CN106669778A - Light oil type hydrocracking catalyst and preparation method thereof - Google Patents
Light oil type hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a light oil type hydrocracking catalyst and a preparation method thereof. The method is characterized by taking amorphous silicon aluminum and modified Y zeolite as carriers, taking group VIB and group VIII metal as hydrogenation components, and taking group IVB metal as an auxiliary agent, wherein according to the weight percentage of the catalyst, the amorphous silicon aluminum accounts for 10 to 20%, the modified Y zeolite accounts for 40 to 65%, group VIB metal oxide accounts for 10 to 20%, group VIII metal oxide accounts for 1 to 10%, and group IVB metal oxide accounts for 1 to 10%, the surface area of the catalyst BET is 350 to 650m<2>/g, the pore volume is 0.35 to 0.6ml/g, and pores with a size of 10 to 20nm account for 5% to 15% of the total pore volume. The preparation method of the catalyst adopts a mixing kneading method or sol method. The catalyst is highly adaptable to the raw materials, has relatively high cracking activity and hydrogenation activity, and is suitable for a one-stage series process for producing naphtha as a main target product.
Description
Technical field
The present invention relates to a kind of light oil type hydrogen cracking catalyst and preparation method thereof, the catalyst is suitable for processing inferior heavy oil production high-quality naphtha.
Background technology
As the feedstock oil that oil refining enterprise processes becomes weight, degradation, while the environmental consciousness of people is improved constantly, it is desirable to which oil refining enterprise produces the cry more and more higher of clean fuel using process for cleanly preparing.The production technology of cleaning must be adopted, most effectively using petroleum resources, the friendly oil product of production environment.The process for cleanly preparing as heavy oil deep processing is hydrocracked, meets the requirement of sustainable development, therefore, hydrocracking process will play more and more important effect in following petroleum refining industry.Hydrocracking catalyst is a kind of bifunctional catalyst, and it is simultaneously containing acidic components and hydrogenation component.Hydrogenation activity generally chooses VI B races of the periodic table of elements and group VIII metal is provided；And the source of lytic activity includes the carrier such as zeolite and inorganic oxide, while the carrier of hydrocracking catalyst also needs to provide specific surface and pore volume to carry hydrogenation metal and reaction compartment.
Because crude oil is constantly deteriorated, becomes weight, imported high sulfur crude oil is increased considerably, and refinery is to increase economic efficiency, start generally to adopt crude oil deep vacuum distillation technology, so that doing for vacuum distillate has brought up to 600 DEG C or so by original 520 DEG C, the impurity contents such as its density is increasing, the molecular weight of boiling range more and more higher, contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulphur nitrogen are also more and more, the difficulty being hydrocracked is considerably increased, these are proposed higher requirement to hydrocracking technology and hydrocracking catalyst.For the catalytic reaction for having the big size molecule of heavy distillate to participate in, impact of the wide-aperture hole to catalysis activity can not be ignored, under identical reaction conditions, the hole of catalyst body phase is bigger, and reactant diffusional resistance is less, more favourable to catalysis activity；There is the diffusional resistance that macropore advantageously reduces reactant in catalyst, so as to improve catalysis activity, and as the size of reaction molecular increases, its impact is more notable.There is the diffusional resistance that macropore advantageously reduces product in catalyst, so as to improve the selectivity of catalyst.Because microporous molecular mesh size is less, the molecule being relatively large in diameter in reaction raw materials is hardly diffused to inside molecular sieve pore passage, and less pore passage structure has an effect on the quick diffusion spilling of product molecule after reaction, so as to cause overcracking, reduces liquid product yield.Aperture appears as solving the problem there is provided new approaches in 2～50nm mesopore molecular sieves.But because mesopore molecular sieve hole wall is amorphous, its acid and hydrothermal stability is far short of what is expected compared with micro porous molecular sieve, which greatly limits its application as catalysis material in petroleum chemical industry.Therefore it is required that the pore structure of the catalyst of our developments is conducive to the diffusion of reactant, product to improve reaction rate and avoid excessive fragmentation as far as possible；The acidity of catalyst should have beneficial to the activity for improving catalyst and reduce the possibility that excessive fragmentation occurs.
