CN106140282A - Middle oil type hydrocracking catalyst and preparation method thereof - Google Patents
Middle oil type hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses oil type hydrocracking catalyst and preparation method thereof in one.This catalyst includes carrier and hydrogenation active component, described carrier includes beta-molecular sieve, Y molecular sieve, amorphous silica-alumina and binding agent, on the basis of the weight of carrier, the content of beta-molecular sieve is 2～20wt%, the content of Y molecular sieve is 10～30wt%, the content of amorphous silica-alumina is 20～60wt%, and the content of binding agent is 15～40wt%, and wherein beta-molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 505～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.This catalyst has higher activity and middle distillates oil selectivity, and product property is high.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, be predominant cracking component especially with beta-molecular sieve and Y type molecular sieve, produce the hydrocracking catalyst of high-quality intermediate oil.
Background technology
The problems such as the market demand it have been not suitable with for being faced with petroleum resources shortage, environmental requirement increasingly stringent and oil product structure at present, the application of hydrocracking technology improves petroleum product-quality, reduction environmental pollution, the effective technology measure of increase market adaptability to changes by becoming, it has also become the of paramount importance process unit in modernization refinery.The problem that the strictest automotive fuel discharge standard makes processing inferior heavy oil be directly produced high-quality cleaning fuel becomes increasingly conspicuous, and hydrocracking technology and the supporting middle oil type catalyst development thereof of maximum production intermediate oil are the most active.
Hydrocracking technology core is hydrocracking catalyst, and the progress of its technology depends on the raising of levels of catalysts, and molecular sieve, as the main acidic components of hydrocracking catalyst, plays conclusive effect to activity, selectivity and the product quality of catalyst.The most industrialized molecular sieve type hydrocracking catalyst is generally based on Modified Zeolite Y at present, hydrocracking catalyst containing Y type molecular sieve is active good, open-loop performance is high, to the heavy constituent selective splitting performance advantages of higher rich in cyclic hydrocarbon, but it is the highest to there is intermediate oil yield, the weak points such as diesel product low temperature flow difference, especially in diesel oil deep drawing or time back-end crop oil does not produces wide cut diesel fuel, this problem is more prominent.Relative to Y type molecular sieve, beta-molecular sieve has three-dimensional twelve-ring pore structure, but not supercage structure as Y type molecular sieve, it is mainly characterized by double 6 ring unit bug hole structures of two 4 rings and four 5 rings, main channel diameter is at 0.56-0.75nm, the duct feature of beta-molecular sieve makes it in cracking reaction, the fracture of chain hydrocarbon-selective be had well effect, and there is the strongest isomery performance, can be used for Low Freezing Point middle oil fraction as cracking component, be industrially widely used.
US4847055 discloses the method for the synthesis beta-molecular sieve of a kind of improvement, wherein uses a kind of special silicon source, with TEABr as template, prepares beta-molecular sieve under conditions of crystal seed exists.This silicon source is to be added precipitant under certain condition by soluble silicon solution to prepare.The large usage quantity of the method template, and easily produce modenite and ZSM-5 stray crystal.Only as (TEA)2O/SiO2> 0.14, i.e. TEA+/SiO2> 0.28 time, the growing amount of stray crystal could be reduced.
Above-mentioned water heat transfer β zeolite needs a large amount of expensive organic formwork agent tetraethyl ammonium hydroxide, the cost major part of beta-molecular sieve synthesis to come from template, typically constitute from about 70%.Reduce template consumption, thus reduce β zeolite synthesis cost, always the focus of this area research.
Furthermore, the organic formwork agent being blocked in zeolite cavity removing must be fallen just can make it have before beta-molecular sieve uses as catalyst catalysis activity.The method of conventional removing organic formwork agent is high-temperature roasting, and owing to high-temperature roasting will destroy the structure of beta-molecular sieve so that it is degree of crystallinity declines, heat stability and hydrothermal stability are deteriorated, and consumption of template agent is the biggest, and this destructiveness is the most serious.And using the beta-molecular sieve adding a small amount of template synthesizing high-silicon aluminum ratio, the degree of crystallinity of products obtained therefrom can be the lowest, and heat stability and hydrothermal stability are poor.
CN1351959A relates to the synthetic method of a kind of molecular sieve.First Al is pressed2O3: (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, then Alusil A and Alusil B is pressed the weight ratio mixing of 1:10, proceed to after stirring in autoclave pressure, after sealing at a temperature of 100-200 DEG C, stir crystallization 15-150 hour under static or 10-150rpm rotating speed, end product through sucking filtration, wash and be dried to obtain beta-molecular sieve.Although the consumption of organic formwork can be reduced to TEAOH/SiO by this synthetic method2=0.05, but beta-molecular sieve silica alumina ratio prepared by the method is relatively low, and also the characteristic peak of beta-molecular sieve has a small amount of miscellaneous peak, has stray crystal to generate.
