CN106140317B - Diesel oil hydrogenation modification catalyst carrier and preparation method thereof - Google Patents
Diesel oil hydrogenation modification catalyst carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of diesel oil hydrogenation modification catalyst carriers and preparation method thereof.The carrier includes beta-molecular sieve, macroporous aluminium oxide and adhesive, and on the basis of the weight of carrier, composition includes：The content of beta-molecular sieve is 5~30wt%, and the content of macroporous aluminium oxide is 20~65wt%, and the content of adhesive is 15~50wt%, and the 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 more than 95%.Hydrocracking catalyst prepared by the carrier has the characteristics that diesel product yield height and good product quality.
Description
Technical field
The present invention relates to a kind of diesel oil hydrogenation modification catalyst carriers and preparation method thereof, and more specifically one kind can
Using poor ignition quality fuel as raw material, production have the characteristics that high cetane number, low condensation point, compared with low-density diesel oil containing beta-molecular sieve
Diesel oil hydrogenation modification catalyst carrier and preparation method thereof.
Background technology
As crude oil heaviness, in poor quality degree are aggravated, secondary processing diesel oil fraction especially catalytic cracking diesel oil quality
It is deteriorated, on the other hand, to improve yield of light oil, the processing that each refiner in countries in the world improves catalytic cracking process one after another is deep
Degree, and then the quality of catalytic cracking diesel oil is caused further to be deteriorated.With environmental requirement increasingly stringent, diesel quality standard
Constantly upgrading, especially discharge standard Central Europe IV, V standard of Europe to the sulphur in diesel oil and arene content, Cetane number, density,
The indexs such as T95 propose more strict requirements.In addition, the people of extremely frigid zones or winter life come to the low of diesel product
Warm mobile performance compares attention, and only low freezing point diesel fuel product can be met the actual needs.Winter north cold area
Need a large amount of low-coagulation diesel oils, the low temperature flow of diesel oil（Condensation point, cold filter plugging point, pour point etc.）Index seems even more important.
At present, the production technology for cleaning diesel product mainly has the technologies such as hydrofinishing and Medium Pressure Hydrogenation Modification.Add hydrogen smart
System can effectively reduce the sulfur content of modification diesel oil, but effect is general in terms of improving Cetane number and reducing T95 temperature.Middle pressure adds
Hydrogen modification is suitably to crack diesel oil under the conditions of middle pressure, changes catalytic cracking diesel oil hydro carbons composition structure, reaches improvement diesel oil
Product quality, production meet the purpose of the cleaning diesel product of harsh diesel oil standard.Institute in pressure diesel modifying catalyst in current
The Cracking Component of use is mainly modified Y type molecular sieve, since Y type molecular sieve has the supercage structure of twelve-ring so that
Dry large-minded, diesel product the yield of existing diesel modifying catalyst is low, the amplitude of Cetane number raising is small, the recycling of T95 points
Small, the shortcomings of condensation point is high and density is big.For example, CN1184843A and CN101463271A.CN1184843A discloses a kind of bavin
Oily hydrogenation conversion catalyst, the composition of the catalyst is 40 ~ 80wt% of aluminium oxide, 0 ~ 20wt% of amorphous silica-alumina, molecular sieve 5 ~
30wt%, the molecular sieve hold 0.4 ~ 0.52mL/g, 750 ~ 900m of specific surface area for hole2/ g, lattice constant 2.420 ~
2.500nm, silica alumina ratio are 7 ~ 15 Y type molecular sieve.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel
And preparation method thereof, mainly mixed using the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y type molecular sieve,
Molding and roasting introduce a effective amount of hydrogenation metal in molding species later.Above-mentioned catalyst has higher desulfurization and denitrogenation
Activity, but the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is small, the shortcomings of condensation point is high and density is big.
Relative to Y type molecular sieves, beta-molecular sieve has three-dimensional twelve-ring pore structure, but without as Y type molecular sieves
Supercage structure, be mainly characterized by double 6 round rings unit bug hole structures of two 4 round ringss and four 5 round ringss, main channel diameter exists
0.56-0.75nm, the duct feature of beta-molecular sieve cause it has the fracture of chain hydrocarbon-selective in cracking reaction to make well
With, and with very strong isomery performance, can be used for producing low condensation point oil distillate as cracking component, industrially obtain extensively
Application.