US6174429 discloses a kind of hydrocracking catalyst.The catalyst contains the [amorphous containing aluminium of at least one acidifying of 1 ~ 99wt%, and a kind of cell parameter of 0.1 ~ 80wt% is 2.438nm, SiO2/Al2O3Chemical mol ratio is 8 or so, SiO2/Al2O3Framework mole ratio is 20 or so Y type molecular sieve, at least metal component of group VIII of 0.1 ~ 30wt%, at least one metal component of group VIB of 1 ~ 40wt%, the auxiliary agent of 0.1 ~ 20wt% and the A races element of at least one VII of 0 ~ 20wt%.The catalyst using first preparing carrier, after support the preparation method of hydrogenation metal, catalyst has preferably activity and stability, but heavy naphtha and boat yield of coal be not high.
CN94117759.9 discloses a kind of light oil type hydrogen cracking catalyst, and catalyst consists of low-Na and high-Si Y-type molecular sieve (preparing by CN90102645.x) 50 ~ 65wt%, little 10 ~ 26wt% of porous aluminum oxide, WO3
18 ~ 26%, NiO 4 ~ 6%.Its preparation method is extruded moulding after low-Na and high-Si Y-type molecular sieve mixes with little porous aluminum oxide, and article shaped high-temperature process under ammonia-water vapour atmosphere, the mixed solution dipping of carrier tungstenic, nickel after process, drying, roasting obtains finished catalyst.Catalyst prepared by the technology has higher lytic activity, but liquid receives low.
《It is hydrocracked》(Sinopec publishing house, direction morning chief editor, page 380) deliver a kind of industrial catalyst FC-24, the catalyst is newest generation industrial catalyst, it is prepared using kneading method, and hydrogenation component is Mo-Ni, cracks the Y zeolites that component is modified using Jing ammonium hexafluorosilicates dealumination complement silicon.Its physico-chemical property is：MoO3
14 ~ 16%, NiO 5 ~ 6%, SiO2
35 ~ 42%, Al2O336 ~ 46%, specific surface area>350m2/ g, pore volume>0.28cm3/ g, heap 0.77 ~ 0.83g/cm of density3.The catalyst heavy naphtha high income, activity is good.But it is to discharge fluorine-containing accessory substance in the acidic cleavage component for preparing catalyst.
CN103191775A discloses a kind of preparation method of hydrocracking catalyst.The method is that first low-temperature hydrothermal processes aluminum oxide dry glue powder, then with the solution impregnation containing hydrogenation active metals component, after drying, together with molecular sieve in the presence of peptizing agent or binding agent, through fully rolling, being molded, be dried and roasting and obtain catalyst.The inventive method can improve the pore structure of catalyst, with big specific surface area and pore volume, be conducive to hydrogenation component to coordinate with the optimization of Cracking Component.But the Modified Zeolite Y silica alumina ratio that catalyst is selected is high, acid site number is few, the low (C of infrared acidityi=0.75mmol/g), and catalyst body phase lacks macropore, and height is done, vacuum distillate inferior is detrimental to the transmission of material processing, affect the performance of catalyst activity, the diffusion of product is had an effect on simultaneously, causes excessive fragmentation, affect liquid yield.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of light oil type hydrogen cracking catalyst and preparation method thereof.The catalyst is strong to adaptability to raw material, with higher lytic activity and hydrogenation activity, is suitable for produce naphtha as the one-stage serial technical process of main purpose product.
A kind of light oil type hydrogen cracking catalyst, with amorphous silicon aluminium and modified Y molecular sieve as carrier, with VI B races and VIII race's metal as hydrogenation component, with IV B races metal as auxiliary agent；By catalyst weight content meter, amorphous silica-alumina accounts for 10 ~ 20%, modified Y molecular sieve accounts for 40 ~ 65%, preferably 50 ~ 60%, and VI B family metal oxides account for 10 ~ 20%, preferably 12 ~ 18%, VIII family metal oxide accounts for 1 ~ 10%, preferably 3 ~ 8%, and IV B family metal oxides account for 1 ~ 10%, preferably 3 ~ 8%, the catalyst BET surface area is 350 ~ 650m2/ g, pore volume is 0.35 ~ 0.6ml/g, and aperture accounts for the 5% ~ 15% of total pore volume for the hole of 10 ~ 20nm, and the modified Y molecular sieve property is as follows：SiO2/Al2O3=8~13（Mol ratio）, Na2O≤0.15wt%, 2.435 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 780 ~ 860m of specific surface area2/ g, 0.42 ~ 0.5ml/g of pore volume, infrared acidity Ci=0.9 ~ 1.3mmol/g, more than 1.5
Nm secondary pores are >=20%, preferably 20% ~ 30%.