CN 1198404A proposes a kind of method synthesizing beta-molecular sieve, uses the composite mould plate agent formed in the basic conditions by halogenide, tetraethyl ammonium hydroxide and the fluoride of tetraethyl ammonium, makes silicon source, aluminum source and crystal seed reaction crystallization produce beta-molecular sieve.Although the method reduces template consumption, adding the productivity of beta-molecular sieve, however it is necessary that addition composite mould plate agent and crystal seed, and after silica alumina ratio is more than 30, degree of crystallinity is relatively low, heat stability and hydrothermal stability are poor.
CN101578353A describes a kind of method utilizing beta-molecular sieve to be optionally hydrocracked.Beta-molecular sieve does not carry out the mol ratio of hydrothermal treatment consists or hydrothermal treatment consists, silicon dioxide and aluminium oxide at relatively low temperatures less than 30:1 and the SF of at least 28wt%6Adsorbance, the catalyst that this beta-molecular sieve obtained by modification is prepared as cracking component, the selectivity of intermediate oil is the highest.
Summary of the invention
For weak point of the prior art, the invention provides good hydrocracking catalyst of a kind of catalytic performance and preparation method thereof.This hydrocracking catalyst uses a kind of high silica alumina ratio, high-crystallinity, bigger serface, the beta-molecular sieve of good stability and Y molecular sieve jointly to do as acidic components, and the catalyst of the present invention has higher activity and middle distillates oil selectivity, and product property is high.
Hydrocracking catalyst of the present invention, including carrier and hydrogenation active component, carrier includes beta-molecular sieve, Y molecular sieve, amorphous silica-alumina and binding agent, on the basis of the weight of carrier, the content of beta-molecular sieve is 2～20wt%, and the content of Y molecular sieve is 10～30wt%, and the content of amorphous silica-alumina is 20～60wt%, the content of binding agent is 15～40wt%, and the character of wherein said beta-molecular sieve is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 505～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.
In hydrocracking catalyst of the present invention, described beta-molecular sieve is Hydrogen beta-molecular sieve.
In hydrocracking catalyst of the present invention, described beta-molecular sieve character is preferably as follows: SiO2/Al2O3Mol ratio is 65～100, and specific surface area is 550～800m2/ g, pore volume 0.40～0.60mL/g, relative crystallinity is 110%～140%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 95%～130%.
Preferably, described beta-molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 65～100, and specific surface area is 600～750 m2/ g, pore volume 0.45～0.55mL/g, relative crystallinity is 115%～140%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 108%～130%.
In the present invention, this beta-molecular sieve was as follows through the condition of water vapour hydrothermal treatment consists: through 750 DEG C of water vapour hydrothermal treatment consists 2 hours.
In hydrocracking catalyst of the present invention, SiO in described amorphous silica-alumina2Weight content be 20%～60%, preferably 25%～40%, the character of amorphous silica-alumina is as follows: pore volume is 0.6～1.1mL/g, preferably 0.8～1.0 mL/g, and specific surface area is 300～500 m2/ g, preferably 350～500 m2/g。
In hydrocracking catalyst of the present invention, described Y molecular sieve, its character is as follows: specific surface area is 700～1000 m2/ g, pore volume is 0.45～0.90 mL/g, relative crystallinity 95%～130%, SiO2/Al2O3Mol ratio 30～100, cell parameter 2.426～2.433nm, meleic acid amount 0.1～0.4mmol/g.This Y type molecular sieve can use prior art to prepare.
In hydrocracking catalyst of the present invention, described binding agent can use binding agent commonly used in the art, it is preferred to use little porous aluminum oxide.
The hydrocracking catalyst of the present invention, described hydrogenation active metals is vib and/or the metal of the VIIIth race, and vib metals is 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, the content of vib metals (in terms of oxide) is as 10wt%～the content of 30wt% and group VIII metal (in terms of oxide) is as 4wt%～15wt%, and the content of carrier is 60.0%～86.0%.
Hydrocracking catalyst character of the present invention is as follows: specific surface area is 300～600 m2/ g, pore volume is 0.3～0.7 mL/g.
The preparation method of hydrocracking catalyst of the present invention, preparation and the load of hydrogenation active metals including carrier, wherein the preparation method of carrier includes: by the mixing of beta-molecular sieve, Y molecular sieve, amorphous silica-alumina and binding agent, molding, is then dried and roasting, makes catalyst carrier.
Beta-molecular sieve described in hydrocracking catalyst of the present invention, including following preparation process:
(1), using preparing amorphous silicon alumnium using carbonization predecessor, described amorphous silica-alumina predecessor is on the basis of the gross weight of silicon dioxide and aluminium oxide, and the content that silicon is counted with silicon dioxide is as 40wt%～75wt%, preferably 55wt%～70wt%；Its preparation process includes:
Preparation sodium aluminate solution and silicon-containing compound solution respectively；Sodium aluminate solution is mixed with part silicon-containing compound solution, 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 described remainder silicon-containing compound solution；
(2), the said mixture in step (1) stablizes 10 ~ 30 minutes in ventilated environment；
(3), by Al2O3: SiO2: Na2O:H2O=1:(62 ~ 110): (0.5～3.0): (100～500), TEAOH/SiO2Total molar ratio of=0.010 ~ 0.095, preferably SiO2/Al2O3Be 70 ~ 110, TEAOH/SiO2=0.020 ~ 0.080, in the amorphous silica-alumina predecessor of step (2) gained, add water, silicon source and template, stir, obtain silica-alumina gel, TEA represents the quaternary amine alkali cation in template；
(4), the silica-alumina gel of step (3) gained through two step dynamic crystallizations, then through filtering, washing, prepare Na beta molecular sieve；
(5), described Na beta molecular sieve carries out ammonium salt exchange and Template removal processes, and prepares beta-molecular sieve.
