CN106140251B - Carrier of hydrocracking catalyst and preparation method thereof - Google Patents
Carrier of hydrocracking catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106140251B CN106140251B CN201510136320.4A CN201510136320A CN106140251B CN 106140251 B CN106140251 B CN 106140251B CN 201510136320 A CN201510136320 A CN 201510136320A CN 106140251 B CN106140251 B CN 106140251B
- Authority
- CN
- China
- Prior art keywords
- preparation
- beta
- silica
- molecular sieve
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of carrier of hydrocracking catalyst and preparation method thereof.The carrier includes beta-molecular sieve, amorphous silica-alumina and adhesive, and wherein beta-molecular sieve property is as follows：SiO2/Al2O3Molar ratio is 60~100, and specific surface area is 505~850m20.35~0.60mL/g of/g, Kong Rongwei, relative crystallinity are 100%~148%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 95% or more.Acidic components of the present invention using the good beta-molecular sieve of high-crystallinity, high silica alumina ratio, stability as carrier, match with amorphous silica-alumina, and the carrier of gained is made hydrocracking catalyst, and active height, middle oil chooses, the feature that product property is good.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, more specifically a kind of to contain beta molecule
Carrier of hydrocracking catalyst of sieve and preparation method thereof.
Background technology
Transportation fuel of the diesel oil as compression ignition engine, being played during the production and living of modernization can not replace
The effect in generation can be used as the delivery vehicles such as automobile, tank, aircraft, tractor, rolling stock or other machinery
Automotive fuel, it is also possible to generate electricity, warm oneself.Industry and the difference of environment, matter of the user for diesel product are used according to it
Amount requires also have prodigious difference, and with the continuous improvement of economic development and environmental consciousness, the requirement for diesel quality is got over
Come higher.For in extremely frigid zones, people are not concerned only with the property such as density, boiling range, impurity content and Cetane number of diesel product
Energy index, also payes attention to the low temperature fluidity of diesel product, and only low freezing point diesel fuel product can be met the actual needs.
The production of clear gusoline depends on the development and application of hydrogen addition technology.In crude oil secondary operation technology, it is hydrocracked
Technology has that adaptability to raw material strong, production operation and products scheme flexibility are big, purpose product selectivity is high and production process ring
The features such as border is friendly, it has also become one of modern times oil refining and the most important heavy oil deep processing technique of petro chemical industry, in the world
Various countries obtain increasingly extensive application.Diesel product is hydrocracked with impurity contents such as saturated hydrocarbon component content height, sulphur nitrogen
Extremely low, the features such as density is small, Cetane number is high is exactly the blend component of very good cleaning diesel oil.
The core of hydrocracking technology is hydrocracking catalyst, progress the carrying dependent on levels of catalysts of technology
Height, main acidic components of the molecular sieve as hydrocracking catalyst, plays the activity, selectivity and product quality of catalyst
Conclusive effect.Current industrialized molecular sieve type hydrocracking catalyst contains Y usually based on Modified Zeolite Y
The hydrocracking catalyst of type molecular sieve is active good, and open-loop performance is high, to the heavy constituent selective splitting rich in cyclic hydrocarbon
The advantages that performance is high, but place the deficiencies of there is midbarrel oil yield is not high, and diesel product low temperature flow is poor, especially
In diesel oil deep drawing or for back-end crop oil come when producing wide cut diesel fuel, this problem is not more prominent.Relative to Y type molecular sieves, β divides
Sub- sifter device has three-dimensional twelve-ring pore structure, but without the supercage structure as Y type molecular sieve, is mainly characterized by two 4
Double 6 membered ring unit bug hole structures of membered ring and four 5 membered rings, for main channel diameter in 0.56 ~ 0.75nm, the duct of beta-molecular sieve is special
Point has good effect so that it is broken chain hydrocarbon-selective in cracking reaction, and has very strong isomery performance, makees
It can be used for Low Freezing Point intermediate oil for cracking component, be industrially widely used.
US4847055 discloses a kind of method of improved synthesis beta-molecular sieve, wherein a kind of special silicon source is used, with
TEABr is template, and beta-molecular sieve is prepared under the conditions of existing for crystal seed.The silicon source is by soluble silicon solution in certain condition
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, beta-molecular sieve to close
At cost largely be derived from template, typically constitute from 70% or so.Reduce template dosage, to reduce beta-molecular sieve synthesis at
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 makes its crystallinity decline, 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 be added 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 is then 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 through suction filtration, wash 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 sial 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 of synthesis 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 be added composite mould plate agent and
Crystal seed, and silica alumina ratio is more than after 30, and 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 passes through the catalyst that modified obtained this beta-molecular sieve is prepared as cracking component, midbarrel
The selectivity of oil is not high.