US4847055 discloses a kind of method of improved synthesis beta-molecular sieve, wherein using a kind of special silicon source, with
TEABr is template, and beta-molecular sieve is prepared under the conditions of existing for crystal seed.The silicon source is in certain condition by soluble silicon solution
Lower addition precipitating reagent is made.The dosage of this method template is larger, and easily generates modenite and ZSM-5 stray crystals.Only
As (TEA)2O/SiO2>0.14, i.e. TEA+/SiO2>When 0.28, the production quantity of stray crystal could be reduced.
Above-mentioned hydro-thermal method synthesis β zeolites need a large amount of expensive organic formwork agent tetraethyl ammonium hydroxides, beta-molecular sieve synthesis
Cost largely derived from template, typically constitute from 70% or so.Template dosage is reduced, so as to reduce β zeolite synthesis costs, one
It is directly the hot spot of the area research.
Furthermore beta-molecular sieve as catalyst use it is preceding must by the organic formwork agent being blocked in zeolite cavity remove fall
Catalytic activity can just be made it have.The method of conventional removing organic formwork agent is high-temperature roasting, since high-temperature roasting will destroy β
The structure of molecular sieve declines its crystallinity, and thermal stability and hydrothermal stability are deteriorated, and consumption of template agent is bigger,
This extent of the destruction is more serious.And use add in a small amount of template synthesizing high-silicon aluminium than beta-molecular sieve when, the crystallinity meeting of product
Very low, thermal stability and hydrothermal stability are poor.
CN1351959A is related to a kind of synthetic method of molecular sieve.Al is pressed first2O3：(30-150)SiO2：(5-20)
(TEA)2O：(1-8.5)Na2O：(650-1200)H2The mol ratio of O prepares Alusil A, by Al2O3：(20-80)SiO2：(5-
15)Na2O：(350-1000)H2The mol ratio of O prepares Alusil B, and Alusil A and Alusil B then is pressed 1：10 weight
It than mixing, is transferred in autoclave pressure after stirring evenly, after sealing at a temperature of 100-200 DEG C, is stirred under static or 10-150rpm rotating speeds
Mix crystallization 15-150 hours, end product is through filtering, washing and be dried to obtain beta-molecular sieve.Although this synthetic method can will have
The dosage of machine template is reduced to TEAOH/SiO2=0.05, but beta-molecular sieve silica alumina ratio prepared by this method is relatively low, and beta-molecular sieve
Characteristic peak have a small amount of miscellaneous peak, have stray crystal generation.
CN 1198404A propose a kind of method for synthesizing beta-molecular sieve, using halide, the tetraethyl by tetraethyl ammonium
The composite mould plate agent that ammonium hydroxide and fluoride are formed under alkaline condition makes silicon source, silicon source and crystal seed reaction crystallization generate β points
Son sieve.Although this method reduces template dosage, increase the yield of beta-molecular sieve, but need add in composite mould plate agent and
Crystal seed, and silica alumina ratio be more than 30 after, crystallinity is relatively low, and thermal stability and hydrothermal stability are poor.
Invention content
For shortcoming of the prior art, the present invention provides a kind of good diesel oil hydrogenation modification catalysis of catalytic performance
Agent carrier and preparation method thereof.The catalyst for hydro-upgrading carrier using a kind of high silica alumina ratio, high-crystallinity, bigger serface,
The good beta-molecular sieve of stability is produced as acidic components by diesel oil hydrogenation modification catalyst prepared by carrier of the present invention with diesel oil
The features such as product high income and good product quality.
Diesel oil hydrogenation modification catalyst carrier of the present invention, including beta-molecular sieve, macroporous aluminium oxide and adhesive, with carrier
On the basis of weight, composition includes：The content of beta-molecular sieve is 5~30wt%, and the content of macroporous aluminium oxide is 20~65 wt%,
The content of adhesive is 15~50wt%, and the beta-molecular sieve property is as follows：SiO2/Al2O3Molar ratio is 60~100, compares table
Area is 505~850m20.35~0.60mL/g of/g, Kong Rongwei, relative crystallinity are 100%~148%；The beta-molecular sieve passes through
Relative crystallinity after water vapour hydro-thermal process is more than 95%.
In catalyst for hydro-upgrading carrier of the present invention, the beta-molecular sieve is Hydrogen beta-molecular sieve.
