CN106140283B - A kind of hydrocracking catalyst and its preparation method - Google Patents
A kind of hydrocracking catalyst and its preparation method Download PDFInfo
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- CN106140283B CN106140283B CN201510136269.7A CN201510136269A CN106140283B CN 106140283 B CN106140283 B CN 106140283B CN 201510136269 A CN201510136269 A CN 201510136269A CN 106140283 B CN106140283 B CN 106140283B
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Abstract
The invention discloses a kind of hydrocracking catalyst and its preparation methods.The catalyst includes carrier and hydrogenation active metal component, and wherein carrier includes that beta-molecular sieve, 15 molecular sieves of SBA, amorphous silica-alumina and adhesive, wherein beta-molecular sieve property are 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 hydrocracking catalyst of the present invention using high-crystallinity, high silica alumina ratio, stability good beta-molecular sieve and SBA 15 as carrier, active height, middle oil chooses, the feature that product property is good.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and its preparation methods, especially with beta-molecular sieve and SBA-15 molecules
Sieve is predominant cracking component, during being suitable for preparing the hydrocracking process for producing high-quality intermediate oil.
Background technology
As the development in fuel oil market and environmental regulation are increasingly strict, various countries' environmentally friendly product requirement quality
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, 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.Currently, 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 membered ring unit bug hole structures of two 4 membered rings and four 5 membered rings, main channel diameter exists
The duct feature of 0.56-0.75nm, beta-molecular sieve make it has the fracture of chain hydrocarbon-selective in cracking reaction to make well
With, and there is very strong isomery performance, it 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 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 of catalytic performance and
Its preparation method.The hydrocracking catalyst is using a kind of high silica alumina ratio, the beta-molecular sieve of high-crystallinity, bigger serface, high stability
With SBA-15 molecular sieves as acidic components, have higher activity and middle distillates oil selectivity, product property good.
The hydrocracking catalyst of the present invention, including carrier and hydrogenation active metal component, wherein carrier includes beta molecule
Sieve, SBA-15 molecular sieves, amorphous silica-alumina and adhesive, wherein the property of the beta-molecular sieve is as follows：SiO2/Al2O3Molar ratio
It is 60~100, specific surface area is 505~850m20.35~0.60mL/g of/g, Kong Rongwei, relative crystallinity be 100%~
148%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 95% or more.
In hydrocracking catalyst of the present invention, the beta-molecular sieve property is preferably as follows：SiO2/Al2O3Molar ratio is 65
~100, specific surface area is 550~800m2/ g, hole hold 0.40~0.60mL/g, and relative crystallinity is 110%~140%；The β
Relative crystallinity of the 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 hydrocracking catalyst of the present invention, the beta-molecular sieve is Hydrogen beta-molecular sieve.
In hydrocracking catalyst of the present invention, the property of the SBA-15 molecular sieves is as follows：Specific surface area be 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 hydrocracking catalyst of the present invention, SiO in the amorphous silica-alumina2Weight content be 20%~60%,
Preferably 25%~40%, the property of amorphous silica-alumina is as follows：0.6~1.1mL/g of Kong Rongwei, preferably 0.8~1.0 mL/g,
Specific surface area is 300~500 m2/ g, preferably 350~500 m2/g。
In hydrocracking catalyst of the present invention, adhesive commonly used in the art may be used in the adhesive, preferably
Using small porous aluminum oxide.
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 be 15wt%~
40wt%, wherein beta-molecular sieve account for the 40% ~ 95% of beta-molecular sieve and SBA-15 molecular sieve total weights.
The hydrocracking catalyst of the present invention, the hydrogenation active metals are the metal of group VIB and/or the VIIIth race,
Vib metals are preferably molybdenum and/or tungsten, and the metal of the VIIIth race is preferably cobalt and/or nickel.On the basis of the weight of catalyst,
Vib metals（In terms of oxide）Content be 10wt%~30wt% and group VIII metal（In terms of oxide）Content be
The content of 4wt%~15wt%, carrier are 60%~86%.
The property of hydrocracking catalyst of the present invention is as follows：Specific surface area is 300~550 m2/ g, Kong Rong are 0.4~1.0
mL/g。
The preparation method of hydrocracking catalyst of the present invention, including the preparation of carrier and bearing for hydrogenation active metal component
It carries, the preparation method of wherein carrier includes：Beta-molecular sieve, SBA-15 molecular sieves, amorphous silica-alumina and adhesive are mixed, molding,
Through dry and roasting, carrier is made.