Invention content
Aiming at the deficiencies in the prior art, the present invention provides a kind of good hydrocracking catalyst loads of catalytic performance
Body and preparation method thereof.The carrier of hydrocracking catalyst is divided using the β of a kind of high silica alumina ratio, high-crystallinity, bigger serface
Son sieve is used as acidic components, catalyst prepared by carrier of the present invention to have higher activity and middle distillates oil selectivity, and product property is good,
Condensation point of diesel oil is low.
Carrier of hydrocracking catalyst of the present invention, including beta-molecular sieve, amorphous silica-alumina and adhesive, wherein the beta molecule
The property of sieve is as follows：SiO2/Al2O3Molar ratio is 60~100, and specific surface area is 505~850m2/ g, Kong Rongwei 0.35~
0.60mL/g, relative crystallinity are 100%~148%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process be
95% or more.
The carrier of hydrocracking catalyst of the present invention, on the basis of the weight of carrier, the content of beta-molecular sieve be 2wt%~
The content of 40wt%, amorphous silica-alumina are 20wt%~85wt%, and the content of adhesive is 13wt%~40wt%.
In carrier of hydrocracking catalyst of the present invention, the beta-molecular sieve is Hydrogen beta-molecular sieve.
In carrier of hydrocracking catalyst of the present invention, the beta-molecular sieve property is preferably as follows：SiO2/Al2O3Molar ratio
It is 65~100, specific surface area is 550~800m2/ g, hole hold 0.40~0.60mL/g, and relative crystallinity is 110%~140%；
Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 95%~130%.
Preferably, the beta-molecular sieve property is as follows：SiO2/Al2O3Molar ratio be 65~100, specific surface area be 600~
750 m2/ g, hole hold 0.45~0.55mL/g, and relative crystallinity is 115%~140%；The beta-molecular sieve is through water vapour hydro-thermal
Treated, and relative crystallinity is 108%~130%.
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 carrier of hydrocracking catalyst of the present invention, SiO in the amorphous silica-alumina2Weight content be 20%~
The property of 60%, preferably 25%~40%, amorphous silica-alumina is as follows：0.6~1.1mL/g of Kong Rongwei, preferably 0.8~1.0
ML/g, specific surface area are 300~500 m2/ g, preferably 350~500 m2/g。
In carrier of hydrocracking catalyst of the present invention, adhesive commonly used in the art may be used in the adhesive,
It is preferred that using small porous aluminum oxide.
The property of carrier of hydrocracking catalyst of the present invention is as follows：Specific surface area is 400~600 m2/ g, Kong Rong are 0.5
~1.0 mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention, including：By beta-molecular sieve, amorphous silica-alumina and adhesive
Carrier is made through dry and roasting in mixing, molding.
Beta-molecular sieve described in carrier of hydrocracking catalyst of the present invention, including following preparation process：
（1）, using preparing amorphous silicon alumnium using carbonization predecessor, the amorphous silica-alumina predecessor is with silica and oxygen
On the basis of the total weight for changing aluminium, content of the silicon in terms of silica is 40wt%~75wt%, preferably 55wt%~70wt%；It is made
Include for process：
Sodium aluminate solution and silicon-containing compound solution are prepared respectively；Sodium aluminate solution and part silicon-containing compound solution are mixed
It closes, then passes to CO2Gas, as the CO being passed through2 When gas flow accounts for the 60% ~ 100% of total intake, preferably 85% ~ 100%, add
Enter the remainder silicon-containing compound solution；
（2）, in step（1）Said mixture stablize in ventilated environment 10 ~ 30 minutes；
（3）, press Al2O3： SiO2： Na2O：H2O=1：(62~110)：(0.5~3.0)：(100~500), TEAOH/
SiO2=0.010 ~ 0.095 total molar ratio, preferably SiO2/Al2O3For 70 ~ 110, TEAOH/SiO2=0.020 ~ 0.080,
To step（2）Water, silicon source and template are added in the amorphous silica-alumina predecessor of gained, stirs evenly, obtains silica-alumina gel,
TEA represents the quaternary amine base cations in template；
（4）, step（3）The silica-alumina gel of gained is through two step dynamic crystallizations, and using filter, Na β type molecules are made in washing
Sieve；
（5）, the Na beta molecular sieves carry out ammonium salt exchange and Template removal processing, beta-molecular sieve is made.
Preferably, in step（1）In, the remainder silicon-containing compound solution accounts for addition silicide-comprising in terms of silica
Polymer solution total amount 5wt% ~ 85wt% in terms of silica, preferably 30wt% ~ 70wt%.
Preferably, in step（1）In, the reaction temperature of the plastic is 10~40 DEG C, preferably 15~35 DEG C, control at
PH values after glue are 8~11.
Preferably, in step（1）In, the silicon-containing compound solution is waterglass and/or sodium silicate solution.
