CN106140286B - The preparation method of carrier of hydrocracking catalyst - Google Patents
The preparation method of carrier of hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of carrier of hydrocracking catalyst.This method is to prepare beta-molecular sieve, 15 molecular sieves of SBA, amorphous silica-alumina and adhesive kneading and compacting, and 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.Carrier of hydrocracking catalyst of the present invention using the good beta-molecular sieve of high-crystallinity, high silica alumina ratio, stability and 15 molecular sieves of SBA as acidic components, the advantages of hydrocracking catalyst prepared therefrom is active good, middle distillates oil selectivity height, good product quality.
Description
Technical field
The present invention relates to a kind of preparation method of carrier of hydrocracking catalyst, especially with beta-molecular sieve and SBA-
15 molecular sieves are predominant cracking component, and hydrocracking catalyst prepared therefrom adds hydrogen suitable for the high-quality intermediate oil of production
During process.
Background technology
As the development in fuel oil market and environmental regulation are increasingly strict, the environmentally friendly type product requirement quality in various countries
Higher and higher, major petrochemical enterprise increases the investment developed to heavy oil conversion process.And hydrocracking technology is production
The main technique technology of low sulfur content and high-quality intermediate oil.
The core of hydrocracking technology is hydrocracking catalyst, and the progress of technology depends on carrying for levels of catalysts
Height, main acidic components of the molecular sieve as hydrocracking catalyst, plays the activity, selectivity and product quality of catalyst
Conclusive effect.At present, common molecular sieve has the micro porous molecular sieves such as Y type molecular sieve, beta-molecular sieve.Wherein, beta molecule sifter device
There is three-dimensional twelve-ring pore structure, be 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 Low Freezing Point intermediate oil as cracking component, industrially obtain
It is widely applied.
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 beta-molecular sieve needs a large amount of expensive organic formwork agent tetraethyl ammonium hydroxides, and beta-molecular sieve closes
Into cost largely derived from template, typically constitute from 70% or so.Reduce template dosage, so as to reduce beta-molecular sieve synthesis into
This, is always the hot spot of the area research.
Furthermore it uses and preceding the organic formwork agent being blocked in zeolite cavity must be removed as catalyst in beta-molecular sieve
Catalytic activity can just be made it have by falling.The method of conventional removing organic formwork agent is high-temperature roasting, since high-temperature roasting will be broken
The structure of bad beta-molecular sieve declines its crystallinity, and thermal stability and hydrothermal stability are deteriorated, and consumption of template agent is got over
Greatly, 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, the knot of products obtained therefrom
Brilliant degree can be very low, and 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.
A kind of method being hydrocracked using beta-molecular sieve selectivity is described in CN101578353A.Beta-molecular sieve is not
The molar ratio of progress hydro-thermal process or at relatively low temperatures hydro-thermal process, silica and aluminium oxide is less than 30：1 and at least
The SF of 28wt%6Adsorbance, by modified obtained this beta-molecular sieve as cracking component and the catalyst prepared, midbarrel
The selectivity of oil is not high.
Invention content
For shortcoming of the prior art, the present invention provides a kind of good hydrocracking catalyst loads of catalytic performance
The preparation method of body.The carrier of hydrocracking catalyst is using a kind of high silica alumina ratio, high-crystallinity, bigger serface, stability
As acidic components, hydrocracking catalyst prepared therefrom has higher activity for good beta-molecular sieve and SBA-15 molecular sieves
And middle distillates oil selectivity, product property are good.
The preparation method of carrier of hydrocracking catalyst of the present invention, including：By beta-molecular sieve, SBA-15 molecular sieves, amorphous
Through dry and roasting, carrier is made in sial and adhesive mixing, molding；The wherein described beta-molecular sieve, including preparing step as follows
Suddenly：
（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 carbon
It is one or more in 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.
In the preparation method of carrier of hydrocracking catalyst 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, amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process, by text
Offer conventional method preparation.SiO in the amorphous silica-alumina2Weight content for 20%~60%, preferably 25%
~40%, 0.6~1.1mL/g of Kong Rongwei of amorphous silica-alumina, preferably 0.8~1.0 mL/g, specific surface area are 300~500
m2/ g, preferably 350~500 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.
The property of beta-molecular sieve used is as follows in carrier of hydrocracking catalyst 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.