Beta-molecular sieve described in 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 catalyst of the present invention, 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 be 300~
500 m2/ g, preferably 350~500 m2/g。
In the preparation method of catalyst of the present invention, beta-molecular sieve and SBA-15 molecular sieves can be individually separately added into and without fixed
Shape sial and adhesive mixed-forming, after beta-molecular sieve and SBA-15 molecular sieves first can also be mixed, then with amorphous silica-alumina and
Adhesive mixed-forming.In order to make beta-molecular sieve and SBA-15 molecular sieves in carrier disperse evenly, the coordination for improving the two is made
With, it is preferred to use following method is added：Inorganic acid solution is added into SBA-15（Such as hydrochloric acid, nitric acid）, wherein addition is
10 ~ 20 times of SBA-15 weight, a concentration of 0.01 ~ 0.05mol/L of inorganic acid solution stir 10 ~ 24 hours, β are then added
Molecular sieve continues stirring 1 ~ 5 hour, after filtering, through drying or does not dry, the beta-molecular sieve and SBA-15 mixed molecular sieves of gained
With amorphous silica-alumina and adhesive mixed-forming.
Catalyst of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..It is carried in catalyst
During body formed, shaping assistant can also be added, such as peptization acid, extrusion aid, 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, specifically 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.
In the preparation method of hydrocracking catalyst of the present invention, the load of hydrogenation active metals can be used in the prior art often
The carrying method of rule, preferably infusion process can be saturation leaching, excessive leaching or complexing leaching, i.e., with molten containing required active component
Then liquid impregnated catalyst support, the carrier after dipping are roasted 100 DEG C~150 DEG C dry l~12 hour at 400 DEG C~750 DEG C
It burns 3~12 hours, final catalyst is made.
The hydrocracking catalyst of the present invention is suitable for the hydrocracking process for producing intermediate oil, operating condition
It 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 oil body
Product ratio 500~2000:1, preferably 800~1500：1,0.5~1.8 h of volume space velocity when liquid-1, preferably 0.8~1.5h-1。
Hydrocracking catalyst of the present invention is suitable for treatment of heavy hydrocarbon material, is suitable for the invention heavy charge range very
Width, including vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking follow
One or more in the various hydrocarbon-type oils such as ring oil, raw material is usually the hydro carbons containing 300~600 DEG C of boiling point, and nitrogen content is generally
50~2500mg/g.
The present invention is in the preparation process of beta-molecular sieve, first by part silicon-containing compound before plastic and/or during plastic
It is added in reaction system, forms stable colloidal state and sial integrated structure.Since this colloid surface has many hydroxyls
Structure can be combined with the remainder silicon-containing compound being added below well, to make amorphous silica-alumina predecessor have more
Add stable structure.Later, amorphous silica-alumina predecessor, template and another part silicon source etc. are mixed and made into silica-alumina gel,
More nucleus can be formed in synthetic system in this way, are evenly dispersed in synthetic system, there is good crystallization to be oriented to and make
With, then through two step dynamic crystallizations, be easy to form complete skeleton structure, the high beta molecular sieve of crystallinity.The method of the present invention is not only
The usage amount of organic formwork agent can be reduced, the beta molecular sieve of high-crystallinity, high silica alumina ratio can also be synthesized, and with more
Good thermal stability and hydrothermal stability, and the beta molecular sieve purity of the present invention is high, without stray crystal.Moreover, β points of the present invention
Son sieve can be obtained by the exchange of simple ammonium salt and Template removal by Na beta molecular sieves, no longer needs to carry out dealuminzation or de-
Aluminium mends the dual-spectrum process such as silicon.
The hydrocracking catalyst of the present invention contains beta-molecular sieve and SBA-15 molecular sieves, makes beta-molecular sieve and SBA-15 molecules
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 molecular sieve productions
Raw concerted catalysis effect, i.e. beta-molecular sieve have good isomerization, while SBA-15 points to the long side chain on alkane or aromatic hydrocarbons
Son sieve has aromatic hydrocarbons very high selectivity of ring-opening, is hydrocracked the hydrocracking catalyst prepared by carrier by the present invention in this way and has
Active height, can high-output qulified midbarrel oil product (boat coal+diesel oil), while can and the good hydrogenation tail oil of production.