In catalyst of the present invention, the VI B family metal oxides are molybdenum oxide and/or tungsten oxide, and IV B family metal oxides are nickel oxide and/or cobalt oxide, and IV B family metal oxides are zirconium oxide and/or titanium oxide.
A kind of preparation method of light oil type hydrogen cracking catalyst, using kneading method or sol method preparation altogether, it is preferred to use altogether prepared by sol method.The sol method preparation process altogether comprises the steps：
（1）The salting liquid of the silicon source for preparing, silicon source, hydrogenation metal and promoter metal is mixed on request, adds precipitating reagent that gelatinous mixture is obtained；
（2）To step（1）Modified Y zeolite and water-soluble resin is added to carry out high temperature ageing in the gelatinous mixture of preparation；
（3）Slurries after aging are filtered, washed, being dried, being molded, roasting is obtained hydrocracking catalyst.
The concrete preparation process of light oil type hydrogen cracking catalyst of the present invention is as follows：Prepare containing silicon source, silicon source, promoter metal, hydrogenation metal salting liquid, by catalyst proportion measure, by each solution add plastic cans in；Mixed solution is warming up into 55 ~ 70 DEG C, adds precipitating reagent to carry out plastic, the amount for adding precipitating reagent is defined by pH=7.5 ~ 8.5 for controlling slurries, makes gelatinous mixture；It is subsequently adding modified Y zeolite and water-soluble resin, the addition of modified Y zeolite accounts for the 40 ~ 65% of final total catalyst weight, the addition of water-soluble resin is the 1% ~ 8% of sediment slurry quality, it is preferred that 2% ~ 5%, the temperature of system is risen into 110 ~ 150 DEG C, aging 1 ~ 6 hour, aging pH value 7.5 ~ 8.5, ageing time was 1.0 ~ 6.0 hours；Slurries cooling after aging, filter, washing, be then more than 60wt% in 105 ~ 120 DEG C of drying and dehydratings to butt, roll, extruded moulding is in 550 ~ 660 DEG C of roastings, 2 ~ 5 hours prepared light oil type hydrogen cracking catalysts.
In said method, described hydrogenation metal is VI B races and VIII race's metal, and promoter metal is IV B races metal.The mode of being preferably added is first to mix the salting liquid of silicon source, silicon source, IV B races metal salt solution, promoter metal, then precipitating reagent is added dropwise, stop being added dropwise when the pH of solution reaches 5-5.5, add VI B family metal oxides, finally continue to be added dropwise precipitating reagent to pH7.5 ~ 8.5.Above-mentioned feed postition can improve the activity of catalyst.
In said method, described silicon source is preferred waterglass one or more in Ludox, waterglass, white carbon.Described silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, preferred aluminium chloride.The salt of hydrogenation metal is ammonium metatungstate, sodium tungstate, ammonium molybdate, sodium molybdate, nickel nitrate, nickel chloride, cobalt nitrate, cobaltous sulfate (CoSO4·7H2O one or more in), the salt of promoter metal is zirconium oxychloride (ZrOCI2·8H2O), titanium tetrachloride (TiCl4) in one or more.Described precipitating reagent be the NaOH aqueous solution, ammonia spirit, at least one of ammonium carbonate solution, preferred ammonia spirit.
In said method, described water-soluble resin includes but is not limited to one or more in water-soluble polypropylene acid resin, water soluble polyurethane resin, water-soluble epoxy resin, water soluble phenol resin, preferred water-soluble polypropylene acid resin.Water-soluble resin can adopt commercial goods or be made by oneself according to prior art.
In said method, modified Y molecular sieve is obtained by carrying out hydrothermal dealumination and chemical dealuminization to conventional Y molecular sieve.Modified Y molecular sieve property is as follows：SiO2/Al2O3=8~13（Mol ratio）, Na2O≤0.15wt%, 2.435 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 780 ~ 860m of specific surface area2/ g, 0.42 ~ 0.5ml/g of pore volume, infrared acidity Ci=0.9 ~ 1.3mmol/g, is >=20%, preferably 20% ~ 30% more than 2nm secondary pores.