Carrier of hydrocracking catalyst property of the present invention is as follows：Specific surface area is 400~600 m2/ g, Kong Rong be 0.5~
1.0 mL/g。
The carrier of hydrocracking catalyst of the present invention, on the basis of the weight of carrier, beta-molecular sieve and SBA-15 molecular sieves
Total content is 5wt%~40wt%, and the content of amorphous silica-alumina is 20wt%~60wt%, the content of adhesive for 15wt%~
40wt%, wherein beta-molecular sieve account for the 40% ~ 95% of beta-molecular sieve and SBA-15 molecular sieve total weights.
In carrier of hydrocracking catalyst of the present invention, the property of the SBA-15 molecular sieves is as follows：Specific surface area is 700
~1000 m2Prior art preparation may be used in 0.9 ~ 1.5mL/g of/g, Kong Rongwei, the SBA-15 type molecular sieves.
In the preparation method of catalyst carrier of the present invention, beta-molecular sieve and SBA-15 molecular sieves can individually be separately added into
Amorphous silica-alumina and adhesive mixed-forming, after beta-molecular sieve and SBA-15 molecular sieves first can also be mixed, then with amorphous silicon
Aluminium and adhesive mixed-forming.In order to which beta-molecular sieve and SBA-15 molecular sieves in carrier is made to disperse evenly, the association of the two is improved
Tune acts on, it is preferred to use following method adds in：Inorganic acid solution is added in into SBA-15（Such as hydrochloric acid, nitric acid）, wherein adding in
Amount is 10 ~ 20 times of SBA-15 weight, and a concentration of 0.01 ~ 0.05mol/L of inorganic acid solution is stirred 10 ~ 24 hours, Ran Houjia
Enter beta-molecular sieve, continue stirring 1 ~ 5 hour, after filtering, through drying or do not dry, the beta-molecular sieve of gained and SBA-15 mixed molecules
Sieve and amorphous silica-alumina and adhesive mixed-forming.
By hydrocracking catalyst prepared by carrier of the present invention suitable for the hydrocracking process for producing intermediate oil,
Its operating condition is as follows：350~420 DEG C of reaction temperature, preferably 360~390 DEG C, 6~20MPa of hydrogen partial pressure, preferably 9~
15MPa, hydrogen to oil volume ratio 500~2000:1, preferably 800~1500：1,0.5~1.8 h of volume space velocity during liquid-1, preferably
0.8~1.5h-1。
The preparation method of the beta-molecular sieve of the present invention, it is first that part is siliceous in the preparation process of amorphous silica-alumina predecessor
Compound is added in before plastic and/or during plastic in reaction system, forms stable colloidal state and sial integrated structure.
Since this colloid surface has many hydroxyl structures, can be combined well with the remainder silicon-containing compound added in below,
So as to make amorphous silica-alumina predecessor that there is more stable structure.Later, by amorphous silica-alumina predecessor, template with it is another
Part silicon source etc. is mixed and made into silica-alumina gel, can form more nucleus in synthetic system in this way, be evenly dispersed in synthesis
In system, there is good crystallization guiding role, then through two step dynamic crystallizations, easily form complete skeleton structure, crystallinity
High Na beta molecular sieves.The method of the present invention can not only reduce the usage amount of organic formwork agent, can also synthesize highly crystalline
The beta-molecular sieve of degree, high silica alumina ratio, and there is better thermal stability and hydrothermal stability, and the beta-molecular sieve purity of the present invention
Height, without stray crystal.Moreover, the beta-molecular sieve of the present invention is to pass through the exchange of simple ammonium salt and Template removal by Na beta molecular sieves,
It can obtain, without carrying out the dual-spectrum process such as dealuminzation or dealumination complement silicon again.
The carrier of hydrocracking catalyst of the present invention contains beta-molecular sieve and SBA-15 molecular sieves, makes beta-molecular sieve and SBA-15
Molecular sieve cooperates in acid and pore structure, has not only given full play to its respective performance characteristics, but also can make two kinds of molecules
Sieve generates concerted catalysis effect, i.e., beta-molecular sieve has good isomerization, while SBA- to the long side chain on alkane or aromatic hydrocarbons
15 molecular sieves have aromatic hydrocarbons very high selectivity of ring-opening, in this way as the hydrocracking catalyst prepared by the present invention is hydrocracked carrier
The active height of agent, can high-output qulified midbarrel oil product (boat coal+diesel oil), while can and the good hydrogenation tail oil of production.