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 16 grams of S β -1 molecular sieves, 7 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 84.3 grams
(hole holds 0.9mL/g, specific surface area 350m to amorphous silica-alumina2/ g, silica weight content be 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 18 grams of S β -2 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), 75 grams of small porous aluminum oxides, and it is dilute
Nitric acid (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 is squeezed
Shaping 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 18 grams of S β -3 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), 75 grams of small porous aluminum oxides, and it is dilute
Nitric acid (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 is squeezed
Shaping 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 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, 18 grams of S β -3 molecular sieves is then added, be mixed 5 hours, warp
Filtering, after 4 hours dry at 110 DEG C, (hole holds 0.9mL/g, specific surface area 350m with 80 grams of amorphous silica-aluminas2/ g, silica weight
Measure content be 30%), the small porous aluminum oxide of 75 grams of adhesives, dust technology（0.25) molar ratio of wherein nitric acid and small porous aluminum oxide is
It is put into mixed grind in roller, adds water, is rolled into paste, extrusion squeezes out item drying 4 hours, then roasting 4 at 550 DEG C at 110 DEG C
Hour, obtain 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 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 18 grams of CS β -1 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), the oxidation of 75 grams of adhesive apertures
Aluminium, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, adds water, is rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCCAT-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 2（With reference to CN1198404A）
16g tetraethylammonium bromides and 1.6g sodium fluorides D are dissolved in 30g deionized waters, are sequentially added under stirring by 1.67g aluminic acids
Sodium B is dissolved in 20g deionized waters acquired solution, 53.7g Ludox and 0.72g crystal seeds, continues stirring 60 minutes, is transferred to stainless steel
In reaction kettle, crystallization 4 days at 160 DEG C.Then it is filtered, washed, dries to obtain 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 18 grams of CS β -2 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), the oxidation of 75 grams of adhesive apertures
Aluminium, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, adds water, is rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 3
（1）The preparation of amorphous silica-alumina predecessor
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 18 grams of CS β -3 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), the oxidation of 75 grams of adhesive apertures
Aluminium, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, adds water, is rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, 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 18 grams of CS β -4 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), the oxidation of 75 grams of adhesive apertures
Aluminium, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller, adds water, is rolled into paste
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-4 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 5
（1）The preparation of amorphous silica-alumina predecessor is the same as embodiment 1；
（2）The preparation of gel is substantially same as Example 1, and difference is：Amorphous silica-alumina predecessor, sodium metasilicate, four
Ethyl ammonium hydroxide and water are according to Al2O3：SiO2：Na2O：H2O=1：80：1.5：240、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 18 grams of CS β -5 molecular sieves, 9 grams of SBA-15 molecular sieves（Hole holds 1.1mL/g, specific surface area 840m2/g）, 80 grams of nothings
(hole holds 0.9mL/g, specific surface area 350m to amorphous silicon-alumina2/ g, silica weight content be 30%), the oxidation of 75 grams of adhesive apertures
Aluminium, 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
Cream, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains support C TCAT-5.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-5 is obtained, carrier and corresponding catalyst property are shown in Table 3.
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
| It feeds intake SiO2/ Al2O3It rubs That ratio | Specific surface Product, m2/g | Kong Rong, mL/g | SiO2/ Al2O3It rubs That ratio | Opposite knot Brilliant degree, % | It is opposite after roasting Crystallinity *, % | It is opposite after hydro-thermal process Crystal retention, % | |
| 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/Al2O3It rubs That ratio | Opposite crystallization Degree, % | Opposite crystallization after hydro-thermal process is protected Office Copy, % | |
| 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 | TCAT-4 |
| Beta-molecular sieve, wt% | 16 | 18 | 18 | 18 |
| SBA-15, wt% | 7 | 9 | 9 | 9 |