In said method, adopt pH the material after filtration is washed for the ammonium acetate solution of 7.5-8.5, wash to sodium mass content and be less than 0.1m%.Catalyst activity can be improved using ammonium acetate solution washing.
The catalyst that the present invention is provided has the advantage that：Active material is carried as carrier using amorphous silica-alumina, active component can be made to be dispersed on carrier surface, improve the catalytic efficiency of unit mass active component, amorphous silica-alumina is both the carrier of hydrogenation metal, be again cracking component donor.The catalyst of the present invention can make modified Y zeolite component and amorphous silicon aluminium be uniformly dispersed using the preparation method of co-precipitation, so as to improve the utilization rate of acidic components；Modified Y zeolite and water-soluble resin is added to carry out high temperature ageing after the co-precipitation of catalyst preparation process, the concentration pore size distribution of larger pore volume, higher specific surface, 10 ~ 20nm can be obtained, improve reaction rate and avoid excessive fragmentation as far as possible, make catalyst obtain high lytic activity and high liquid yield.
Catalyst of the present invention be suitable for produce naphtha be main purpose product one-stage serial technical process process vacuum distillate when, it is strong to adaptability to raw material, show catalyst and there is the advantages of high lytic activity, Hydrogenation are good, and liquid yield is high.
Specific embodiment
Modified Y molecular sieve used is prepared by the method for the description of example 2 in Chinese patent 96119840.0 in the embodiment of the present invention, and specific preparation process is as follows：1. 1000 grams of the NaY zeolite for being produced with Wenzhou catalyst plant is placed in per liter of (NH containing 150g4)2SO4The aqueous solution in stir, be warming up to 90 ~ 100 DEG C and kept for 1 hour, then filter, repeat to wash away SO after aforesaid operations 3 times4 2+；2. product derived above is placed in tube furnace and is passed through nitrogen intensification simultaneously, risen to 600 DEG C and stop logical nitrogen, keep pressure in 0.1MPa, Temperature fall after maintaining 2 hours；3. the product obtained after hydro-thermal process is placed in into 1 liter of CH containing 154g3COONH4With 150g CH3Process in the aqueous solution of COOH, then filter, wash, be dried, that is, obtain modified Y zeolite.Its physico-chemical property is：SiO2/Al2O3=10.98, Na2O=0.10%, degree of crystallinity 96%, lattice constant 2.442nm, specific surface area 807m2/ g, pore volume 0.46ml/g, infrared acidity Ci=1.10mmol/g, is 22% more than 1.7nm secondary pores.
The polyacrylic resin adopted in embodiment is prepared by the method for embodiment 1 in Chinese patent CN101935447B, and concrete preparation process is as follows：First 750 grams of the polyethylene glycol that molecular weight is 600 is mixed for 250 grams with polyvinylpyrrolidone, keeping temperature is 25 ~ 30 DEG C, stirring, solution is obtained after it is completely dissolved, take 20 milliliters of the solution and be mixed into glue for 80 milliliters with transparent Lauxite liquid, it is 10 milliliters by the 10% addition coagulator glacial acetic acid of 100 milliliters of cumulative volumes of glue, pumping gas is controlled in being sufficiently stirred for and using 2 ~ 5 minutes to producing without a large amount of bubbles, standing treats that again bubble-free obtains final product water-soluble resin on surface.
The following examples are used to illustrate in greater detail the present invention, but the scope of the present invention is not limited solely to the scope of these embodiments.
Example 1
Catalyst A prepared by the inventive method, catalyst weight is consisted of：WO3
15.0%, NiO 5.0%, ZrO2
4.5%, amorphous silicon aluminium is 15.5%, and wherein modified Y molecular sieve content is 60.0 %.