In catalyst for hydro-upgrading carrier 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 is 65~100, specific surface area for 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 the present invention, the property of the macroporous aluminium oxide is as follows：0.7 ~ 1.0 mL/g of Kong Rongwei, specific surface area 200 ~
500 m2/g。
In catalyst for hydro-upgrading carrier 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 specific surface area of catalyst for hydro-upgrading carrier of the present invention is 400~600 m2/ g, Kong Rong are 0.50~1.0 mL/
g。
The preparation method of diesel oil hydrogenation modification catalyst carrier of the present invention, including：By beta-molecular sieve, macroporous aluminium oxide and glue
Mixture mixes, molding, and through dry and roasting, carrier is made.
In the preparation method of catalyst for hydro-upgrading carrier of the present invention, the beta-molecular sieve uses 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, silicon is using the content that silica is counted as 40wt%~75wt%, preferably 55wt%~70wt%；It is made
Standby process includes：
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）, by 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 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.
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, is controlled into
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 small for 0.5~18.0
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
It is 60~80 DEG C to spend, 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, Template removal processing uses aerobic high-temperature process, treatment temperature for 400~
800 DEG C, processing time is 5~20 hours, and preferably, treatment temperature is 500~700 DEG C, and processing time is 10~15 hours.
The preferably small porous aluminum oxide of adhesive therefor of the present invention.It is 0.3~0.5 mL/g that aperture alumina pore used, which holds, than
Surface area is 200~400m2/g。
In catalyst carrier of the present invention, 0.7 ~ 1.0 mL/g of Kong Rongwei of macroporous aluminium oxide used, specific surface area 200 ~
500 m2/g。
Catalyst carrier of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..It is being catalyzed
In agent forming process, shaping assistant, such as peptization acid, extrusion aid can also be added in.Catalyst carrier of the present invention is using routine
Method is dried and roasts, specific as follows：It is 3~10 hours dry at a temperature of 80~150 DEG C, in 400~800 DEG C of roastings
3~12 hours.
The present invention is in the preparation process of beta-molecular sieve, first by part silicon-containing compound before plastic and/or during plastic
It adds in reaction system, forms stable colloidal state and sial integrated structure.Since this colloid surface has many hydroxyls
Structure can be combined with the remainder silicon-containing compound added in below well, so as to which amorphous silica-alumina predecessor be made to have more
Add stable structure.Later, amorphous silica-alumina predecessor, template and another part silicon source etc. are mixed and made into silica-alumina gel,
More nucleus can be formed in synthetic system in this way, are evenly dispersed in synthetic system, there is good crystallization to be oriented to and make
With, then through two step dynamic crystallizations, easily form complete skeleton structure, the high beta molecular sieve of crystallinity.The method of the present invention 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 without carrying out dealuminzation again or taking off by Na beta molecular sieves
Aluminium mends the dual-spectrum process such as silicon.
When being modified as the catalyst prepared by diesel oil hydrogenation modification catalyst carrier of the present invention for poor ignition quality fuel, particularly
In middle press strip part（4~12MPa）With very high catalytic activity and diesel yield when handling poor ignition quality fuel, and diesel oil distillate
Condensation point reduction amplitude is big, improves the Cetane number of modification diesel oil by a relatively large margin, and the density of diesel product is also effectively reduced,
Can meet refinery's increase operating flexibility, increase device processing capacity, the diesel oil that further raises productivity and improves the quality needs.
Specific embodiment
In order to which the present invention is better described, further illustrated the present invention with reference to embodiment and comparative example.But this hair
Bright range is not limited solely to the range of these embodiments.Analysis method of the present invention：Specific surface area, Kong Rong use low temperature liquid nitrogen physics
Absorption method, relative crystallinity use x-ray diffraction method, and silica alumina ratio uses chemical method.In the present invention, wt% is mass fraction, v%
For 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.200mL sodium aluminate working solutions is taken to be placed in plastic cans, are then added in
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 logical CO2, 50mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, obtains amorphous silica-alumina predecessor, nothing
Amorphous silicon-alumina predecessor is on the basis of silica and aluminium oxide total weight, using the content that silica is counted as 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 is poured into stainless steel cauldron, is stirred crystallization 5 hours at 80 DEG C, is then heated 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
Product N β -1, measures relative crystallinity；N β -1 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；Nβ-
1 after 750 DEG C of water vapour hydro-thermal process 2 hours, 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, and add a certain amount of ammonium nitrate in Na beta-molecular sieve N β -1, make liquid-solid ratio（Weight）For
10：1, a concentration of 2mol/L of ammonium nitrate, stirring are warming up to 95~100 DEG C, and constant temperature stirs 2 hours, then filters, filter cake is again
Secondary progress ammonium salt exchange, the condition of exchange is identical with first time, until finally washing molecule is sieved to pH value neutrality, is put into dry
It is dry in dry band, it is 8 hours dry at 100~120 DEG C.Dried beta-molecular sieve is taken to carry out abjection template processing, is used
Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and beta-molecular sieve S β -1, XRD determining S β -1 relative crystallinities is made；S
β -1 is after 750 DEG C of water vapour hydro-thermal process 2 hours, then measures the relative crystallinity after hydro-thermal process, the results are shown in Table 2.