| Amorphous silica-alumina, wt% | 62.0 | 54.0 | 54.0 | 56.0 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 502 | 511 | 519 | 525 |
| Kong Rong, mL/g | 0.77 | 0.79 | 0.81 | 0.82 |
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CAT-4 |
| WO3, wt% | 22.0 | 21.9 | 22.2 | 22.2 |
| NiO, wt% | 5.9 | 5.8 | 6.0 | 6.0 |
| Specific surface area, m2/g | 415 | 420 | 431 | 436 |
| Kong Rong, mL/g | 0.57 | 0.58 | 0.59 | 0.60 |
Table 3 is continuous
| Bearer number | CTCAT-1 | CTCAT-2 | CTCAT-3 | CTCAT-4 | CTCAT-5 | CTCAT-6 |
| Beta-molecular sieve, wt% | 18 | 18 | 18 | 18 | 18 | 27 |
| SBA-15, wt% | 9 | 9 | 9 | 9 | 9 | - |
| Amorphous silica-alumina, wt% | 56 | 56 | 56 | 56 | 56 | 56 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 479 | 485 | 486 | 489 | 491 | 498 |
| Kong Rong, mL/g | 0.71 | 0.72 | 0.73 | 0.74 | 0.73 | 0.75 |
| Catalyst is numbered | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 | CCAT-6 |
| WO3, wt% | 22.0 | 22.1 | 22.1 | 22.0 | 22.1 | 22.0 |
| NiO, wt% | 6.0 | 5.9 | 6.2 | 6.1 | 6.0 | 5.9 |
| Specific surface area, m2/g | 386 | 388 | 390 | 400 | 398 | 406 |
| Kong Rong, mL/g | 0.52 | 0.53 | 0.54 | 0.55 | 0.56 | 0.57 |
By aforementioned present invention 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 when 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 | 0.9082 |
| 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-1 | CAT-2 | CAT-3 | CAT-4 |
| Reaction temperature, DEG C | 371 | 370 | 369 | 368 |
| <370 DEG C of conversion ratios, wt% | 66.1 | 66.3 | 66.4 | 66.6 |
| Middle distillates oil selectivity, %（132~370 DEG C） | 90.5 | 89.8 | 88.9 | 90.5 |
| Major product property | ||||
| Heavy naphtha（82~132℃） | ||||
| Virtue is latent, wt% | 66.2 | 66.7 | 66.3 | 66.7 |
| Jet fuel（132~282℃） | ||||
| Freezing point, DEG C | <-60 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 3.1 | 3.3 | 2.8 | 2.6 |
| 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 | 10.2 | 9.7 | 9.1 | 8.7 |
Table 5 is continuous
| Catalyst is numbered | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 | CCAT-6 |
| Reaction temperature, DEG C | 376 | 376 | 380 | 380 | 379 | 370 |
| <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） | 82.7 | 83.0 | 84.8 | 85.5 | 85.7 | 88.2 |
| 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 | -2 | -54 | -58 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 6.7 | 6.9 | 5.8 | 5.2 | 4.8 | 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 | -18 |
| Tail oil（>370℃） | ||||||
| BMCI | 15.7 | 15.9 | 12.2 | 13.4 | 11.8 | 12.0 |
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 is good, and especially condensation point of diesel oil and tail oil BMCI values is relatively low.
Claims (34)
1. a kind of hydrocracking catalyst, including carrier and hydrogenation active metal component, carrier include beta-molecular sieve, SBA-15 points
Son sieve, amorphous silica-alumina and adhesive, wherein beta-molecular sieve property are as follows： SiO2/Al2O3Molar ratio is 60~100, specific surface
Product is 505~850m20.35~0.60mL/g of/g, Kong Rongwei, relative crystallinity are 100%~148%；The beta-molecular sieve is through water
Relative crystallinity after steam hydro-thermal process is 95% or more.
2. catalyst according to claim 1, it is characterised in that：The beta-molecular sieve property is as follows：SiO2/Al2O3It rubs
, than being 65~100, specific surface area is 550~800m for you2/ g, hole hold 0.40~0.60mL/g, relative crystallinity be 110%~
140%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 95%~130%.
3. catalyst according to claim 1, it is characterised in that：The beta-molecular sieve property is as follows：SiO2/Al2O3It rubs
, than being 65~100, specific surface area is 600~750 m for you2/ g, hole hold 0.45~0.55mL/g, relative crystallinity be 115%~
140%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 108%~130%.
4. catalyst according to claim 1,2 or 3, it is characterised in that：The beta-molecular sieve is through water vapour hydro-thermal process
Condition it is as follows：Through 750 DEG C of water vapour hydro-thermal process 2 hours.
5. catalyst according to claim 1, it is characterised in that：The property of the SBA-15 molecular sieves is as follows：Compare table
Area is 700~1000 m20.9 ~ 1.5mL/g of/g, Kong Rongwei.
6. catalyst 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。
7. catalyst according to claim 6, 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。
8. catalyst according to claim 1, it is characterised in that：In the carrier of hydrocracking catalyst, with carrier
Weight on the basis of, the total content of beta-molecular sieve and SBA-15 molecular sieves is 5wt%~40wt%, and the content of amorphous silica-alumina is
The content of 20wt%~60wt%, adhesive are 15wt%~40wt%, and wherein beta-molecular sieve accounts for beta-molecular sieve and SBA-15 molecular sieves are total
The 40% ~ 95% of weight.
9. catalyst according to claim 1, it is characterised in that：The hydrogenation active metals are group VIB and/or the
The metal of VIII race.
10. catalyst according to claim 9, it is characterised in that：The vib metals be molybdenum and/or tungsten, the VIIIth
The metal of race is cobalt and/or nickel.