Preferably, in step (1), described remainder silicon-containing compound solution accounts for addition silicon-containing compound solution total amount 5wt% ~ 85wt% in terms of silicon dioxide, preferably 30wt% ~ 70wt% in terms of silicon dioxide.
Preferably, in step (1), the reaction temperature of described plastic is 10～40 DEG C, preferably 15～35 DEG C, and controlling the pH value after cemented into bundles is 8～11.
Preferably, in step (1), described silicon-containing compound solution is waterglass and/or sodium silicate solution.
Preferably, in step (1), with A12O3Quality meter, the concentration of described sodium aluminate solution is 15～55g Al2O3/
L, with SiO2Quality meter, the concentration of described silicon-containing compound solution is 50～150 gSiO2/ L, described CO2The concentration of gas is 30v% ~ 60v%.
Preferably, in step (3), generating the reaction temperature 0 of described silica-alumina gel～40 DEG C, pH value is 9.5～12.0；Being preferably, the reaction temperature generating described silica-alumina gel is 10～30 DEG C, and pH value is 10～11.
Preferably, in step (3), described silicon source is one or more in White Carbon black, silica gel, Ludox and waterglass, and described template is tetraethyl ammonium hydroxide.
Preferably, in step (4), the silica-alumina gel of step (2) gained includes through the concrete steps of two step dynamic crystallizations: the condition of first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 50～90 DEG C, and the time is 0.5～18.0 hour；The condition of second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 100～200 DEG C, and the time is 40～120 hours.
Preferably, in step (4), the condition of described first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 60～80 DEG C, and the time is 1～10 hour；The condition of described second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 120～170 DEG C, and the time is 50～100 hours.
Preferably, in step (5), ammonium salt exchange uses conventional method to carry out, as one or many ammonium salt exchanges, and Na in the beta-molecular sieve after ammonium salt exchange2O weight content is less than 0.3%；Can be through washing and the step being dried after ammonium salt exchange, the condition being wherein dried is as follows: be dried 3～6 hours at 80 DEG C ~ 150 DEG C.
Preferably, in step (5), described Template removal processes and uses aerobic high-temperature process, and treatment temperature is 400～800 DEG C, and the process time is 5～20 hours, is preferably, and treatment temperature is 500～700 DEG C, and the process time is 10～15 hours.
The preferred little porous aluminum oxide of adhesive therefor of the present invention.Aperture aluminium oxide pore volume used is 0.3～0.5 mL/g, and specific surface area is 200～400m2/g。
Y molecular sieve of the present invention, its character is as follows: specific surface area is 700～1000 m2/ g, total pore volume 0.45～0.90 mL/g, relative crystallinity 95%～130%, SiO2/Al2O3Mol ratio 30～100, cell parameter 2.426～2.433nm, meleic acid amount 0.1～0.4mmol/g.This Y type molecular sieve can use prior art to prepare.
In catalyst carrier of the present invention, amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process, prepares by conventional method in document.SiO in the amorphous silica-alumina prepared2Weight content be 20%～60%, preferably 25%～40%, the pore volume of amorphous silica-alumina is 0.6～1.1mL/g, preferably 0.8～1.0 mL/g, and specific surface area is 300～500 m2/ g, preferably 350～500 m2/g。
Catalyst of the present invention can be shaped according to actual needs, and shape can be cylindrical bars, Herba Trifolii Pratentis etc..During shaping of catalyst, it is also possible to add shaping assistant, such as peptization acid, extrusion aid etc..Catalyst carrier of the present invention used conventional method to be dried and roasting, specific as follows: be dried 3～10 hours at a temperature of 80～150 DEG C, 400～800 DEG C of roastings 3～12 hours.
In the preparation method of hydrocracking catalyst of the present invention, the load of hydrogenation active metals can use carrying method conventional in prior art, preferably infusion process, can be saturated leaching, excess leaching or complexation leaching, i.e. with the solution impregnated catalyst carrier containing required active component, carrier after dipping, at 100 DEG C～150 DEG C of dry l～12 hours, then 400 DEG C～750 DEG C of roastings 3～12 hours, prepares final catalyst.