Preferably, in step（1）In, with A12O3Quality meter, a concentration of 15~55g Al of the sodium aluminate solution2O3/
L, with SiO2Quality meter, a concentration of 50~150 gSiO of the silicon-containing compound solution2/ L, the CO2Gas it is a concentration of
30v%~60v%。
Preferably, in step（3）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.
Preferably, in step（3）In, the silicon source is one kind or more in White Carbon black, silica gel, Ludox and waterglass
Kind, the template is tetraethyl ammonium hydroxide.
Preferably, in step（4）In, step（3）Specific steps of the silica-alumina gel of gained through two step dynamic crystallizations include：
The condition of first step dynamic crystallization is：Crystallization is carried out under agitation, and temperature is 50~90 DEG C, and the time is 0.5~18.0 small
When；The condition of second step dynamic crystallization is：Crystallization is carried out under agitation, and temperature is 100~200 DEG C, and the time is 40~120
Hour.
Preferably, in step（4）In, the condition of the first step dynamic crystallization is：Crystallization is carried out under agitation, temperature
Degree is 60~80 DEG C, and the time is 1~10 hour；The condition of the second step dynamic crystallization is：Crystallization is carried out under agitation,
Temperature is 120~170 DEG C, and the time is 50~100 hours.
Preferably, step（5）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（5）In, the Template removal processing use aerobic high-temperature process, treatment temperature be 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 be 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, 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 preparation method of Na beta molecular sieves of the present invention first will partly contain in the preparation process of amorphous silica-alumina predecessor
Silicon compound solution is mixed with sodium aluminate solution, then passes to CO2Gas combines to form stable colloidal state and sial
Structure.Since this colloid surface has many hydroxyl structures, can well with the remainder silicon-containing compound that is added below
In conjunction with to make amorphous silica-alumina predecessor that there is more stable structure.Later, by amorphous silica-alumina predecessor, template
It is mixed and made into silica-alumina gel with another part silicon source etc., more nucleus can be formed in synthetic system in this way, be uniformly dispersed
In synthetic system, there is good crystallization guiding role, then through two step dynamic crystallizations, be easy to form complete skeleton structure,
The high Na beta molecular sieves of crystallinity.The method of the present invention can not only reduce the usage amount of organic formwork agent, can also synthesize height
The Na beta molecular sieves of crystallinity, high silica alumina ratio, and there is better thermal stability and hydrothermal stability.
By the present invention Na beta molecular sieves by simple ammonium salt exchange and Template removal, can obtain high silica alumina ratio,
The good beta-molecular sieve of high-crystallinity, stability no longer needs to carry out the dual-spectrum process such as dealuminzation or dealumination complement silicon, and the β of the present invention
Molecular sieve purity is high, without stray crystal.
The present invention beta-molecular sieve, to the long side chain n- alkyl of long chain alkane and aromatic hydrocarbons, cycloalkane have suitable splitting action and
Good isomerization while so that hydrogenation catalyst prepared therefrom is shown with excellent activity, has higher middle oil
Selectivity, while low freezing point diesel fuel product can also be obtained.
Specific implementation mode
In order to better illustrate the present invention, it is 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, the relative crystallinity and purity of molecular sieve use x-ray diffraction method, silica alumina ratio to use chemical method.In the present invention,
Wt% is mass fraction, and v% is volume fraction.
Embodiment 1
（1）The preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solutions, take containing SiO2The sodium silicate solution of 28wt%, then be diluted to
A concentration of 120g SiO2/ L sodium metasilicate working solutions.It takes 200mL sodium aluminate working solutions to be placed in plastic cans, is then added
50mL sodium metasilicate working solutions, 18 DEG C of controlling reaction temperature, are passed through the CO of a concentration of 50v%2Gas, when pH value reaches 10.2
Stop leading to CO2, 50mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, and amorphous silica-alumina predecessor, nothing are obtained
For amorphous silicon-alumina predecessor on the basis of silica and aluminium oxide total weight, the content in terms of silica is 60wt%.
（2）The preparation of gel
By Al2O3： SiO2： Na2O：H2O=1：80 ：1.5 : 240、TEAOH/SiO2=0.070 total molar ratio,
To step（1）Water, sodium silicate solution and tetraethyl ammonium hydroxide, and control ph are added in the amorphous silica-alumina predecessor of gained
It is 11,25 DEG C of reaction temperature, uniform stirring 30 minutes obtains silica-alumina gel.
（3）Crystallization
By step（2）Obtained gel pours into stainless steel cauldron, crystallization is stirred at 80 DEG C 5 hours, then heats up
To 150 DEG C, then stirring crystallization 30 hours is filtered, washed, dry at 120 DEG C after washing to neutrality, obtains the production of Na beta-molecular sieves
β -1 product N, 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, measures the relative crystallinity after hydro-thermal process, specific N β -1 properties are shown in Table 1.