Concrete preparation process is as follows：
(1) prepare and contain WO3Concentration is the sodium tungstate solution of 75g/L；
(2) it is 150g/L to prepare concentration containing NiO respectively
Nickel chloride solution, containing ZrO2Concentration for 150g/L zirconyl chloride solution, containing Al2O3Concentration is the liquor alumini chloridi of 100g/L, and 3 kinds of solution mix and add deionization to dilute；
(3) prepare and contain SiO2Concentration is the water glass solution of 75g/L, under agitation waterglass is added in (2)；
(4) (3) are heated into 50 DEG C, the ammoniacal liquor of 10wt% is added dropwise under agitation carries out plastic, stop that ammoniacal liquor is added dropwise when slurries pH reaches 5.2；
(5) ammoniacal liquor that 10wt% is added dropwise will in (1) addition (4), be continued under agitation to slurries pH arrival 8.0；
(6) finely ground modified Y molecular sieve (SiO is added while slurries heat up2/Al2O3=10.98, Na2O=0.10%, relative crystallinity 96%, lattice constant 2.442nm, specific surface area 807m2/ g, pore volume 0.46ml/g, infrared acidity Ci=1.10mmol/g, more than 1.7nm secondary pores for 22%), polyacrylic resin, the addition of water-soluble resin is the 2% of sediment slurry quality, is sufficiently mixed；
(7) system temperature is risen into 120 ± 2 DEG C, control ph 8.0 ± 0.1, aging 4 hours；
(8) slurries carry out cooling filtration, and the filter cake ammonium acetate solution of pH=8.0 is washed to sodium content and is less than 0.1m%；
(9) filter cake is more than 60% in 105 DEG C of drying and dehydratings to butt, rolls, extruded moulding；It is last hydrocracking catalyst finished product A of the present invention, specific surface area 405m of catalyst to be obtained within 3 hours in 650 DEG C of roastings2/ g, pore volume 0.46ml/g, aperture accounts for the 5% of total pore volume for the hole of 10 ~ 20nm.
Example 2
Catalyst B prepared by the inventive method, catalyst weight is consisted of：WO3
15.5%, NiO 5.0%, ZrO2
4.5%, amorphous silicon aluminium 10%, modified Y molecular sieve content is 65.0 %.
Concrete preparation process is as follows：
(1) prepare and contain WO3Concentration is the sodium tungstate solution of 75g/L；
(2) it is 150g/L to prepare concentration containing NiO respectively
Nickel chloride solution, containing ZrO2Concentration for 150g/L zirconyl chloride solution, containing Al2O3Concentration is the liquor alumini chloridi of 100g/L, and 3 kinds of solution mix and add deionized water to dilute；
(3) prepare and contain SiO2Concentration is the water glass solution of 75g/L, under agitation waterglass is added in (2)；
(4) (3) are heated into 50 DEG C, the ammoniacal liquor of 10wt% is added dropwise under agitation carries out plastic, stop that ammoniacal liquor is added dropwise when slurries pH reaches 5.2；
(5) ammoniacal liquor that 10wt% is added dropwise will in (1) addition (4), be continued under agitation to slurries pH arrival 8.0；
(6) finely ground modified Y molecular sieve (SiO is added while slurries heat up2/Al2O3=10.98, Na2O=0.10%, relative crystallinity 96%, lattice constant 2.442nm, specific surface area 807m2/ g, pore volume 0.46ml/g, infrared acidity Ci22%) and polyacrylic resin=1.10mmol/g, more than 1.7nm secondary pores for, the addition of water-soluble resin is the 5% of sediment slurry quality, is sufficiently mixed；
(7) system temperature is risen into 120 ± 2 DEG C, control ph 8.0 ± 0.1, aging 4 hours；
(8) slurries carry out cooling filtration, and the filter cake ammonium acetate solution of pH=8.0 is washed to sodium content and is less than 0.1m%；
(9) filter cake is more than 60% in 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；It is last hydrocracking catalyst finished product B of the present invention, specific surface area 412m of catalyst to be obtained within 3 hours in 650 DEG C of roastings2/ g, pore volume 0.47ml/g, aperture accounts for the 15% of total pore volume for the hole of 10 ~ 20nm.
Example 3
Catalyst C prepared by the inventive method, preparation method changes Mo into example 1, the hydrogenation component of catalyst by W.Specific surface area 407m of catalyst2/ g, pore volume 0.46ml/g, aperture accounts for the 10% of total pore volume for the hole of 10 ~ 20nm.