Part silicon-containing compound, in the preparation process of beta-molecular sieve, is first added in reaction system before plastic and/or during plastic by the present invention, forms stable colloidal state and sial integrated structure.Owing to this colloid surface has a lot of hydroxyl structures, can be combined with the remainder silicon-containing compound added below well, so that amorphous silica-alumina predecessor has more stable structure.Afterwards, amorphous silica-alumina predecessor, template are mixed and made into silica-alumina gel with another part silicon source etc., so can form more nucleus in synthetic system, it is evenly dispersed in synthetic system, there is good crystallization guide effect, again through two step dynamic crystallizations, easily form complete framing structure, the beta-molecular sieve that degree of crystallinity is high.The inventive method not only can reduce the usage amount of organic formwork agent, it is also possible to synthesizes the beta-molecular sieve of high-crystallinity, high silica alumina ratio, and has more preferable heat stability and hydrothermal stability, and the beta-molecular sieve purity of the present invention is high, does not has stray crystal.And, the beta-molecular sieve of the present invention is through the exchange of simple ammonium salt and Template removal by Na beta molecular sieve, just can obtain, it is not necessary to carry out the dual-spectrum process such as dealuminzation or dealumination complement silicon again.
Beta-molecular sieve of the present invention and Y molecular sieve are collectively as cracking center, both its respective performance characteristics had been given full play to, the concerted catalysis effect that two kinds of molecular sieves produce can be made again, i.e. modified beta molecular sieve has good isomerization to the long side chain on alkane or aromatic hydrocarbons, can effectively reduce the condensation point of product, Y type molecular sieve has the highest selectivity of ring-opening to aromatic hydrocarbons simultaneously, improves the product property of purpose product.The active height of hydrocracking catalyst of the present invention, can high-output qulified midbarrel oil product (boat coal+diesel oil), can hold concurrently simultaneously and produce the hydrogenation tail oil of high-quality.
Detailed description of the invention
In order to the present invention is better described, further illustrate the present invention below in conjunction with embodiment and comparative example.But the scope of the present invention is not limited solely to the scope of these embodiments.The present invention analyzes method: specific surface area, pore volume use low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter to use x-ray diffraction method, and silica alumina ratio uses chemical method.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 50mL sodium silicate working solution, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, adding 50mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel
By Al2O3: SiO2: Na2O:H2O=1:80: 1.5: 240, TEAOH/SiO2=0.070
Total molar ratio, adds water, sodium silicate solution and tetraethyl ammonium hydroxide in the amorphous silica-alumina predecessor of step (1) gained, and control ph is 11, reaction temperature 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.
(3) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 80 DEG C, then heat to 150 DEG C, stirring crystallization 30 hours, then filters, washs, and washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve product N β-1, record relative crystallinity；N β-1, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-1, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete N β-1 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Adding appropriate water purification in Na beta-molecular sieve N β-1, and add a certain amount of ammonium nitrate, making liquid-solid ratio (weight) is 10:1, the concentration of ammonium nitrate is 2mol/L, stirring, is warmed up to 95～100 DEG C, and constant temperature stirs 2 hours, then filter, filter cake secondary again carries out ammonium salt exchange, and the condition of exchange is identical with first time, till finally washing molecule is sieved to pH value neutrality, put in dry zone and be dried, be dried 8 hours at 100～120 DEG C.Taking dried beta-molecular sieve to carry out deviating from template process, use open kiln to process, 570 DEG C of constant temperature process 15 hours, make beta-molecular sieve S β-1, XRD determining S β-1 relative crystallinity；S β-1 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 2
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 50gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 60mL sodium silicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.02, adding 40mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 50wt%.
(2) preparation of gel
By Al2O3: SiO2: Na2O:H2O=1:90: 1.7: 260, TEAOH/SiO2=
0.060 total molar ratio, adds water, sodium silicate solution and tetraethyl ammonium hydroxide in the amorphous silica-alumina predecessor of step (1) gained, and control ph is 11, reaction temperature 25 DEG C, and uniform stirring 30 minutes obtains silica-alumina gel.
(3) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 90 DEG C, then heat to 160 DEG C, stirring crystallization 30 hours, then filters, washs, and washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve product N β-2, record relative crystallinity；N β-2, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-2, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete N β-2 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Adding appropriate water purification in Na beta-molecular sieve N β-2, and add a certain amount of ammonium nitrate, making liquid-solid ratio (weight) is 10:1, the concentration of ammonium nitrate is 2mol/L, stirring, is warmed up to 95～100 DEG C, and constant temperature stirs 2 hours, then filter, filter cake secondary again carries out ammonium salt exchange, and the condition of exchange is identical with first time, till finally washing molecule is sieved to pH value neutrality, put in dry zone and be dried, be dried 8 hours at 100～120 DEG C.Taking dried beta-molecular sieve to carry out deviating from template process, use open kiln to process, 570 DEG C of constant temperature process 15 hours, make beta-molecular sieve S β-2, XRD determining S β-2 relative crystallinity；S β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 3
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 50gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO2/ L sodium silicate working solution.Take 160mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 45mL sodium silicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.02, adding 35mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 50wt%.
(2) preparation of gel is with embodiment 1, and difference is: according to Al2O3: SiO2: Na2O:H2O=1:70: 1.4: 250, TEAOH/SiO2Each material is mixed by total molar ratio of=0.062.