Embodiment 2
（1）The preparation of amorphous silica-alumina predecessor
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.200mL sodium aluminate working solutions is taken to be placed in plastic cans, are then added in
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 logical CO2, 40mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, obtains amorphous silica-alumina predecessor, nothing
Amorphous silicon-alumina predecessor is on the basis of silica and aluminium oxide total weight, using the content that silica is counted as 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 is poured into stainless steel cauldron, is stirred crystallization 5 hours at 90 DEG C, is then heated 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
Product N β -2, measure relative crystallinity；N β -2 measure the relative crystallinity after roasting after being roasted 3 hours in 550 DEG C of air；Nβ-
2 after 750 DEG C of water vapour hydro-thermal process 2 hours, 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, and add a certain amount of ammonium nitrate in Na beta-molecular sieve N β -2, make liquid-solid ratio（Weight）For
10：1, a concentration of 2mol/L of ammonium nitrate, stirring are warming up to 95~100 DEG C, and constant temperature stirs 2 hours, then filters, filter cake is again
Secondary progress ammonium salt exchange, the condition of exchange is identical with first time, until finally washing molecule is sieved to pH value neutrality, is put into dry
It is dry in dry band, it is 8 hours dry at 100~120 DEG C.Dried beta-molecular sieve is taken to carry out abjection template processing, is used
Open kiln processing, 570 DEG C of constant temperature are handled 15 hours, and beta-molecular sieve S β -2, XRD determining S β -2 relative crystallinities is made；S
β -2 is after 750 DEG C of water vapour hydro-thermal process 2 hours, then measures the relative crystallinity after hydro-thermal process, the results are shown in Table 2.
Embodiment 3
（1）The preparation of amorphous silica-alumina predecessor
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.160mL sodium aluminate working solutions is taken to be placed in plastic cans, are then added in
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 logical CO2, 35mL sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes, obtains amorphous silica-alumina predecessor, nothing
Amorphous silicon-alumina predecessor is on the basis of silica and aluminium oxide total weight, using the content that silica is counted as 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 molecular sieve N β -3, 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 Na beta-molecular sieve N β -3 are made beta-molecular sieve S β -3, XRD
Measure S β -3 relative crystallinities；S β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure the opposite knot after hydro-thermal process
Brilliant degree, the results are shown in Table 2.