（4）Ammonium salt exchanges and Template removal
Suitable water purification is added in Na beta-molecular sieve N β -1, and adds a certain amount of ammonium nitrate, makes 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 as 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.It takes the beta-molecular sieve after drying to carry out abjection template processing, uses
Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and β -1 beta-molecular sieve S, 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
Compound concentration is 50gAl2O3/ L sodium aluminate working solutions, take containing SiO2The sodium silicate solution of 28wt%, then be diluted to
A concentration of 100g SiO2/ L sodium metasilicate working solutions.It takes 200mL sodium aluminate working solutions to be placed in plastic cans, is then added
60mL sodium metasilicate working solutions, 20 DEG C of controlling reaction temperature, are passed through the CO of a concentration of 50v%2Gas, when pH value reaches 10.0
Stop leading to CO2, 40mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, and amorphous silica-alumina predecessor, nothing are obtained
For amorphous silicon-alumina predecessor on the basis of silica and aluminium oxide total weight, the content in terms of silica is 50wt%.
（2）The preparation of gel
By Al2O3： SiO2： Na2O：H2O=1：90 ：1.7 : 260、TEAOH/SiO2=0.060 total molar ratio,
To step（1）Water, sodium silicate solution and tetraethyl ammonium hydroxide, and control ph are added in the amorphous silica-alumina predecessor of gained
It is 11,25 DEG C of reaction temperature, uniform stirring 30 minutes obtains silica-alumina gel.
（3）Crystallization
By step（2）Obtained gel pours into stainless steel cauldron, crystallization is stirred at 90 DEG C 5 hours, then heats up
To 160 DEG C, then stirring crystallization 30 hours is filtered, washed, dry at 120 DEG C after washing to neutrality, obtains the production of Na beta-molecular sieves
β -2 product N, 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, measure the relative crystallinity after hydro-thermal process, specific N β -2 properties are shown in Table 1.
（4）Ammonium salt exchanges and Template removal
Suitable water purification is added in Na beta-molecular sieve N β -2, and adds a certain amount of ammonium nitrate, makes 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 as 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.It takes the beta-molecular sieve after drying to carry out abjection template processing, uses
Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and β -2 beta-molecular sieve S, 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
Compound concentration is 50gAl2O3/ L sodium aluminate working solutions, take containing SiO2The sodium silicate solution of 28wt%, then be diluted to
A concentration of 100g SiO2/ L sodium metasilicate working solutions.It takes 160mL sodium aluminate working solutions to be placed in plastic cans, is then added
45mL sodium metasilicate working solutions, 20 DEG C of controlling reaction temperature, are passed through the CO of a concentration of 50v%2Gas, when pH value reaches 10.0
Stop leading to CO2, 35mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, and amorphous silica-alumina predecessor, nothing are obtained
For amorphous silicon-alumina predecessor on the basis of silica and aluminium oxide total weight, the content in terms of silica is 50wt%.
（2）With embodiment 1, difference is for the preparation of gel：According to Al2O3：SiO2：Na2O：H2O=1：70 ：1.4 :
250、TEAOH/SiO2=0.062 total molar ratio mixes each material.
（3）Crystallization obtains β -3 molecular sieve N, measures relative crystallinity with embodiment 1；N β -3 in 550 DEG C of air through roasting 3
After hour, the relative crystallinity after roasting is measured；N β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, after measuring hydro-thermal process
Relative crystallinity, 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 beta-molecular sieve S β -3, XRD is made in Na beta-molecular sieve N β -3
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 10 grams of S β -1 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 125.5 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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-1, property is shown in Table 3.
Embodiment 5
By 30 grams of S β -2 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica weight
Measure content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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-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 30 grams of S β -3 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica weight
Measure content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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-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 to raw material be uniformly mixed：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 to raw material and be uniformly mixed, and obtain silicon
Aluminium glue B.5g Alusils A and 50g Alusil B is mixed under room temperature and mechanical agitation, 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, takes out and be quickly cooled down pressure
Kettle.Product is dry at 120 DEG C after washing to neutrality through filtering, washing, and obtains β -1 Na beta-molecular sieve products C N, measures opposite knot
Brilliant 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 vapours
After hydro-thermal process 2 hours, the relative crystallinity after hydro-thermal process is measured, specific CN β -1 properties are shown in Table 1.The characterization result of CN β -1
Show that product is the characteristic peak for having beta-molecular sieve, but have a small amount of miscellaneous peak, that is, has a small amount of stray crystal.
Ammonium salt exchange and Template removal are carried out according to the method for embodiment 1, beta-molecular sieve production is made in Na beta-molecular sieve CN β -1
β -1 product CS, 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 at hydro-thermal
Relative crystallinity after reason, the results are shown in Table 2.