(3) crystallization is with embodiment 1, obtains molecular sieve N β-3, records relative crystallinity；N β-3, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；N β-3, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete N β-3 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve N β-3, with embodiment 1, is made beta-molecular sieve S β-3, XRD determining S β-3 relative crystallinity by the method for ammonium salt exchange and Template removal；S β-3 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
Embodiment 4
By 6.7 grams of S β-1 molecular sieves, 17.8 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 82.9 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtaining carrier TCAT-1, character is shown in Table 3.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CAT-1, carrier and corresponding catalyst character and are shown in Table 3.
Embodiment 5
By 11.1 grams of S β-2 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, carrier TCAT-2 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CAT-2, carrier and corresponding catalyst character and are shown in Table 3.
Embodiment 6
By 11.1 grams of S β-3 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, carrier TCAT-3 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CAT-3, carrier and corresponding catalyst character and are shown in Table 3.
Comparative example 1 (with reference to CN1351959A)
By 20.5g White Carbon black, 2mL sodium aluminate solution, 59g tetraethyl ammonium hydroxide and 0.9g sodium hydroxide, mix under room temperature and mechanical agitation, and continue stirring to raw material mix homogeneously: mixture is proceeded in autoclave pressure, after static state is aged 5 hours at a temperature of 130 DEG C after sealing, takes out and quick cooling pressure still, obtain Alusil A.120g Ludox, 6.3mL sodium metaaluminate, 6g sodium hydroxide and 17mL distilled water are mixed under room temperature and mechanical agitation, and stirs to raw material mix homogeneously, obtain Alusil B.5g Alusil A and 50g Alusil B is mixed under room temperature and mechanical agitation, and stirs and proceed in autoclave pressure to raw material mix homogeneously, after sealing at a temperature of 130 DEG C, to stir crystallization 48 hours under 60rpm rotating speed, take out and quick cooling pressure still.Product, through sucking filtration, washing, washs and is dried at 120 DEG C to neutrality, obtain Na beta-molecular sieve products C N β-1, record relative crystallinity.CN β-1, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-1, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-1 character is shown in Table 1.The characterization result of CN β-1 shows, product is the characteristic peak possessing beta-molecular sieve, but has a small amount of miscellaneous peak, i.e. has a small amount of stray crystal.
Carry out ammonium salt exchange and Template removal according to the method for embodiment 1, Na beta-molecular sieve CN β-1 is made beta-molecular sieve products C S β-1, XRD determining CS β-1 relative crystallinity；CS β-1 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
By 11.1 grams of CS β-1 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CCAT-1, carrier and corresponding catalyst character and are shown in Table 3.
Comparative example 2(is with reference to CN1198404A)
16g tetraethylammonium bromide and 1.6g sodium fluoride D are dissolved in 30g deionized water, it is sequentially added under stirring and is dissolved in 20g deionized water gained solution, 53.7g Ludox and 0.72g crystal seed by 1.67g sodium aluminate B, continue stirring 60 minutes, proceed in stainless steel cauldron, crystallization 4 days at 160 DEG C.Then filter, wash, be dried to obtain Na beta-molecular sieve products C N β-2, record relative crystallinity.CN β-2, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-2, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-2 character is shown in Table 1.
Carry out ammonium salt exchange and Template removal according to the method for embodiment 1, Na beta-molecular sieve CN β-2 is made beta-molecular sieve products C S β-2, XRD determining CS β-2 relative crystallinity；CS β-2 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
By 11.1 grams of CS β-2 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, support C TCAT-2 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CCAT-2, carrier and corresponding catalyst character and are shown in Table 3.
Comparative example 3
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, be subsequently adding 100mL sodium silicate working solution, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, then ventilating and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel is with embodiment 1；
(3) crystallization is with embodiment 1, obtains molecular sieve CN β-3, records relative crystallinity.CN β-3, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-3, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-3 character is shown in Table 1.
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-3, with embodiment 1, is made beta-molecular sieve products C S β-3, XRD determining CS β-3 relative crystallinity by the method for ammonium salt exchange and Template removal；CS β-3 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
By 11.1 grams of CS β-3 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, carrier TCCAT-3 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CCAT-3, carrier and corresponding catalyst character and are shown in Table 3.
Comparative example 4
(1) preparation of amorphous silica-alumina predecessor
Compound concentration is 40gAl2O3/ L sodium aluminate working solution, takes containing SiO2The sodium silicate solution of 28wt%, then to be diluted to concentration be 120g SiO2/ L sodium silicate working solution.Take 200mL sodium aluminate working solution to be placed in plastic cans, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%2Gas, stops logical CO when pH value reaches 10.22, adding 100mL sodium silicate working solution, then ventilate and stablize 20 minutes, obtain amorphous silica-alumina predecessor, amorphous silica-alumina predecessor is on the basis of silicon dioxide and aluminium oxide gross weight, and the content counted with silicon dioxide is as 60wt%.
(2) preparation of gel is with embodiment 1；
(3) crystallization is with embodiment 1, obtains molecular sieve CN β-4, records relative crystallinity.CN β-4, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-4, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-4 character is shown in Table 1；
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-4, with embodiment 1, is made and obtains beta-molecular sieve products C S β-4 by the method for ammonium salt exchange and Template removal, XRD determining CS β-4 relative crystallinity；CS β-4 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
By 11.1 grams of CS β-4 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, support C TCAT-4 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CCAT-4, carrier and corresponding catalyst character and are shown in Table 3.