Embodiment 4
By 25 grams of S β -1 molecular sieves, (hole holds 0.9mLg, specific surface area 350m to 106.5 grams of macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is mixed 0.25) to be put into roller
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
TCAT-1, property are shown in Table 3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 5
By 30 grams of S β -2 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of macroporous aluminium oxides2/ g), 90 grams it is viscous
The small porous aluminum oxide of mixture, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller,
Add water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT-
2。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 6
By 30 grams of S β -3 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of macroporous aluminium oxides2/ g), 90 grams it is viscous
The small porous aluminum oxide of mixture, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25) to be put into mixed grind in roller,
Add water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier TCAT-
3。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 1（With reference to CN1351959A）
By 20.5g White Carbon blacks, 2mL sodium aluminate solutions, 59g tetraethyl ammonium hydroxides and 0.9g sodium hydroxides, in room temperature
With mixed under mechanical agitation, and continue stirring and be uniformly mixed to raw material：Mixture is transferred in autoclave pressure, at 130 DEG C after sealing
At a temperature of after static ageing 5 hours, take out and be quickly cooled down autoclave pressure, obtain Alusil A.By 120g Ludox, the inclined aluminium of 6.3mL
Sour sodium, 6g sodium hydroxides and 17mL distilled water mix under room temperature and mechanical agitation, and stir and be uniformly mixed to raw material, obtain silicon
Aluminium glue B.5g Alusils A and 50g Alusil B under room temperature and mechanical agitation is mixed, and stirs and turns after mixing to raw material
Enter in autoclave pressure, after sealing at a temperature of 130 DEG C, to stir crystallization under 60rpm rotating speeds 48 hours, take out and be quickly cooled down pressure
Kettle.Product is dry at 120 DEG C after washing to neutrality through filtering, washing, and obtains Na beta-molecular sieve products C N β -1, 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
It is the characteristic peak for having beta-molecular sieve to show product, but has 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
Product CS β -1, XRD determining CS β -1 relative crystallinities；CS β -1 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure 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 macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is mixed 0.25) to be put into roller
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
TCCAT-1。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 2（With reference to CN1198404A）
16g tetraethylammonium bromides and 1.6g sodium fluorides D are dissolved in 30g deionized waters, are sequentially added under stirring by 1.67g aluminic acids
Sodium B is dissolved in 20g deionized waters acquired solution, 53.7g Ludox and 0.72g crystal seeds, continues stirring 60 minutes, is transferred to stainless steel
In reaction kettle, crystallization 4 days at 160 DEG C.Then it is filtered, washed, dries to obtain Na beta-molecular sieve products C N β -2, measure 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
Product CS β -2, XRD determining CS β -2 relative crystallinities；CS β -2 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then measure 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 macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is mixed 0.25) to be put into roller
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
CTCAT-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.200mL sodium aluminate working solutions is taken to be placed in plastic cans, are then added in
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 logical 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, using the content that silica is counted as 60wt%.
（2）The preparation of gel is the same as embodiment 1；
（3）Crystallization obtains molecular sieve CN β -3, 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, by Na beta-molecular sieve CN β -3 be made beta-molecular sieve products C S β -
3, XRD determining CS β -3 relative crystallinities；CS β -3 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then after measuring hydro-thermal process
Relative crystallinity the results are shown in Table 2.
By 30 grams of CS β -3 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is mixed 0.25) to be put into roller
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
TCCAT-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 is 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 logical 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, using the content that silica is counted as 60wt%.
（2）The preparation of gel is the same as embodiment 1；
（3）Crystallization obtains molecular sieve CN β -4, 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, and Na beta-molecular sieve CN β -4 are made to obtain beta-molecular sieve product
CS β -4, XRD determining CS β -4 relative crystallinities；CS β -4 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then 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 macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is mixed 0.25) to be put into roller
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
CTCAT-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 molecular sieve CN β -5, 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, by Na beta-molecular sieve CN β -5 be made beta-molecular sieve products C S β -
5, XRD determining CS β -5 relative crystallinities；CS β -5 are after 750 DEG C of water vapour hydro-thermal process 2 hours, then after measuring hydro-thermal process
Relative crystallinity the results are shown in Table 2.
By 30 grams of CS β -5 molecular sieves, (hole holds 0.9mL/g, specific surface area 350m to 100 grams of macroporous aluminium oxides2/ g), 90 grams
The small porous aluminum oxide of adhesive, with dust technology（The molar ratio of wherein nitric acid and small porous aluminum oxide is 0.25）It is put into roller and mixes
It grinds, adds water, be rolled into paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, is then roasted 4 hours at 550 DEG C, obtains carrier
CTCAT-5。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-5 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Table 1
| Feed intake SiO2/Al2O3Molar ratio | Specific surface area, m2/g | Kong Rong, mL/g | SiO2/Al2O3Molar ratio | Relative crystallinity, % | Relative crystallinity *, % after roasting | Opposite crystallization reservation degree after hydro-thermal process, % | |
| 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 crystallization reservation degree 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 3 carrier of table and catalyst
| Bearer number | TCAT-1 | TCAT-2 | TCAT-3 | CTCAT-1 | CTCAT-2 | CTCAT-3 | CTCAT-4 | CTCAT-5 |
| Beta-molecular sieve, wt% | 12 | 16 | 16 | 16 | 16 | 16 | 16 | 16 |
| Macroporous aluminium oxide, wt% | 68 | 64 | 64 | 64 | 64 | 64 | 64 | 64 |
| Adhesive, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 486 | 483 | 475 | 458 | 445 | 462 | 455 | 460 |
| Kong Rong, mL/g | 0.75 | 0.74 | 0.73 | 0.67 | 0.68 | 0.68 | 0.68 | 0.69 |
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 |
| WO3, wt% | 22.0 | 21.9 | 22.2 | 22.0 | 22.1 | 22.1 | 22.0 | 22.1 |
| NiO, wt% | 5.9 | 5.8 | 6.0 | 6.0 | 5.9 | 6.2 | 6.1 | 6.0 |
| Specific surface area, m2/g | 416 | 412 | 408 | 382 | 376 | 390 | 380 | 395 |
| Kong Rong, mL/g | 0.59 | 0.59 | 0.57 | 0.49 | 0.49 | 0.51 | 0.50 | 0.52 |
By the invention described above catalyst CAT-1, CAT-2, CAT-3 and comparative example catalyst CCAT-1, CCAT-2, CCAT-
3rd, CCAT-4, CCAT-5 carry out active evaluation test.Evaluation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 800, during liquid
Volume space velocity 1.5h-1, using catalytic diesel oil as feedstock oil, raw material oil nature is shown in Table 4.Catalyst Activating Test the results are shown in Table 5.