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, for the relative crystallinity and purity of molecular sieve using x-ray diffraction method, 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 14 grams of S β -1 molecular sieves, 6 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 88.6 grams
(hole holds 0.9mL/g, specific surface area 350m to amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides, with
Dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25) is put into mixed grind in roller, adds water, is rolled into paste, extrusion,
It is 4 hours dry at 110 DEG C to squeeze out item, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT-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 CAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 5
By 19.5 grams of S β -2 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9mL/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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 19.5 grams of S β -3 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9mL/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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.
Embodiment 7
To 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）Middle addition hydrochloric acid solution（It is a concentration of
0.03mol/L, addition 150mL）, it is mixed 20 hours, then adds in 19.5 grams of S β -3 molecular sieves, be mixed 5 hours,
Filtered, after 110 DEG C 4 hours dry, (hole holds 0.9mL/g, specific surface area 350m with 77 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), the small porous aluminum oxide of 75 grams of adhesives, dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then at 550 DEG C
Roasting 4 hours, obtains carrier 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 CAT-4 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 19.5 grams of CS β -1 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9ml/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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 19.5 grams of CS β -2 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9ml/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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 19.5 grams of CS β -3 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、75
(hole holds 0.9mL/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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 19.5 grams of CS β -4 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9mL/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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 19.5 grams of CS β -5 molecular sieves, 9.5 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）、77
(hole holds 0.9mL/g, specific surface area 350m for gram amorphous silica-alumina2/ g, silica weight content for 30%), 75 grams of small porous aluminum oxides,
Mixed grind in roller is put into dust technology (molar ratio of nitric acid and small porous aluminum oxide is 0.25), adds water, is rolled into paste, squeeze
Item, 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.
Comparative example 6
SBA-15 molecular sieves in embodiment 6 are replaced with into S β -3 molecular sieves, other processes obtain carrier with embodiment 6
CTCAT-6。
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-6 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 | TCAT-4 |
| Beta-molecular sieve, wt% | 12.6 | 15.6 | 15.6 | 15.6 |
| SBA-15, wt% | 5.4 | 10.4 | 10.4 | 10.4 |
| Amorphous silica-alumina, wt% | 62 | 54 | 54 | 54 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 498 | 507 | 515 | 520 |
| Kong Rong, mL/g | 0.75 | 0.77 | 0.79 | 0.80 |
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CAT-4 |
| WO3, wt% | 22.0 | 21.8 | 22.1 | 22.0 |
| NiO, wt% | 5.9 | 5.8 | 6.0 | 6.0 |
| Specific surface area, m2/g | 413 | 418 | 430 | 433 |
| Kong Rong, mL/g | 0.56 | 0.57 | 0.58 | 0.59 |
Continued 3
| Bearer number | CTCAT-1 | CTCAT-2 | CTCAT-3 | CTCAT-4 | CTCAT-5 | CTCAT-6 |
| Beta-molecular sieve, wt% | 15.6 | 15.6 | 15.6 | 15.6 | 15.6 | 26 |
| SBA-15, wt% | 10.4 | 10.4 | 10.4 | 10.4 | 10.4 | - |
| Amorphous silica-alumina, wt% | 54 | 54 | 54 | 54 | 54 | 54 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 475 | 482 | 479 | 485 | 487 | 490 |
| Kong Rong, mL/g | 0.69 | 0.70 | 0.71 | 0.72 | 0.71 | 0.73 |
| Catalyst is numbered | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 | CCAT-6 |
| WO3, wt% | 22.1 | 22.2 | 22.3 | 22.1 | 22.2 | 22.1 |
| NiO, wt% | 6.0 | 5.9 | 6.2 | 6.1 | 6.0 | 6.0 |
| Specific surface area, m2/g | 385 | 387 | 388 | 399 | 395 | 400 |