Comparative example 5
(1) preparation of amorphous silica-alumina predecessor is with embodiment 1；
(2) preparation of gel is the most same as in Example 1, and difference is: amorphous silica-alumina predecessor, sodium silicate, tetraethyl ammonium hydroxide and water are according to Al2O3: SiO2: Na2O:H2O=1:80:1.5:240, TEAOH/SiO2Total molar ratio of=0.2；
(3) crystallization is with embodiment 1, obtains molecular sieve CN β-5, records relative crystallinity.CN β-5, after roasting in 550 DEG C of air 3 hours, records the relative crystallinity after roasting；CN β-5, after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, records the relative crystallinity after hydrothermal treatment consists, and concrete CN β-5 character is shown in Table 1；
(4) ammonium salt exchange and Template removal
Na beta-molecular sieve CN β-5, with embodiment 1, is made beta-molecular sieve products C S β-5, XRD determining CS β-5 relative crystallinity by the method for ammonium salt exchange and Template removal；CS β-5 is after 750 DEG C of water vapour hydrothermal treatment consists 2 hours, then records the relative crystallinity after hydrothermal treatment consists, the results are shown in Table 2.
By 11.1 grams of CS β-5 molecular sieves, 20 grams of Y molecular sieve (specific surface areas 740m2/ g, total pore volume 0.75mL/g, relative crystallinity 101%, SiO2/Al2O3Mol ratio 48, cell parameter 2.430nm, meleic acid amount 0.2mmol/g), 74.3 grams of amorphous silica-aluminas (pore volume 0.9mL/g, specific surface areas 350m2/ g, silicon oxide weight content 30%), 75 grams of little porous aluminum oxides of binding agent, mixed grind in chaser is put into dust technology (wherein nitric acid is 0.25 with the mol ratio of little porous aluminum oxide), add water, being rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, support C TCAT-5 is obtained.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C are dried 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst CCAT-5, carrier and corresponding catalyst character and are shown in Table 3.
Table
1
Table 1
| Feed intake SiO2/Al2O3Mol ratio | Specific surface area, m2/g | Pore volume, mL/g | SiO2/Al2O3Mol ratio | Relative crystallinity, % | Relative crystallinity *, % after roasting | The reservation degree of crystallization relatively after hydrothermal treatment consists, % | |
| 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, Na beta molecular sieve is as follows through the condition of air roasting: roasting 3 hours in 550 DEG C of air.
Table 2
| Specific surface area, m2/g | Pore volume, mL/g | SiO2/Al2O3Mol ratio | Relative crystallinity, % | The reservation degree of crystallization relatively after hydrothermal treatment consists, % | |
| 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 |
Table 3 carrier and the physico-chemical property of catalyst
| Bearer number | TCAT-1 | TCAT-2 | TCAT-3 | CTCAT-1 | CTCAT-2 | CTCAT-3 | CTCAT-4 | CTCAT-5 |
| Beta-molecular sieve, wt% | 6 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Y molecular sieve, wt% | 15 | 18 | 18 | 18 | 18 | 18 | 18 | 18 |
| Amorphous silica-alumina, wt% | 59 | 52 | 52 | 52 | 52 | 52 | 52 | 52 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 505 | 515 | 521 | 475 | 482 | 479 | 485 | 487 |
| Pore volume, mL/g | 0.75 | 0.77 | 0.79 | 0.69 | 0.70 | 0.71 | 0.72 | 0.71 |
| 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 | 412 | 417 | 430 | 384 | 382 | 387 | 396 | 394 |
| Pore volume, mL/g | 0.56 | 0.57 | 0.58 | 0.50 | 0.51 | 0.52 | 0.53 | 0.52 |
The invention described above catalyst CAT-1, CAT-2, CAT-3 and comparative example catalyst CCAT-1, CCAT-2, CCAT-3, CCAT-4, CCAT-5 are carried out active evaluation test.Test is carried out on 200mL small hydrogenation device, uses the raw materials used oil nature of one-stage serial technique to be shown in Table 4.Operating condition is as follows: hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1200:1, volume space velocity 1.5h during liquid- 1, control cracking zone nitrogen content 5～10 g/g.Catalyst Activating Test the results are shown in Table 5.