4 raw material oil nature of table
| Feedstock oil | Iranian VGO |
| Density (20 DEG C), g/cm3 | 0.9082 |
| IBP/10% | 153/227 |
| 30%/50% | 270/303 |
| 70%/90% | 326/355 |
| 95%/EBP | 378/391 |
| Condensation point, DEG C | 8 |
| S, wt% | 0.91 |
| N, wt% | 0.1201 |
| C, wt% | 85.91 |
| H, wt% | 12.48 |
| Cetane number | 23 |
5 catalyst activity evaluation result of table
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 |
| Feedstock oil | Urge bavin | Urge bavin | Urge bavin | Urge bavin | Urge bavin | Urge bavin | Urge bavin | Urge bavin |
| Reaction temperature, DEG C | 370 | 368 | 366 | 370 | 371 | 373 | 372 | 372 |
| Major product property | ||||||||
| Naphtha | ||||||||
| Yield, wt% | 2.4 | 2.2 | 1.9 | 4.3 | 4.2 | 3.8 | 3.7 | 3.6 |
| Virtue is latent, wt% | 53.7 | 54.1 | 54.6 | 48.6 | 49.7 | 50.2 | 51.0 | 50.6 |
| Diesel oil | ||||||||
| Yield, wt% | 96.6 | 96.9 | 97.3 | 91.4 | 92.0 | 93.5 | 93.8 | 93.7 |
| Density（20℃） | ||||||||
| T95, DEG C | 346 | 345 | 344 | 368 | 362 | 357 | 354 | 353 |
| Cetane number | 52.8 | 53.0 | 53.3 | 48.5 | 49.2 | 50.1 | 50.9 | 50.8 |
| Condensation point, DEG C | -24 | -25 | -27 | -6 | -9 | -12 | -14 | -13 |
| Sulphur, μ g/g | 3.0 | 3.0 | 3.0 | 6.2 | 5.9 | 5.2 | 4.9 | 5.0 |
| Total liquid yield, wt% | 99 | 99.1 | 99.2 | 95.7 | 96.2 | 97.2 | 97.5 | 97.3 |
Can be seen that by the evaluation result of 5 catalyst of table, carrier prepared catalyst of the present invention under identical process conditions,
Diesel yield and product quality are superior to reference catalyst.
Claims (18)
1. a kind of preparation method of diesel oil hydrogenation modification catalyst carrier, it is characterised in that including：Beta-molecular sieve, macropore are aoxidized
Through dry and roasting, carrier is made in aluminium and adhesive mixing, molding, and the beta-molecular sieve uses following preparation process：
（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, silicon is using the content that silica is counted as 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 through2 When gas flow accounts for the 60% ~ 100% of total intake, the siliceous chemical combination of remainder is added in
Object solution；
（2）, in step（1）Said mixture stablize in ventilated environment 10 ~ 30 minutes；
（3）, by 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
Agent stirs evenly, and obtains silica-alumina gel, and 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,
Prepared catalyst carrier, on the basis of the weight of carrier, composition includes：The content of beta-molecular sieve is 5~30wt%,
The content of macroporous aluminium oxide is 20~65wt%, and the content of adhesive is 15~50wt%；The 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 is opposite to crystallize
Spend is 100%~148%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is more than 95%.