11. catalyst according to claim 9, it is characterised in that：On the basis of the weight of catalyst, vib metals
Content in terms of oxide is 10wt%~30wt%, and content of the group VIII metal in terms of oxide is 4wt%~15wt%, carrier
Content is 60.0%~86.0%.
12. the preparation method of any hydrocracking catalyst of claim 1 ~ 11, including：By beta-molecular sieve, SBA-15 molecules
Carrier is made through dry and roasting in sieve, amorphous silica-alumina and adhesive mixing, molding.
13. preparation method according to claim 12, it is characterised 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）, by 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 ammonium 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.
14. preparation method according to claim 13, 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%.
15. preparation method according to claim 13, 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.
16. preparation method according to claim 13, 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, Xiang Bu
Suddenly（2）Water, silicon source and template are added in the amorphous silica-alumina predecessor of gained.
17. preparation method according to claim 13, 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.
18. preparation method according to claim 17, 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.
19. preparation method according to claim 13, 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.
20. preparation method according to claim 19, which is characterized in that in step（1）In, controlling reaction temperature be 15~
35℃。
21. preparation method according to claim 13, which is characterized in that in step（1）In, the silicon-containing compound solution
For waterglass and/or sodium silicate solution.
22. the preparation method according to claim 13 or 19, 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 silicon-containing compound solution it is a concentration of
50~150gSiO2/ L, the CO2A concentration of 30v% ~ 60v% of gas.
23. preparation method according to claim 13, 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.
24. preparation method according to claim 23, 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.
25. preparation method according to claim 13, it is characterised in that：In step（3）In, the silicon source be White Carbon black,
One or more in silica gel, Ludox and waterglass, the template is tetraethyl ammonium hydroxide.
26. preparation method according to claim 13, it is characterised in that：In step（4）In, step（3）The sial of gained
Specific steps of the gel through two step dynamic crystallizations include：The condition of first step dynamic crystallization is：Crystallization is carried out under agitation,
Temperature is 50~90 DEG C, and the time is 0.5~18.0 hour；The condition of second step dynamic crystallization is：It carries out under agitation brilliant
Change, temperature is 100~200 DEG C, and the time is 40~120 hours.
27. preparation method according to claim 26, 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.
28. preparation method according to claim 13, which is characterized in that through step（5）After ammonium salt exchanges in beta-molecular sieve
Na2O weight contents are less than 0.3%.
29. the preparation method according to claim 13 or 28, 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.
30. preparation method according to claim 29, which is characterized in that step（5）In, Template removal processing is adopted
With aerobic high-temperature process, treatment temperature is 500~700 DEG C, and processing time is 10~15 hours.
31. preparation method according to claim 12, it is characterised in that：When prepared by carrier, beta-molecular sieve and SBA-15 molecules
Sieve be individually separately added into amorphous silica-alumina and adhesive mixed-forming, or beta-molecular sieve and SBA-15 molecular sieves first mixed
Afterwards, then with amorphous silica-alumina and adhesive mixed-forming.
32. preparation method according to claim 31, it is characterised in that：When prepared by carrier, β points are added with the following method
Son sieve and SBA-15 molecular sieves：It is added 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, beta-molecular sieve is then added, 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.
33. preparation method according to claim 12, 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.
34. preparation method according to claim 12, which is characterized in that the carrying method of hydrogenation active metals is using dipping
Method uses the solution impregnated catalyst carrier containing required hydrogenation active component, the carrier after dipping is done at 100 DEG C~150 DEG C
Then dry l~12 hour roast 3~12 hours at 400 DEG C~750 DEG C, final catalyst is made.
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| CN109529926A (en) * | 2018-12-06 | 2019-03-29 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene is hydrocracked the catalyst and preparation method and application of light aromatics processed |
| CN111167509B (en) * | 2019-08-20 | 2022-09-20 | 中国石油化工股份有限公司 | Carbon tetraolefin cracking catalyst, preparation method thereof and catalytic cracking method |
| CN113023745B (en) * | 2019-12-25 | 2022-08-12 | 中国石油化工股份有限公司 | Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| CN113522350B (en) * | 2020-04-22 | 2023-07-21 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing doughnut-shaped mesoporous material, and preparation method and application thereof |
| CN114433208B (en) * | 2020-10-19 | 2024-01-12 | 中国石油化工股份有限公司 | Method for producing middle distillate by hydrocracking |
| CN114433210B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrodearene catalyst and preparation method and application thereof |
| CN114453010B (en) * | 2020-10-21 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst, and preparation method and application thereof |
| CN114453018B (en) * | 2020-10-21 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method of hydrocracking catalyst |
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