Table 4 raw oil character
| Raw oil | Iran VGO |
| Density (20 DEG C), g/cm3 | 0.9082 |
| Boiling range, DEG C | 308～560 |
| Condensation point, DEG C | 30 |
| Acid number, 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 value | 47.5 |
| Refractive power/nD 70 | 1.48570 |
Table 5 catalyst activity evaluation result
| Catalyst is numbered | CAT-1 | CAT-2 | CAT-3 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 | CCAT-5 |
| Reaction temperature, DEG C | 371 | 370 | 368 | 376 | 377 | 380 | 381 | 379 |
| < 370 DEG C of conversion ratios, wt% | 66.1 | 66.4 | 66.6 | 65.4 | 65.4 | 65.5 | 65.7 | 65.6 |
| Middle distillates oil selectivity, %(132～370 DEG C) | 89.8 | 88.9 | 88.1 | 81.9 | 82.1 | 83.8 | 84.5 | 84.8 |
| Major product character | ||||||||
| Heavy naphtha (82 ~ 132 DEG C) | ||||||||
| Virtue is latent, wt% | 66.7 | 66.8 | 66.9 | 59.4 | 59.6 | 61.2 | 61.2 | 61.5 |
| Jet fuel (132 ~ 282 DEG C) | ||||||||
| Freezing point, DEG C | <-60 | <-60 | <-60 | -52 | -54 | -58 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 3.2 | 3.3 | 3.1 | 7.0 | 7.1 | 6.0 | 5.6 | 5.0 |
| Smoke point, mm | 27 | 27 | 27 | 21 | 22 | 23 | 24 | 24 |
| Diesel oil (282 ~ 370 DEG C) | ||||||||
| Cetane number | 72 | 71 | 73 | 54 | 56 | 57 | 58 | 59 |
| Condensation point, DEG C | -21 | -20 | -23 | -6 | -7 | -8 | -9 | -10 |
| Tail oil (> 370 DEG C) | ||||||||
| BMCI | 10.5 | 10.8 | 11.0 | 17.6 | 17.1 | 14.5 | 14.6 | 14.3 |
Be can be seen that by the evaluation result of table 5 catalyst, catalyst of the present invention, on the basis of greater activity, has good selectivity, and product property is good, and especially condensation point of diesel oil and tail oil BMCI value is relatively low.
Claims (24)
1. a hydrocracking catalyst, including carrier and hydrogenation active component, carrier includes beta-molecular sieve, Y molecular sieve, amorphous silica-alumina and binding agent, on the basis of the weight of carrier, the content of beta-molecular sieve is 2～20wt%, the content of Y molecular sieve is 10～30wt%, and the content of amorphous silica-alumina is 20～60wt%, and the content of binding agent is 15～40wt%；It is characterized in that: beta-molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 60～100, and specific surface area is 505～850m2/ g, pore volume is 0.35～0.60mL/g, and relative crystallinity is 100%～148%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is more than 95%.
Catalyst the most according to claim 1, it is characterised in that: described beta-molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 65～100, and specific surface area is 550～800m2/ g, pore volume 0.40～0.60mL/g, relative crystallinity is 110%～140%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 95%～130%.
Catalyst the most according to claim 1, it is characterised in that: described beta-molecular sieve character is as follows: SiO2/Al2O3Mol ratio is 65～100, and specific surface area is 600～750 m2/ g, pore volume 0.45～0.55mL/g, relative crystallinity is 115%～140%；This beta-molecular sieve relative crystallinity after water vapour hydrothermal treatment consists is 108%～130%.
4. according to the catalyst described in claim 1,2 or 3, it is characterised in that: described beta-molecular sieve was as follows through the condition of water vapour hydrothermal treatment consists: through 750 DEG C of water vapour hydrothermal treatment consists 2 hours.
Catalyst the most according to claim 1, it is characterised in that: SiO in described amorphous silica-alumina2Weight content be 20%～60%, the character of amorphous silica-alumina is as follows: pore volume is 0.6～1.1mL/g, and specific surface area is 300～500 m2/g；It is preferably as follows: SiO in described amorphous silica-alumina2Weight content be 25%～40%, character is as follows: pore volume is 0.8～1.0 mL/g, and specific surface area is 350～500 m2/g。
Catalyst the most according to claim 1, it is characterised in that: described Y molecular sieve, its character is as follows: specific surface area 700～1000 m2/ g, total pore volume 0.45～0.90 mL/g, relative crystallinity 95%～130%, SiO2/Al2O3Mol ratio 30～100, cell parameter 2.426～2.433nm, meleic acid amount 0.1～0.4mmol/g.
Catalyst the most according to claim 1, it is characterised in that: the specific surface area of described catalyst is 300～600 m2/ g, pore volume is 0.3～0.7 mL/g.
Catalyst the most according to claim 1, it is characterised in that: described hydrogenation active metals is vib and/or the metal of the VIIIth race, and vib metals is preferably molybdenum and/or tungsten, and the metal of the VIIIth race is preferably cobalt and/or nickel.
Catalyst the most according to claim 8, it is characterized in that: on the basis of the weight of catalyst, the content that vib metals is counted with oxide is as 10wt%～30wt%, and the content that group VIII metal is counted with oxide is as 4wt%～15wt%, and the content of carrier is 60.0%～86.0%.
10. the preparation method of the arbitrary described catalyst of claim 1 ~ 9, including preparation and the load of hydrogenation active metals component of carrier, wherein the preparation method of carrier includes: beta-molecular sieve, Y molecular sieve, amorphous silica-alumina and binding agent are mixed, molding, drying and roasting, make carrier.