By 30 grams of CS β -1 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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 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 β -2 Na beta-molecular sieve products C N, measure opposite crystallization
Degree.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 of water vapour water
After heat treatment 2 hours, 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, beta-molecular sieve production is made in Na beta-molecular sieve CN β -2
β -2 product CS, 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 at hydro-thermal
Relative crystallinity after reason, the results are shown in Table 2.
By 30 grams of CS β -2 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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 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
Compound concentration is 40gAl2O3/ L sodium aluminate working solutions, take containing SiO2The sodium silicate solution of 28wt%, then be diluted to
A concentration of 120g SiO2/ L sodium metasilicate working solutions.It takes 200mL sodium aluminate working solutions to be placed in plastic cans, is then added
100mL sodium metasilicate working solutions, 18 DEG C of controlling reaction temperature, are passed through the CO of a concentration of 50v%2Gas, when pH value reaches 10.2
Stop leading to CO2, then divulge information and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is with silica
On the basis of aluminium oxide total weight, the content in terms of silica is 60wt%.
（2）The preparation of gel is the same as embodiment 1；
（3）Crystallization obtains β -3 molecular sieve CN, measures relative crystallinity with embodiment 1.CN β -3 in 550 DEG C of air through roasting
After burning 3 hours, the relative crystallinity after roasting is measured；CN β -3 are measured after 750 DEG C of water vapour hydro-thermal process 2 hours at hydro-thermal
Relative crystallinity after reason, 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, and beta-molecular sieve products C S β-are made in Na beta-molecular sieve CN β -3
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 30 grams of CS β -1 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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 TCCAT-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
Compound concentration is 40gAl2O3/ L sodium aluminate working solutions, take containing SiO2The sodium silicate solution of 28wt%, then be diluted to
A concentration of 120g SiO2/ L sodium metasilicate working solutions.200mL sodium aluminate working solutions are taken to be placed in plastic cans, control reaction temperature
18 DEG C of degree, is passed through the CO of a concentration of 50v%2Gas stops leading to CO when pH value reaches 10.22, add the work of 100mL sodium metasilicate
Solution, then ventilation are stablized 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is with silica and oxidation
On the basis of aluminium total weight, the content in terms of silica is 60wt%.
（2）The preparation of gel is the same as embodiment 1；
（3）Crystallization obtains β -4 molecular sieve CN, measures relative crystallinity with embodiment 1.CN β -4 in 550 DEG C of air through roasting
After burning 3 hours, the relative crystallinity after roasting is measured；CN β -4 are measured after 750 DEG C of water vapour hydro-thermal process 2 hours at hydro-thermal
Relative crystallinity after reason, 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, is made Na beta-molecular sieve CN β -4 to obtain beta-molecular sieve product
β -4 CS, XRD determining CS β -4 relative crystallinities；CS β -4 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure hydro-thermal process
Relative crystallinity afterwards, the results are shown in Table 2.
By 30 grams of CS β -4 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25) it is put into mixed grind in roller, 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 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=1：80：1.5：240、TEAOH/SiO2=0.2 always feeds intake mole
Than；
（3）Crystallization obtains β -5 molecular sieve CN, measures relative crystallinity with embodiment 1.CN β -5 in 550 DEG C of air through roasting
After burning 3 hours, the relative crystallinity after roasting is measured；CN β -5 are measured after 750 DEG C of water vapour hydro-thermal process 2 hours at hydro-thermal
Relative crystallinity after reason, 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, and beta-molecular sieve products C S β-are made in Na beta-molecular sieve CN β -5
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 30 grams of CS β -4 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of amorphous silica-aluminas2/ g, silica
Weight content be 30%), 80 grams of small porous aluminum oxides of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is
0.25）It is put into mixed grind in roller, 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 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 Product, m2/g | Kong Rong, mL/g | SiO2/Al2O3 Molar ratio | Opposite crystallization Degree, % | It is opposite after roasting Crystallinity *, % | Opposite knot after hydro-thermal process Brilliant reservation degree, % | |
| Nβ-1 | 80 | 665 | 0.53 | 74 | 124 | 120 | 112 |
| Nβ-2 | 90 | 680 | 0.55 | 83 | 122 | 112 | 107 |
| Nβ-3 | 70 | 630 | 0.52 | 65 | 128 | 119 | 115 |
| CNβ-1 | 86 | 581 | 0.46 | 28 | 102 | 93 | 80 |
| CNβ-2 | 43 | 570 | 0.44 | 33 | 98 | 78 | 56 |
| CNβ-3 | 80 | 610 | 0.47 | 52 | 102 | 93 | 82 |
| CNβ-4 | 80 | 605 | 0.48 | 55 | 106 | 98 | 87 |
| CNβ-5 | 80 | 603 | 0.49 | 65 | 104 | 96 | 84 |
Note：* in the present invention, condition of the Na beta molecular sieves through air roasting is as follows：Through being roasted 3 hours in 550 DEG C of air.
