	12.48
		Cetane number	22

5 catalyst activity evaluation result of table

Catalyst is numbered	CAT-1	CAT-2	CAT-3	CCAT-1	CCAT-2	CCAT-3	CCAT-4	CCAT-5
									Feedstock oil	Urge bavin	Urge bavin	Urge bavin	Urge bavin	Urge bavin	Urge bavin	Urge bavin	Urge bavin
Reaction temperature, DEG C	370	368	366	370	371	373	372	372
									Major product property
Naphtha
									Yield, wt%	2.3	2.0	1.8	4.3	4.2	3.8	3.7	3.6
Virtue is latent, wt%	53.2	53.6	54.1	48.6	49.7	50.2	51.0	50.6
									Diesel oil
Yield, wt%	96.5	96.8	97.2	91.4	92.0	93.5	93.8	93.7
									Density（20℃）
T95, DEG C	347	346	345	368	362	357	354	353
									Cetane number	51.8	52.0	52.3	48.5	49.2	50.1	50.9	50.8
Condensation point, DEG C	-23	-24	-25	-6	-9	-12	-14	-13
									Sulphur, μ g/g	3.1	3.2	3.2	6.2	5.9	5.2	4.9	5.0
Liquid is received, wt%	98.8	98.8	99.0	95.7	96.2	97.2	97.5	97.3

Can be seen that by the evaluation result of 5 catalyst of table, carrier prepared catalyst of the present invention under identical process conditions, Diesel yield and product quality are superior to reference catalyst.

Claims

1. a kind of preparation method of diesel oil hydrogenation modification catalyst carrier, including：By beta-molecular sieve, macroporous aluminium oxide and adhesive Through dry and roasting, carrier is made in mixing, molding；On the basis of the weight of carrier, carrier composition includes：The content of beta-molecular sieve For 5~30wt%, the content of macroporous aluminium oxide is 20~65wt%, and the content of adhesive is 15~50wt%；It is characterized in that：β Molecular sieve is prepared with the following method：

（1）, amorphous silica-alumina predecessor is prepared using acid-base precipitation method, the amorphous silica-alumina predecessor is with silica and oxygen On the basis of the total weight for changing aluminium, silicon is using the content that silica is counted as 40wt%~75wt%；Its preparation process includes acid-base neutralization Plastic, the method that aging, wherein silicon are introduced into reaction system is in aluminum contained compound and precipitating reagent and before plastic and/or plastic mistake Introducing portion silicon-containing compound in journey, remainder silicon-containing compound be in aluminum contained compound and precipitating reagent and after plastic and It is introduced before aging；

（2）, by Al₂O₃：SiO₂：Na₂O：H₂O=1：(62~130)：(0.5~3.0)：(100~500), TEAOH/SiO₂= 0.010 ~ 0.095 total molar ratio, to step under conditions of 0~40 DEG C of quick stirring（1）The amorphous silica-alumina of gained Water, silicon source and template are added in predecessor, and control ph is 9.5 ~ 12.0, stirs evenly, obtains silica-alumina gel, TEA generations Quaternary amine base cations in table template；

（3）, step（2）The silica-alumina gel of gained is through two step dynamic crystallizations, and using filter, Na beta molecular sieves are made in washing；

（4）By step（3）The Na beta molecular sieves of gained carry out ammonium salt and exchange and Template removal processing, obtained beta-molecular sieve.

2. preparation method according to claim 1, it is characterised in that：It is described in aluminum contained compound and precipitating reagent and plastic The mode of introducing portion silicon-containing compound is during preceding and/or plastic：The part silicon-containing compound is closed with described containing calorize Object and/or precipitating reagent are pre-mixed or are individually added by silicon-containing compound in aluminum contained compound and during plastic anti- It answers in system or the combination of the above method.

3. preparation method according to claim 1, it is characterised in that：In step（1）In, in the aluminum contained compound and The silicon-containing compound being introduced into after plastic and before ageing accounts for silicon in amorphous silica-alumina predecessor with titanium dioxide in terms of silica 5wt% ~ 85wt% of silicon meter.

4. according to the preparation method described in any one in claim 1-3, it is characterised in that：The aluminum contained compound is selected from Al₂ (SO₄)₃、AlCl₃、Al(NO₃)₃It is one or more in solution, with A1₂O₃Quality meter, a concentration of the 30 of the aluminum contained compound ~150g A1₂O₃/L；It is molten that precipitating reagent is selected from sodium hydroxide solution, ammonium hydroxide, sodium carbonate liquor, sodium bicarbonate solution, sodium metaaluminate It is one or more in liquid.

5. preparation method according to claim 1, it is characterised in that：The aluminum contained compound is sodium aluminate solution, with A1₂O₃Quality meter, a concentration of 40~100g A1 of the sodium aluminate solution₂O₃/L。

6. according to the preparation method described in any one in claim 1-3, it is characterised in that：The silicon-containing compound is selected from water It is one or more in glass, Ludox and organo-silicon compound, with SiO₂Quality meter, a concentration of the 40 of the silicon-containing compound ~200g SiO₂/L。

7. according to the preparation method described in any one in claim 1-3, it is characterised in that：In step（2）In, the silicon source One or more in White Carbon black, silica gel, Ludox, waterglass, the template is tetraethyl ammonium hydroxide.

8. according to the preparation method described in any one in claim 1-3, it is characterised in that：In step（1）In, the plastic Condition be：Temperature is 20~85 DEG C, and pH value is 7.0~10.0；The condition of the aging is：Temperature is 20~85 DEG C, and pH is 7.0~10.0,0.2~8.0 hour time.

9. according to the preparation method described in any one in claim 1-3, it is characterised in that：In step（2）In, described in generation 0~40 DEG C of the reaction temperature of silica-alumina gel, pH value are 9.5~12.0.

10. according to the preparation method described in any one in claim 1-3, it is characterised in that：In step（3）In, step（2） Specific steps of the silica-alumina gel of gained through two step dynamic crystallizations include：The condition of first step dynamic crystallization is：In stirring condition Lower carry out crystallization, temperature are 50~90 DEG C, and the time is 0.5~18.0 hour；The condition of second step dynamic crystallization is：In stirring bar Crystallization is carried out under part, temperature is 100~200 DEG C, and the time is 40~120 hours.

11. preparation method according to claim 10, it is characterised in that：In step（3）In, the first step dynamic crystallization Condition be：Crystallization is carried out under agitation, and temperature is 60~80 DEG C, and the time is 1~10 hour；The second step dynamic is brilliant The condition of change is：Crystallization is carried out under agitation, and temperature is 120~170 DEG C, and the time is 50~100 hours.

12. preparation method according to claim 1, which is characterized in that step（4）Described in ammonium salt exchange after beta-molecular sieve Middle Na₂O weight contents are less than 0.3%.

13. preparation method according to claim 1, which is characterized in that step（4）Described in Template removal processing use Aerobic high-temperature process, treatment temperature are 400~800 DEG C, and processing time is 5~20 hours.

14. preparation method according to claim 1, it is characterised in that：The Kong Rongwei 0.7 ~ 1.0 of the macroporous aluminium oxide ML/g, 200 ~ 500 m of specific surface area²/g。

15. preparation method according to claim 1, it is characterised in that：Adhesive therefor is small porous aluminum oxide, and used is small 0.3~0.5 mL/g of Kong Rongwei of porous aluminum oxide, specific surface area are 200~400m²/g。

16. preparation method according to claim 1, which is characterized in that the drying of the carrier use and roasting condition are such as Under：It is 3~10 hours dry at a temperature of 80~150 DEG C, it is roasted 3~12 hours at 400~800 DEG C.