2. according to the method described in claim 1, it is characterized 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, relative crystallinity for 110%~
140%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 95%~130%.
3. according to the method described in claim 1, it is characterized 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, relative crystallinity for 115%~
140%；Relative crystallinity of the beta-molecular sieve after water vapour hydro-thermal process is 108%~130%.
4. according to the method described in claim 1, it is characterized in that：Condition of the beta-molecular sieve through water vapour hydro-thermal process is such as
Under：Through 750 DEG C of water vapour hydro-thermal process 2 hours.
5. according to the method described in claim 1, it is characterized in that：0.7 ~ 1.0 mL/g of Kong Rongwei of the macroporous aluminium oxide,
200 ~ 500 m of specific surface area2/g。
6. according to the method described in claim 1, it is characterized in that：The specific surface area of carrier is 400~600 m2/ g, Kong Rong are
0.50~1.0 mL/g.
7. according to the method described in claim 1, it is characterized in that：In step（1）In, the remainder silicon-containing compound is molten
Liquid accounts for the 5wt% ~ 85wt% for adding in silicon-containing compound solution total amount in terms of silica in terms of silica.
8. according to the method described in claim 1, it is characterized in that：In step（1）In, reaction temperature is 10~40 DEG C, control
PH values after reaction are 8~11.
9. according to the method described in claim 1, it is characterized in that：In step（1）In, the silicon-containing compound solution is water glass
Glass solution.
10. according to the method described in claim 1, it is characterized in that：In step（1）In, with A12O3Quality meter, the sodium aluminate
A concentration of 15~55g Al of solution2O3/ L, with SiO2Quality meter, a concentration of the 50~150 of the silicon-containing compound solution
gSiO2/ L, the CO2A concentration of 30v% ~ 60v% of gas.
11. according to the method described in claim 1, it is characterized in that：In step（3）In, generate the reaction of the silica-alumina gel
0~40 DEG C of temperature, pH value are 9.5~12.0.
12. according to the method described in claim 1, it is characterized in that：In step（3）In, the silicon source for White Carbon black, silica gel,
One or more in Ludox and waterglass, the template is tetraethyl ammonium hydroxide.
13. according to the method described in claim 1, it is characterized in that：In step（4）In, step（3）The silica-alumina gel warp of gained
The specific steps of 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, the time is 0.5~18.0 hour；The condition of second step dynamic crystallization is：Crystallization, temperature are carried out under agitation
It it is 100~200 DEG C, the time is 40~120 hours.
14. according to the method for claim 13, it is characterised in that：In step（4）In, the item of the first step dynamic crystallization
Part is：Crystallization is carried out under agitation, and temperature is 60~80 DEG C, and the time is 1~10 hour；The second step dynamic crystallization
Condition is：Crystallization is carried out under agitation, and temperature is 120~170 DEG C, and the time is 50~100 hours.
15. according to the method described in claim 1, it is characterized in that：In step（5）In, ammonium salt exchange using conventional method into
Row, one or many ammonium salts exchange, Na in the beta-molecular sieve after ammonium salt exchange2O weight contents are less than 0.3%；Ammonium salt can after exchanging
With the step by washing and drying, wherein dry condition is as follows：In 80 DEG C ~ 150 DEG C dryings 3~6 hours.
16. according to the method described in claim 1, it is characterized in that：In step（5）In, Template removal processing uses
Aerobic high-temperature process, treatment temperature are 400~800 DEG C, and processing time is 5~20 hours.
17. according to the method described in claim 1, it is characterized in that：In step（5）In, adhesive therefor is small porous aluminum oxide,
It is 0.3~0.5mL/g that aperture alumina pore used, which holds, and specific surface area is 200~400m2/g。
18. according to the method described in claim 1, it is characterized in that：The drying and roasting condition that the carrier uses are 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.
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| CN1712499A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Diesel production from hydrogenation upgrading isomerizing pour-point reduction |
| CN103100429A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Diesel oil hydro-upgrading catalyst carrier and preparation method thereof |
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| CN1362362A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Beta-zeolite and its prepn |
| CN1712499A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Diesel production from hydrogenation upgrading isomerizing pour-point reduction |
| CN103100429A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Diesel oil hydro-upgrading catalyst carrier and preparation method thereof |
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