Comparative example 1
Catalyst is constituted with embodiment 1, and difference is that polyacrylic resin is added without in preparation process, and reference catalyst D is obtained.
Comparative example 2
Industrial catalyst FC-24 is used as reference catalyst E.
Comparative example 3
Catalyst is constituted with embodiment 1, and difference is that high temperature ageing process is changed into conventional aging at temperature in preparation process, and aging temperature is 80 DEG C（Less than 100 DEG C）.Prepared reference catalyst F
Example 4
Catalyst A, B, C and reference catalyst D, E, F prepared by the inventive method carries out performance evaluation in small-sized being hydrocracked on evaluating apparatus, reaction raw materials are vacuum distillate, flow process is once passed through using one-stage serial, feedstock oil enters cracking zone after an anti-refining stage is refined, and evaluation result see the table below 1.
Table 1
①
2. heavy naphtha relative selectivity=heavy naphtha yield/(heavy naphtha yield+light naphthar yield)
Evaluating data from table can be seen that：When the catalyst of the present invention is used to process heavy raw oil, hydrogenation cracking activity is better than reference catalyst, and liquid yield is higher than reference catalyst, and heavy naphtha yield is also higher, and heavy naphtha relative selectivity is apparently higher than reference agent.Catalyst A, B, C of the present invention can reach The effect of invention, and catalyst B modified Y molecular sieves consumption is the 5/6 of catalyst A, and lytic activity reduces by 3 DEG C, it is seen that modified Y molecular sieve consumption is obvious to the activity influence of catalyst.The modified Y molecular sieve of catalyst C is identical with catalyst A, and hydrogenation metal is changed to Mo-Ni by W-Ni, and the reactivity worth of catalyst does not have significant change.
Claims (14)
1. a kind of light oil type hydrogen cracking catalyst, it is characterised in that：The catalyst with amorphous silicon aluminium and modified Y molecular sieve as carrier, with VI B races and VIII race's metal as hydrogenation component, with IV B races metal as auxiliary agent；By catalyst weight content meter, amorphous silica-alumina accounts for 10 ~ 20%, and modified Y molecular sieve accounts for 40 ~ 65%, and VI B family metal oxides account for 10 ~ 20%, and VIII family metal oxide accounts for 1 ~ 10%, and IV B family metal oxides account for 1 ~ 10%, and the catalyst BET surface area is 350 ~ 650m2/ g, pore volume is 0.35 ~ 0.6ml/g, and aperture accounts for the 5% ~ 15% of total pore volume for the hole of 10 ~ 20nm, and the modified Y molecular sieve property is as follows：SiO2/Al2O3=8~13（Mol ratio）, Na2O≤0.15wt%, 2.435 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 780 ~ 860m of specific surface area2/ g, 0.42 ~ 0.5ml/g of pore volume, infrared acidity Ci=0.9 ~ 1.3mmol/g, is >=20% more than 1.5 nm secondary pores.
2. catalyst according to claim 1, it is characterised in that：Modified Y molecular sieve accounts for 50 ~ 60%, and VI B family metal oxides account for 12 ~ 18%, and VIII family metal oxide accounts for 3 ~ 8%, and IV B family metal oxides account for 3 ~ 8%, is 20% ~ 30% more than 1.5 nm secondary pores.
3. catalyst according to claim 1, it is characterised in that：The VI B family metal oxides are molybdenum oxide and/or tungsten oxide, and IV B family metal oxides are nickel oxide and/or cobalt oxide, and IV B family metal oxides are zirconium oxide and/or titanium oxide.
4. the method for the arbitrary catalyst preparation of a kind of claims 1 to 3, it is characterised in that：Using kneading method or sol method preparation altogether.
5. method according to claim 4, it is characterised in that：The sol method preparation process altogether comprises the steps：
（1）The salting liquid of the silicon source for preparing, silicon source, hydrogenation metal and promoter metal is mixed on request, adds precipitating reagent that gelatinous mixture is obtained, described hydrogenation metal is VI B races and VIII race's metal, and promoter metal is IV B races metal；
（2）To step（1）Modified Y zeolite and water-soluble resin is added to carry out high temperature ageing in the gelatinous mixture of preparation；
（3）Slurries after aging are filtered, washed, being dried, being molded, roasting is obtained hydrocracking catalyst.