| Kong Rong, mL/g | 0.51 | 0.52 | 0.53 | 0.54 | 0.54 | 0.55 |
By the invention described above catalyst CAT-1, CAT-2, CAT-3, CAT-4 and comparative example catalyst CCAT-1, CCAT-2,
CCAT-3, CCAT-4, CCAT-5, CCAT-6 carry out active evaluation test.Experiment is carried out on 200mL small hydrogenation devices
, it is shown in Table 4 using the raw materials used oil nature of one-stage serial technique.Operating condition is as follows：Hydrogen partial pressure 14.7MPa, hydrogen to oil volume ratio
1200：1, volume space velocity 1.5h during liquid- 1, 5~10 μ g/g of control cracking zone nitrogen content.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 | 0.9078 |
| Boiling range, DEG C | 289~560 |
| Condensation point, DEG C | 28 |
| Acid value, mgKOH/g | 0.53 |
| Carbon residue, wt% | 0.2 |
| S, wt% | 2.02 |
| N, wt% | 0.1450 |
| C, wt% | 84.93 |
| H, wt% | 12.52 |
| Aromatic hydrocarbons, wt% | 38.6 |
| BMCI values | 46.5 |
| Refractive power/nD 70 | 1.47570 |
5 catalyst activity evaluation result of table
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CAT-4 |
| Reaction temperature, DEG C | 372 | 371 | 370 | 369 |
| <370 DEG C of conversion ratios, wt% | 66.1 | 66.3 | 66.4 | 66.6 |
| Middle distillates oil selectivity, %（132~370 DEG C） | 90.3 | 89.5 | 88.6 | 89.4 |
| Major product property | ||||
| Heavy naphtha（82~132℃） | ||||
| Virtue is latent, wt% | 66.2 | 66.7 | 66.3 | 66.6 |
| Jet fuel（132~282℃） | ||||
| Freezing point, DEG C | <-60 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 3.2 | 3.4 | 2.9 | 2.8 |
| Smoke point, mm | 28 | 28 | 28 | 28 |
| Diesel oil（282~370℃） | ||||
| Cetane number | 72 | 71 | 74 | 75 |
| Condensation point, DEG C | -20 | -19 | -22 | -23 |
| Tail oil（>370℃） | ||||
| BMCI | 10.5 | 10.0 | 9.5 | 9.3 |
Continued 5
| Catalyst is numbered | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 | CCAT-6 |
| Reaction temperature, DEG C | 377 | 377 | 381 | 381 | 380 | 369 |
| <370 DEG C of conversion ratios, wt% | 65.4 | 65.4 | 65.5 | 65.7 | 65.6 | 65.9 |
| Middle distillates oil selectivity, %（132~370 DEG C） | 82.5 | 82.8 | 84.6 | 85.2 | 85.5 | 87.7 |
| Major product property | ||||||
| Heavy naphtha（82~132℃） | ||||||
| Virtue is latent, wt% | 59.3 | 59.6 | 61.1 | 61.2 | 61.4 | 65.4 |
| Jet fuel（132~282℃） | ||||||
| Freezing point, DEG C | -52 | -54 | -58 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 6.8 | 7.0 | 5.9 | 5.3 | 4.9 | 3.2 |
| Smoke point, mm | 21 | 22 | 23 | 24 | 24 | 27 |
| Diesel oil（282~370℃） | ||||||
| Cetane number | 55 | 57 | 58 | 59 | 60 | 70 |
| Condensation point, DEG C | -6 | -7 | -8 | -9 | -10 | -20 |
| Tail oil（>370℃） | ||||||
| BMCI | 16.0 | 16.1 | 12.4 | 13.6 | 12.0 | 11.8 |
It can be seen that by the evaluation result of 5 catalyst of table, the catalyst prepared by the present invention is on the basis of greater activity, tool
There is good selectivity, product property is good, and especially condensation point of diesel oil and tail oil BMCI values is relatively low.
Claims (27)
1. a kind of preparation method of carrier of hydrocracking catalyst, including：By beta-molecular sieve, SBA-15 molecular sieves, amorphous silica-alumina
It is mixed with adhesive, molding, through dry and roasting, carrier is made；Wherein beta-molecular sieve preparation method includes：
（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：Step（1）The amorphous silica-alumina predecessor is with two
On the basis of the total weight of silica and aluminium oxide, silicon is using the content that silica is counted as 55wt%~70wt%.
3. preparation method according to claim 1, it is characterised in that：Step（2）By Al2O3：SiO2：Na2O：H2O=1：(70
~110)：(0.5~3.0)：(100~500), TEAOH/SiO2=0.020 ~ 0.080 total molar ratio, to step（1）Institute
Water, silicon source and template are added in the amorphous silica-alumina predecessor obtained.
4. 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.
5. 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.
6. preparation method according to claim 5, 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
30wt% ~ 70wt% of silicon meter.
7. according to the preparation method described in any one in claim 1-6, 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.
8. according to the preparation method described in any one in claim 1-6, it is characterised in that：The aluminum contained compound is inclined
Sodium aluminate solution, with A12O3Quality meter, a concentration of 40~100g A1 of the sodium aluminate solution2O3/ L, the precipitating reagent are
Nitric acid.