Table 2
| Specific surface area, m2/g | Kong Rong, mL/g | SiO2/Al2O3Molar ratio | Relative crystallinity, % | Opposite crystal retention after hydro-thermal process, % | |
| Sβ-1 | 670 | 0.54 | 74 | 122 | 116 |
| Sβ-2 | 685 | 0.56 | 83 | 117 | 109 |
| Sβ-3 | 635 | 0.53 | 65 | 122 | 116 |
| CSβ-1 | 578 | 0.46 | 28 | 95 | 83 |
| CSβ-2 | 567 | 0.44 | 33 | 80 | 57 |
| CSβ-3 | 611 | 0.48 | 52 | 94 | 84 |
| CSβ-4 | 606 | 0.49 | 55 | 99 | 88 |
| CSβ-5 | 605 | 0.50 | 65 | 97 | 86 |
The physico-chemical property of table 3 carrier and catalyst
| Bearer number | TCAT-1 | TCAT-2 | TCAT-3 | CTCAT-1 | CTCAT-2 | CTCAT-3 | CTCAT-4 | CTCAT-5 |
| Beta-molecular sieve, wt% | 9 | 22 | 22 | 22 | 22 | 22 | 22 | 22 |
| Amorphous silica-alumina, wt% | 71 | 58 | 58 | 58 | 58 | 58 | 58 | 58 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 491 | 477 | 472 | 445 | 438 | 455 | 450 | 453 |
| Kong Rong, mL/g | 0.66 | 0.65 | 0.64 | 0.61 | 0.60 | 0.63 | 0.62 | 0.62 |
| Catalyst is numbered | CAT-2 | CAT-3 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 | |
| WO3, wt% | 21.9 | 22.2 | 22.0 | 22.1 | 22.1 | 22.0 | 22.1 | |
| NiO, wt% | 5.8 | 6.0 | 6.0 | 5.9 | 6.2 | 6.1 | 6.0 | |
| Specific surface area, m2/g | 405 | 402 | 380 | 375 | 389 | 385 | 386 | |
| Kong Rong, mL/g | 0.57 | 0.56 | 0.50 | 0.49 | 0.51 | 0.50 | 0.52 |
By aforementioned present invention catalyst CAT-2, CAT-3 and comparative example catalyst CCAT-1, CCAT-2, CCAT-3, CCAT-
4, CCAT-5 carries out active evaluation test.Experiment carries out on 200mL small hydrogenation devices, using one-stage serial technique institute
It is shown in Table 4 with raw material oil nature.Operating condition is as follows：Hydrogen partial pressure 14.7MPa, hydrogen to oil volume ratio 1500：1, volume space velocity when liquid
1.5h- 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 | 0.9082 |
| Boiling range, DEG C | 308~560 |
| Condensation point, DEG C | 30 |
| Acid value, mgKOH/g | 0.53 |
| Carbon residue, wt% | 0.2 |
| S, wt% | 2.11 |
| N, wt% | 0.1475 |
| C, wt% | 84.93 |
| H, wt% | 12.52 |
| Aromatic hydrocarbons, wt% | 39.2 |
| BMCI values | 47.5 |
| Refractive power/nD 70 | 1.48570 |
5 catalyst activity evaluation result of table
| Catalyst is numbered | CAT-2 | CAT-3 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 |
| Reaction temperature, DEG C | 373 | 375 | 374 | 376 | 377 | 378 | 377 |
| <370 DEG C of conversion ratios, wt% | 65.0 | 65.1 | 65.0 | 64.8 | 64.9 | 64.5 | 65.1 |
| Middle distillates oil selectivity, %（132~370 DEG C） | 88.5 | 87.9 | 81.6 | 82.5 | 83.5 | 84.1 | 85.1 |
| Major product property | |||||||
| Jet fuel（132~282℃） | |||||||
| Freezing point, DEG C | <-60 | <-60 | -52 | -55 | -58 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 2.9 | 3.1 | 7.2 | 7.5 | 6.0 | 5.2 | 4.9 |
| Smoke point, mm | 28 | 27 | 21 | 21 | 23 | 23 | 24 |
| Diesel oil（282~370℃） | |||||||
| Cetane number | 64 | 65 | 54 | 56 | 57 | 60 | 59 |
| Condensation point, DEG C | -21 | -20 | -8 | -6 | -12 | -9 | -14 |
It can be seen that by the evaluation result of 5 catalyst of table, catalyst of the present invention has good on the basis of greater activity
Selectivity, product property are good.
Claims (28)
1. a kind of carrier of hydrocracking catalyst, composition includes beta-molecular sieve, amorphous silica-alumina and adhesive, wherein beta-molecular sieve
Property is as follows：SiO2/Al2O3Molar ratio is 60~100, and specific surface area is 505~850m20.35~0.60mL/ of/g, Kong Rongwei
G, relative crystallinity are 115%~140%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process be 108%~
130% or more.