11. methods according to claim 10, it is characterised in that: the preparation method of described beta-molecular sieve, including:
(1), using preparing amorphous silicon alumnium using carbonization predecessor, described amorphous silica-alumina predecessor is on the basis of the gross weight of silicon dioxide and aluminium oxide, and the content that silicon is counted with silicon dioxide is as 40wt%～75wt%, preferably 55wt%～70wt%；Its preparation process includes:
Preparation sodium aluminate solution and silicon-containing compound solution respectively；Sodium aluminate solution is mixed with part silicon-containing compound solution, 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 described remainder silicon-containing compound solution；
(2), the said mixture in step (1) stablizes 10 ~ 30 minutes in ventilated environment；
(3), by Al2O3: SiO2: Na2O:H2O=1:(62 ~ 110): (0.5～3.0): (100～500), TEAOH/SiO2Total molar ratio of=0.010 ~ 0.095, preferably SiO2/Al2O3Be 70 ~ 110, TEAOH/SiO2=0.020 ~ 0.080, in the amorphous silica-alumina predecessor of step (2) gained, add water, silicon source and template, stir, obtain silica-alumina gel, TEA represents the quaternary amine alkali cation in template；
(4), the silica-alumina gel of step (3) gained through two step dynamic crystallizations, then through filtering, washing, prepare Na beta molecular sieve；
(5), described Na beta molecular sieve carries out ammonium salt exchange and Template removal processes, and prepares beta-molecular sieve.
12. methods according to claim 11, it is characterised in that: in step (1), described remainder silicon-containing compound solution accounts for addition silicon-containing compound solution total amount 5wt% ~ 85wt% in terms of silicon dioxide, preferably 30wt% ~ 70wt% in terms of silicon dioxide.
13. methods according to claim 11, it is characterised in that: in step (1), the reaction temperature of described plastic is 10～40 DEG C, preferably 15～35 DEG C, and controlling the pH value after cemented into bundles is 8～11.
14. methods according to claim 11, it is characterised in that: in step (1), described silicon-containing compound solution is waterglass and/or sodium silicate solution.
15. methods according to claim 11, it is characterised in that: in step (1), with A12O3Quality meter, the concentration of described sodium aluminate solution is 15～55g Al2O3/
L, with SiO2Quality meter, the concentration of described silicon-containing compound solution is 50～150 gSiO2/ L, described CO2The concentration of gas is 30v% ~ 60v%.
16. methods according to claim 11, it is characterised in that: in step (3), generating the reaction temperature 0 of described silica-alumina gel～40 DEG C, pH value is 9.5～12.0；Being preferably, the reaction temperature generating described silica-alumina gel is 10～30 DEG C, and pH value is 10～11.
17. methods according to claim 11, it is characterised in that: in step (3), described silicon source is one or more in White Carbon black, silica gel, Ludox and waterglass, and described template is tetraethyl ammonium hydroxide.
18. methods according to claim 11, it is characterized in that: in step (4), the silica-alumina gel of step (3) gained includes through the concrete steps of two step dynamic crystallizations: the condition of first step dynamic crystallization is: carry out crystallization 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: carry out crystallization under agitation, and temperature is 100～200 DEG C, and the time is 40～120 hours.
19. methods according to claim 11, it is characterised in that: in step (4), the condition of described first step dynamic crystallization is: carry out crystallization under agitation, and temperature is 60～80 DEG C, and the time is 1～10 hour；The condition of described second step dynamic crystallization is: carry out crystallization under agitation, and temperature is 120～170 DEG C, and the time is 50～100 hours.
20. methods according to claim 11, it is characterised in that: in step (5), ammonium salt exchange uses conventional method to carry out, and one or many ammonium salt exchanges, Na in the beta-molecular sieve after ammonium salt exchange2O weight content is less than 0.3%；Can be through washing and the step being dried after ammonium salt exchange, the condition being wherein dried is as follows: be dried 3～6 hours at 80 DEG C ~ 150 DEG C.
21. methods according to claim 11, it is characterised in that: in step (5), described Template removal processes and uses aerobic high-temperature process, treatment temperature is 400～800 DEG C, and the process time is 5～20 hours, is preferably, treatment temperature is 500～700 DEG C, and the process time is 10～15 hours.
22. methods according to claim 10, it is characterised in that: adhesive therefor is little porous aluminum oxide, and aperture aluminium oxide pore volume used is 0.3～0.5 mL/g, and specific surface area is 200～400m2/g。
23. methods according to claim 10, it is characterised in that: what described carrier used be dried and roasting condition is as follows: is dried 3～10 hours at a temperature of 80～150 DEG C, 400～800 DEG C of roastings 3～12 hours.
24. methods according to claim 10, it is characterized in that, the carrying method of hydrogenation active metals uses infusion process, i.e. with the solution impregnated catalyst carrier containing required hydrogenation active component, carrier after dipping is at 100 DEG C～150 DEG C of dry l～12 hours, then 400 DEG C～750 DEG C of roastings 3～12 hours, final catalyst is prepared.
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| CN116020540A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Supported catalyst and preparation method and application thereof |
| CN116060107A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116020540A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Supported catalyst and preparation method and application thereof |
| CN116020540B (en) * | 2021-10-25 | 2024-05-31 | 中国石油化工股份有限公司 | Supported catalyst and preparation method and application thereof |
| CN116060107A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
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| CN106140282B (en) | 2018-10-12 |
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