9. according to the preparation method described in any one in claim 1-6, it is characterised in that：The silicon-containing compound is selected from
It is one or more in waterglass, Ludox and organo-silicon compound, with SiO2Quality meter, the silicon-containing compound it is a concentration of
40~200g SiO2/L。
10. preparation method according to claim 9, it is characterised in that：The organo-silicon compound are silanol, silicon ether and silicon
It is one or more in oxygen alkane.
11. according to the preparation method described in any one in claim 1-6, it is characterised in that：In step（2）In, the silicon
Source is one or more in White Carbon black, silica gel, Ludox, waterglass, and the template is tetraethyl ammonium hydroxide.
12. according to the preparation method described in any one in claim 1-6, it is characterised in that：In step（1）In, it is described into
The condition of glue is：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.
13. preparation method according to claim 12, it is characterised in that：In step（1）In, the condition of the plastic is：
Temperature is 40~80 DEG C, and pH value is 7.5~9.0；
The condition of the aging is：Temperature is 40~80 DEG C, and pH is 7.0~9.5, and the time is 0.5~5.0 hour.
14. according to the preparation method described in any one in claim 1-6, it is characterised in that：In step（2）In, generation institute
0~40 DEG C of the reaction temperature of silica-alumina gel is stated, pH value is 9.5~12.0.
15. preparation method according to claim 14, it is characterised in that：In step（2）In, generate the silica-alumina gel
Reaction temperature is 10~30 DEG C, and pH value is 10~11.
16. according to the preparation method described in any one in claim 1-6, 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.
17. preparation method according to claim 16, 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.
18. 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%.
19. 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.
20. preparation method according to claim 19, which is characterized in that step（4）Described in Template removal processing adopt
With aerobic high-temperature process, treatment temperature is 500~700 DEG C, and processing time is 10~15 hours.
21. preparation method according to claim 1, it is characterised in that：The property of the SBA-15 molecular sieves is as follows：Than
Surface area is 700~1000 m20.9 ~ 1.5mL/g of/g, Kong Rongwei.
22. preparation method according to claim 1, it is characterised in that：SiO in the amorphous silica-alumina2Weight content
It is 20%~60%, the property of amorphous silica-alumina is as follows：0.6~1.1mL/g of Kong Rongwei, specific surface area are 300~500 m2/g。
23. preparation method according to claim 22, it is characterised in that：SiO in the amorphous silica-alumina2Weight contain
It is 25%~40% to measure, and the property of amorphous silica-alumina is as follows：0.8~1.0 mL/g of Kong Rongwei, specific surface area are 350~500
m2/g。
24. preparation method according to claim 1, it is characterised in that：In the carrier of hydrocracking catalyst, to carry
On the basis of the weight of body, the total content of beta-molecular sieve and SBA-15 molecular sieves is 5wt%~40wt%, and the content of amorphous silica-alumina is
20wt%~60wt%, the content of adhesive is 15wt%~40wt%, and wherein beta-molecular sieve accounts for beta-molecular sieve and SBA-15 molecular sieves are total
The 40% ~ 95% of weight.
25. preparation method according to claim 1, it is characterised in that：When prepared by carrier, beta-molecular sieve and SBA-15 molecules
Sieve is individually separately added into amorphous silica-alumina and adhesive mixed-forming or first mixes beta-molecular sieve and SBA-15 molecular sieves
Afterwards, then with amorphous silica-alumina and adhesive mixed-forming.
26. preparation method according to claim 25, it is characterised in that：When prepared by carrier, β points are added in the following method
Son sieve and SBA-15 molecular sieves：Add in inorganic acid solution into SBA-15, wherein addition is 10 ~ 20 times of SBA-15 weight,
A concentration of 0.01 ~ 0.05mol/L of inorganic acid solution is stirred 10 ~ 24 hours, is then added in beta-molecular sieve, it is small to continue stirring 1 ~ 5
When, it after filtering, through drying or does not dry, beta-molecular sieve and SBA-15 mixed molecular sieves and amorphous silica-alumina and the adhesive of gained
Mixed-forming.
27. 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.
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| CN113083271A (en) * | 2021-04-15 | 2021-07-09 | 天津凯文特科技有限公司 | Novel preparation method of amorphous silica-alumina dry gel with large pore volume and large specific surface area |
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| US5427765A (en) * | 1993-02-02 | 1995-06-27 | Tosoh Corporation | Method of producing zeolite β |
| CN1198404A (en) * | 1997-05-07 | 1998-11-11 | 北京燕山石油化工公司研究院 | Zeolite synthesizing method |
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