2. carrier according to claim 1, it is characterised in that：The beta-molecular sieve property is as follows：SiO2/Al2O3Mole
Than being 65~100, specific surface area is 550~800m2/ g, hole hold 0.40~0.60mL/g.
3. carrier according to claim 1, it is characterised in that：The beta-molecular sieve property is as follows：SiO2/Al2O3Mole
Than being 65~100, specific surface area is 600~750 m2/ g, hole hold 0.45~0.55mL/g.
4. carrier according to claim 1,2 or 3, it is characterised in that：The beta-molecular sieve is through water vapour hydro-thermal process
Condition is as follows：Through 750 DEG C of water vapour hydro-thermal process 2 hours.
5. carrier according to claim 1, it is characterised in that：SiO in the amorphous silica-alumina2Weight content be
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。
6. carrier according to claim 1, it is characterised in that：SiO in the amorphous silica-alumina2Weight content be
25%~40%, 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。
7. carrier according to claim 1, it is characterised in that：In the carrier of hydrocracking catalyst, with carrier
On the basis of weight, the content of beta-molecular sieve is 2wt%~40wt%, and the content of amorphous silica-alumina is 20wt%~85wt%, adhesive
Content is 13wt%~40wt%.
8. the preparation method of any carrier of hydrocracking catalyst of claim 1 ~ 7, including：By beta-molecular sieve, amorphous silicon
Carrier is made through dry and roasting in aluminium and adhesive mixing, molding.
9. according to the method described in claim 8, it is characterized in that：The preparation method of the beta-molecular sieve, including：
（1）, using preparing amorphous silicon alumnium using carbonization predecessor, the amorphous silica-alumina predecessor is with silica and aluminium oxide
Total weight on the basis of, content of the silicon in terms of silica is 40wt%~75wt%；Its preparation process includes：
Sodium aluminate solution and silicon-containing compound solution are prepared respectively；Sodium aluminate solution is mixed with part silicon-containing compound solution,
Then pass to CO2Gas, as the CO being passed through2When gas flow accounts for the 60% ~ 100% of total intake, remainder silicon-containing compound is added
Solution；
（2）, in step（1）Said mixture stablize in ventilated environment 10 ~ 30 minutes；
（3）, press Al2O3：SiO2：Na2O：H2O=1：(62~110)：(0.5~3.0)：(100~500), TEAOH/SiO2=0.010
~ 0.095 total molar ratio, to step（2）Water, silicon source and template are added in the amorphous silica-alumina predecessor of gained, stirs
It mixes uniformly, obtains silica-alumina gel, TEA represents the quaternary amine base cations in template；
（4）, step（3）The silica-alumina gel of gained is through two step dynamic crystallizations, and using filter, Na beta molecular sieves are made in washing；
（5）, the Na beta molecular sieves carry out ammonium salt exchange and Template removal processing, beta-molecular sieve is made.
10. preparation method according to claim 9, which is characterized in that in step（1）In, the amorphous silica-alumina forerunner
For object on the basis of the total weight of silica and aluminium oxide, content of the silicon in terms of silica is 55wt%~70wt%.
11. preparation method according to claim 9, which is characterized in that in step（1）In, as the CO being passed through2Gas flow accounts for
The 85% ~ 100% of total intake, is added remainder silicon-containing compound solution.
12. preparation method according to claim 9, which is characterized in that in step（3）In, 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
（2）Water, silicon source and template are added in the amorphous silica-alumina predecessor of gained.
13. preparation method according to claim 9, which is characterized in that in step（1）In, the remainder silicide-comprising
Polymer solution accounts for 5wt% ~ 85wt% that silicon-containing compound solution total amount is added in terms of silica in terms of silica.
14. preparation method according to claim 9, which is characterized in that in step（1）In, the remainder silicide-comprising
Polymer solution accounts for 30wt% ~ 70wt% that silicon-containing compound solution total amount is added in terms of silica in terms of silica.
15. preparation method according to claim 9, which is characterized in that in step（1）In, controlling reaction temperature be 10~
40 DEG C, it is 8~11 to control the pH value after cemented into bundles.
16. preparation method according to claim 15, which is characterized in that in step（1）In, controlling reaction temperature be 15~
35℃。
17. preparation method according to claim 9, which is characterized in that in step（1）In, the silicon-containing compound solution
For waterglass.
18. preparation method according to claim 17, which is characterized in that in step（1）In, the silicon-containing compound solution
For sodium silicate solution.
19. according to the preparation method described in claim 9,17 or 18, which is characterized in that in step（1）In, with A12O3Quality
Meter, a concentration of 15~55g Al of the sodium aluminate solution2O3/ L, with SiO2Quality meter, the concentration of the silicon-containing compound solution
For 50~150gSiO2/ L, the CO2A concentration of 30v% ~ 60v% of gas.