6. method according to claim 5, it is characterised in that：Altogether the concrete preparation process of sol method is as follows：Prepare containing silicon source, silicon source, promoter metal, hydrogenation metal salting liquid, by catalyst proportion measure, by each solution add plastic cans in；Mixed solution is warming up into 55 ~ 70 DEG C, adds precipitating reagent to carry out plastic, the amount for adding precipitating reagent is defined by pH=7.5 ~ 8.5 for controlling slurries, makes gelatinous mixture；It is subsequently adding modified Y zeolite and water-soluble resin, the addition of modified Y zeolite accounts for the 40 ~ 65% of final total catalyst weight, the addition of water-soluble resin is the 1% ~ 8% of sediment slurry quality, the temperature of system is risen into 110 ~ 150 DEG C, aging 1 ~ 6 hour, aging pH value 7.5 ~ 8.5, ageing time is 1.0 ~ 6.0 hours；Slurries cooling after aging, filter, washing, be then more than 60wt% in 105 ~ 120 DEG C of drying and dehydratings to butt, roll, extruded moulding is in 550 ~ 660 DEG C of roastings, 2 ~ 5 hours prepared light oil type hydrogen cracking catalysts.
7. method according to claim 5, it is characterised in that：The salting liquid of silicon source, silicon source, IV B races metal salt solution, promoter metal is mixed first, precipitating reagent is then added dropwise, stop being added dropwise when the pH of solution reaches 5-5.5, add VI B family metal oxides, finally continue to be added dropwise precipitating reagent to pH7.5 ~ 8.5.
8. method according to claim 6, it is characterised in that：Described silicon source is one or more in Ludox, waterglass, white carbon.
9. method according to claim 6, it is characterised in that：Described silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate.
10. method according to claim 6, it is characterised in that：The salt of hydrogenation metal is one or more in ammonium metatungstate, sodium tungstate, ammonium molybdate, sodium molybdate, nickel nitrate, nickel chloride, cobalt nitrate, cobaltous sulfate, and the salt of promoter metal is one or more in zirconium oxychloride, titanium tetrachloride.
11. methods according to claim 6, it is characterised in that：Described precipitating reagent is at least one in the NaOH aqueous solution, ammonia spirit, ammonium carbonate solution.
12. methods according to claim 6, it is characterised in that：Described water-soluble resin includes but is not limited to one or more in water-soluble polypropylene acid resin, water soluble polyurethane resin, water-soluble epoxy resin, water soluble phenol resin.
13. methods according to claim 5, it is characterised in that：Modified Y molecular sieve is obtained by carrying out hydrothermal dealumination and chemical dealuminization to conventional Y molecular sieve, and modified Y molecular sieve property is as follows：SiO2/Al2O3=8~13（Mol ratio）, Na2O≤0.15wt%, 2.435 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 780 ~ 860m of specific surface area2/ g, 0.42 ~ 0.5ml/g of pore volume, infrared acidity Ci=0.9 ~ 1.3mmol/g, is >=20%, preferably 20% ~ 30% more than 2nm secondary pores.
14. methods according to claim 5, it is characterised in that：Adopt pH the material after filtration is washed for the ammonium acetate solution of 7.5-8.5, wash to sodium mass content and be less than 0.1%.
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| CN114433134A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| CN114471594A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
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| CN109718834A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Modified molecular screen and its preparation method and application |
| CN109718834B (en) * | 2017-10-30 | 2022-03-11 | 中国石油化工股份有限公司 | Modified molecular sieve and preparation method and application thereof |
| CN111087015A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Vanadium removal process for crude titanium tetrachloride |
| CN111468097A (en) * | 2020-03-24 | 2020-07-31 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN111468097B (en) * | 2020-03-24 | 2023-03-03 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN111672534A (en) * | 2020-06-10 | 2020-09-18 | 中国石油天然气集团有限公司 | Hydrocracking catalyst, preparation method and application thereof |
| CN111672534B (en) * | 2020-06-10 | 2023-10-03 | 中国石油天然气集团有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
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| CN114471594B (en) * | 2020-10-26 | 2024-01-12 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN114433134A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| CN114433134B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| CN114713270A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Light oil type hydrocracking catalyst, preparation method thereof and vulcanization type hydrocracking catalyst |
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