20. preparation method according to claim 9, it is characterised in that：In step（3）In, generate the silica-alumina gel
0~40 DEG C of reaction temperature, pH value are 9.5~12.0.
21. preparation method according to claim 9, it is characterised in that：In step（3）In, generate the silica-alumina gel
Reaction temperature is 10~30 DEG C, and pH value is 10~11.
22. preparation method according to claim 9, it is characterised in that：In step（3）In, the silicon source is White Carbon black, silicon
One or more in glue, Ludox and waterglass, the template is tetraethyl ammonium hydroxide.
23. preparation method according to claim 9, it is characterised in that：In step（4）In, step（3）The sial of gained is solidifying
Specific steps of the glue through two step dynamic crystallizations include：The condition of first step dynamic crystallization is：Crystallization is carried out under agitation, temperature
Degree is 50~90 DEG C, and the time is 0.5~18.0 hour；The condition of second step dynamic crystallization is：Crystallization is carried out under agitation,
Temperature is 100~200 DEG C, and the time is 40~120 hours.
24. preparation method according to claim 23, it is characterised in that：In step（4）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.
25. preparation method according to claim 9, which is characterized in that through step（5）Na in beta-molecular sieve after ammonium salt exchanges2O
Weight content is less than 0.3%.
26. the preparation method according to claim 9 or 25, which is characterized in that step（5）In, at the Template removal
It is 400~800 DEG C that reason, which uses aerobic high-temperature process, treatment temperature, and processing time is 5~20 hours.
27. according to the preparation method described in claim 9 or 25, which is characterized in that step（5）In, Template removal processing
Using aerobic high-temperature process, treatment temperature is 500~700 DEG C, and processing time is 10~15 hours.
28. preparation method according to claim 8, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510136320.4A CN106140251B (en) | 2015-03-27 | 2015-03-27 | Carrier of hydrocracking catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510136320.4A CN106140251B (en) | 2015-03-27 | 2015-03-27 | Carrier of hydrocracking catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106140251A CN106140251A (en) | 2016-11-23 |
| CN106140251B true CN106140251B (en) | 2018-07-20 |
Family
ID=57340516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510136320.4A Active CN106140251B (en) | 2015-03-27 | 2015-03-27 | Carrier of hydrocracking catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106140251B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1377827A (en) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | Process for preparing beta-zeolite |
| CN1597868A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Hydrogenating catalyst for petroleum wax and its preparation process |
| CN1712498A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst of diesel production at most amount and production thereof |
| CN102909048A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
-
2015
- 2015-03-27 CN CN201510136320.4A patent/CN106140251B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1377827A (en) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | Process for preparing beta-zeolite |
| CN1597868A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Hydrogenating catalyst for petroleum wax and its preparation process |
| CN1712498A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst of diesel production at most amount and production thereof |
| CN102909048A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106140251A (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106140283B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN106140253B (en) | Diesel oil hydrogenation modification catalyst and preparation method thereof | |
| CN106140287B (en) | The preparation method of hydrocracking catalyst | |
| CN106140284B (en) | A kind of carrier of hydrocracking catalyst and preparation method thereof | |
| CN104588078B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN104826652B (en) | The method for preparing hydrocracking catalyst | |
| CN106140282B (en) | Middle oil type hydrocracking catalyst and preparation method thereof | |
| CN104826667B (en) | The method for preparing carrier of hydrocracking catalyst | |
| CN106140281B (en) | A kind of preparation method of middle oil type hydrocracking catalyst | |
| CN106140319B (en) | A kind of preparation method of middle oil type hydrocracking catalyst carrier | |
| CN104588122B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN106140285B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN106140280B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN106140286B (en) | The preparation method of carrier of hydrocracking catalyst | |
| CN106140248B (en) | A kind of preparation method of diesel oil hydrogenation modification catalyst carrier | |
| CN106140250B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN106140279B (en) | A kind of preparation method of diesel oil hydrogenation modification catalyst | |
| CN106140249B (en) | A kind of preparation method of carrier of hydrocracking catalyst | |
| CN106140251B (en) | Carrier of hydrocracking catalyst and preparation method thereof | |
| CN104826653B (en) | A kind of method for preparing hydrocracking catalyst | |
| CN106140317B (en) | Diesel oil hydrogenation modification catalyst carrier and preparation method thereof | |
| CN106140318B (en) | Middle oil type hydrocracking catalyst carrier and preparation method thereof | |
| CN107344112A (en) | A kind of hydrocracking catalyst for producing high-quality catalytic reforming raw material and its preparation method and application | |
| CN107344116B (en) | Hydrocracking catalyst and its preparation method and application | |
| CN105709844B (en) | Carrier of hydrocracking catalyst and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |