CN106669770B - A kind of silica-alumina supports and preparation method thereof containing molecular sieve - Google Patents

A kind of silica-alumina supports and preparation method thereof containing molecular sieve Download PDF

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CN106669770B
CN106669770B CN201510750641.3A CN201510750641A CN106669770B CN 106669770 B CN106669770 B CN 106669770B CN 201510750641 A CN201510750641 A CN 201510750641A CN 106669770 B CN106669770 B CN 106669770B
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molecular sieve
silica
water
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silicon source
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CN106669770A (en
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阮彩安
杜艳泽
秦波
柳伟
张晓萍
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The present invention discloses a kind of silica-alumina supports and preparation method thereof containing molecular sieve.The silica-gel carrier containing modified Y zeolite 5% ~ 30%, contains amorphous silicon aluminium 70% ~ 95%, the support is as follows: BET surface area is 350 ~ 650m in terms of weight content2/ g, Kong Rong are 0.60 ~ 1.20ml/g, and aperture is that the hole of 10 ~ 20nm accounts for the 15% ~ 35% of total pore volume.The preparation step of silica-gel carrier is as follows: (1) preparing the mixed solution containing silicon source and silicon source and the obtained gelatinous mixture of precipitating reagent is added；(2) modified Y zeolite is added in the gelatinous mixture prepared to step (1) and water-soluble resin carries out high temperature ageing；(3) slurries after aging are filtered, wash, drying, forming, roasting the obtained silica-alumina supports containing molecular sieve.The carrier comprehensive performance is prominent, the hydrocracking catalyst suitable for heavy distillate secondary operation fecund intermediate oil.

Description

A kind of silica-alumina supports and preparation method thereof containing molecular sieve
Technical field
The silica-alumina supports and preparation method thereof containing molecular sieve that the present invention relates to a kind of relate in particular to a kind of be used as plus hydrogen Silica-alumina supports of Cracking catalyst and preparation method thereof, the carrier add suitable for petroleum secondary operation fecund intermediate oil Hydrogen Cracking catalyst.
Background technique
Be hydrocracked is that heavy raw oil carries out adding hydrogen, desulfurization, denitrogenation, hydrocarbon in the presence of high temperature and pressure faces hydrogen and catalyst Molecule recurring structure is reset and a kind of conversion process of the reactions such as cracking.Hydrocracking technology has adaptability to raw material strong, product It is high-quality, the advantages that intermediate oil high income, tail oil added value is high.Hydrocracking catalyst is by hydrogenation component and acid group The bifunctional catalyst being grouped as, its lytic activity derive from the acidity of carrier.The raw material for being hydrocracked processing mainly subtracts It presses distillate (VGO), boiling range is generally 350~550 DEG C, and carbon atom number is usually 22~35, molecular weight substantially 280~450. For the catalysis reaction for having big size molecule to participate in, influence of the hole of large aperture to catalytic activity be can not be ignored, identical anti- Under the conditions of answering, the hole of caltalyst phase is bigger, and reactant diffusional resistance is smaller, more advantageous to catalytic activity；Exist in catalyst Macropore advantageously reduces the diffusional resistance of reactant, so that catalytic activity is improved, and as the size of reaction molecular increases, It influences more significant.Carbon atom number and molecular weight additionally, due to diesel oil distillate are about the half of VGO, to evaporate among fecund Point oil, must just reduce the second pyrolysis of raw molecule to the greatest extent, there are the diffusions that macropore advantageously reduces product in catalyst Resistance, to improve the selectivity of catalyst.Since microporous molecular mesh size is smaller, the molecule being relatively large in diameter in reaction raw materials is very Difficulty is diffused into inside molecular sieve pore passage, and lesser cellular structure has an effect on the quick diffusion spilling of product molecule after reaction, So as to cause secondary cracking, liquid product yield is reduced.Aperture 2~50nm mesopore molecular sieve appearance to solve this problem Provide new approaches.But since mesopore molecular sieve hole wall is amorphous, acid and hydrothermal stability wants difference very compared with micro porous molecular sieve More, which greatly limits its applications as catalysis material in petrochemical industry.Therefore it is required that we develop carrier and The pore structure of catalyst is conducive to the diffusion of reactant, product to improve reaction rate and avoid excessive fragmentation as far as possible；Carrier Acidity should have be conducive to improve catalyst activity and reduce second pyrolysis occur a possibility that.
103100436 B of CN discloses a kind of preparation method of catalyst carrier dry gel powder.This method comprises: without fixed The mixture of molecular sieve and organic amine is added during shape sial plastic, carries out aging after amorphous silica-alumina cemented into bundles, so By being filtered, washed, drying, catalyst carrier dry gel powder is obtained.The inventive method can be such that sial arranges in molecular sieve surface Orderly, it equably deposits, and enhances the binding force of molecular sieve and sial, avoid amorphous silica-alumina and occur between molecular sieve The phenomenon that reuniting or even blocking duct, and it is mutually communicated the duct of sial and molecular sieve, send out sial and molecular sieve sufficiently Synergistic effect is waved, the service performance of catalyst is improved.Kong Rongjun≤0.75ml/g that the inventive embodiments obtain, i.e. carrier are dry Rubber powder hole Rong Bu great, the aperture of carrier dry gel powder are also little.
CN00123131.6 discloses a kind of middle oil type hydrocracking catalyst, it is carried using amorphous silica-alumina as main carrier Contain modified Y molecular sieve, the quality composition and physico-chemical property of catalyst are as follows: WO in body322.0%, NiO9.0%, ZrO27.0%, SiO233.0%, Al2O329.0%, specific surface area 260m2/ g, Kong Rong 0.36ml/g.Modified Y molecular sieve accounts for total catalyst weight 7.0%, modified molecular screen SiO2/Al2O3Molar ratio is 17, relative crystallinity 93%, specific surface area 800m2/ g, > 1.7 × 10-10m The total hole hole Zhan 45%.The catalyst is mainly used in the technical process of voluminous intermediate oil, however since the molecular sieve is used Amount is few, causes the activity of catalyst not high, this requires improving hydrocracking reaction temperature, so that the thermal cracking trend of molecular sieve Enhance and inhibit hydrogenation reaction, improves the middle distillates oil selectivity of catalyst unobvious, product quality is also impacted.
CN102553650B discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, it is characterised in that: 1. by Y It is mixed with Beta molecular sieve and deionized water, is then added to cetyl trimethylammonium bromide and alkylphenol-polyethenoxy In the mixed solution of ether, after mixing evenly, silicon source and silicon source solution is added dropwise, the pH value for adjusting system is 8 ~ 12, steady to system Material is transferred in crystallizing kettle 80 ~ 120 DEG C, 24 ~ 72h of crystallization after fixed, filters, dry, roasting obtains hydrogen after ammonium exchanges again The bis- microporous-mesoporous composite molecular sieves of type Y-Beta/MCM-41；2. by double microporous-mesoporous composite molecular sieves, amorphous silica-alumina, big Porous aluminum oxide, adhesive and extrusion aid are uniformly mixed, after extrusion after 2 ~ 4h of resulting wet carrier strip elder generation room temperature health, in 80 ~ Then 150 DEG C of dry 2 ~ 4h roast 4 ~ 8h at 400 ~ 600 DEG C and obtain the carrier of hydrocracking catalyst.The catalyst Carrier wishes acidity and MC M- that Y-Beta micro porous molecular sieve is obtained in conjunction with micropore, the respective advantage of mesoporous two kinds of molecular sieves The macropore of 41 mesopore molecular sieves.It is well-known the reason is that the thermal stability of MCM-41 mesopore molecular sieve is bad, so far not Realize industrial application.
CN1253988A discloses a kind of using hydrocracking catalyst oily in the fecund of glue method preparation altogether, the catalyst Containing the modified Y molecular sieve by the preparation of CN96119840.0 method, weight composition are as follows: WO323.0%, NiO9.0%, ZrO2 7.0%, SiO230.0%, Al2O3Surplus, its specific surface area 290m2/ g, Kong Rong 0.37ml/g.Change selected by the catalyst Property Y molecular sieve acid amount height (Ci=0.9 ~ 1.1mmol/g), good catalyst activity, but middle distillates oil selectivity is bad.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of sial as hydrocracking catalyst Carrier and preparation method thereof.The carrier comprehensive performance is prominent, suitable for heavy distillate secondary operation fecund intermediate oil Hydrocracking catalyst.
A kind of preparation method of the silica-alumina supports containing molecular sieve, includes the following steps:
(1) it prepares the mixed solution containing silicon source and silicon source and precipitating reagent is added and gelatinous mixture is made；
(2) modified Y zeolite is added in the gelatinous mixture prepared to step (1) and water-soluble resin progress high temperature is old Change；
(3) slurries after aging are filtered, wash, drying, forming, roasting the obtained silica-alumina supports containing molecular sieve.
The specific preparation process of silica-alumina supports of the present invention containing molecular sieve is as follows: by the mixed solution containing silicon source and silicon source It is added in plastic cans, silicon source, the proportion of silicon source are SiO in mixed solution2/ Al2O3=0.1~1.2；Mixed solution is warming up to 55 ~ 70 DEG C, precipitating reagent is added, the amount that precipitating reagent is added is subject to pH=7.5 ~ 8.5 for controlling slurries, and gelatinous mixture is made； Modified Y zeolite is added after precipitating and water-soluble resin, the additional amount of modified Y zeolite account for the 5 ~ 30% of final total weight of carrier, The additional amount of water-soluble resin is the 1% ~ 8%, preferably 2% ~ 6% of sediment slurry quality, and the temperature of system is risen to 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, filtering after aging；Washing It is greater than 60wt% in 105 ~ 120 DEG C of drying and dehydratings to butt afterwards, rolls, extruded moulding is roasted 2 ~ 5 hours at 550 ~ 660 DEG C and is made Silica-alumina supports containing molecular sieve.
In the above method, the silicon source is silica solution, waterglass, one or more in white carbon black, preferably waterglass.Institute The silicon source stated is one of sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate or a variety of, preferably aluminium chloride.The precipitating reagent is At least one of NaOH aqueous solution, ammonia spirit, ammonium carbonate solution, preferably ammonia spirit.
In the above method, the water-soluble resin includes but is not limited to water-soluble polypropylene acid resin, water-soluble poly ammonia One or more of ester resin, water-soluble epoxy resin, water soluble phenol resin, preferably water-soluble polypropylene acid resin.Water Soluble resin can use commercial goods or be made by oneself according to the prior art.
In the above method, modified Y molecular sieve is by being made conventional Y molecular sieve progress hydrothermal dealumination and chemical dealuminization.Change Y molecular sieve property after property is as follows: SiO2/Al2O3=8 ~ 15(molar ratio), Na2O≤0.15wt%, lattice constant 2.426 ~ 2.445nm, relative crystallinity 92 ~ 99%, 750 ~ 860m of specific surface area2/ g, Kong Rong 0.42 ~ 0.55ml/g, infrared acidity Ci= 0.48 ~ 1.3mmol/g, being greater than 2nm secondary pore is >=20%, water adsorption amount (25 DEG C of P/P0It=0.1) is 2.5 ~ 5.5wt%；It is preferred that SiO2/Al2O3=10 ~ 15(molar ratio), Na2O≤0.15wt%, lattice constant be 2.426 ~ 2.432nm, specific surface area 750 ~ 850m2/ g, Kong Rong 0.45 ~ 0.55ml/g, infrared acidity Ci=0.48 ~ 0.58mmol/g, being greater than 2nm secondary pore is >=50%.
In the above method, pH is used to wash for the ammonium acetate solution of 7.5-8.5 to filtered material, washing to sodium Content is less than 0.1m%.The meleic acid amount that can be improved carrier using ammonium acetate solution washing, improves Carriers Active.
A kind of silica-alumina supports containing molecular sieve prepared using the above method, in terms of weight content, containing modified Y zeolite 5% ~ 30%, contain amorphous silicon aluminium 70% ~ 95%, the support is as follows: BET surface area is 350 ~ 650m2/ g, Kong Rong be 0.60 ~ 1.20ml/g, aperture are that the hole of 10 ~ 20nm accounts for the 15% ~ 35% of total pore volume.
Catalyst carrier provided by the invention has the advantages that carrier is can to carry active material, can make active group Dispersion on the surface of the carrier, improves the catalytic efficiency of unit mass active component, and active component is prevented to burn in use Knot, improves the heat resistance of catalyst.For carrier of hydrocracking catalyst, it is both the carrier and cracking component of hydrogenation metal Donor.Modified Y zeolite and water-soluble resin are added carrier of the invention after co-precipitation and carries out high temperature ageing, can obtain compared with The concentration pore size distribution of big Kong Rong, higher specific surface, 10 ~ 20nm；Modified Y zeolite component and amorphous silicon aluminium are uniformly dispersed, To improve the utilization rate of acidic components.
Specific embodiment
Modified Y molecular sieve used in the embodiment of the present invention is the side described by example 3 in Chinese patent CN1053429C Method preparation, specific preparation process is as follows: 1. by 2.0kg NaY zeolite (SiO2/Al2O3=5.1, Na2O=11.3% is opposite to be tied Brilliant degree 93%, lattice constant 2.468nm, butt 50w%) it is added in the ammonium nitrate solution that 16 liters of concentration are 3M, it is stirred at 150 DEG C Ion exchange 0.5 hour, coion exchanged 12 times, obtained Na2The Y zeolite that O content is 0.17%, drying；2. above-mentioned drying is dry Y zeolite be put into high-pressure rotary furnace, 700 DEG C, 0.01MPa, roast 4 hours under 100% water vapour pressure；3. water intaking heat treatment Product 400g afterwards is put into 4 liters of hydrochloric acid solutions that concentration is 0.4M, handles 2 hours, be filtered, washed to neutrality, drying obtains Modified Y zeolite.Its physico-chemical property are as follows: SiO2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ G, infrared acidity Ci=0.53mmol/g, being greater than 2nm secondary pore is 56%, water adsorption amount (25 DEG C of P/P0It=0.1) is 4w%.
Polyacrylic resin used in the examples is the method preparation by embodiment 1 in Chinese patent CN101935447B , specific preparation process is as follows: first by molecular weight be 600 750 grams of polyethylene glycol and 250 grams of polyvinylpyrrolidone it is mixed It closes, keeping temperature is 25 ~ 30 DEG C, and stirring obtains solution after it is completely dissolved, and takes 20 milliliters of the solution and transparent ureaformaldehyde tree 80 milliliters of rouge liquid are mixed into glue, and coagulator glacial acetic acid i.e. 10 milliliter are added by the 10% of 100 milliliters of total volumes of glue, fill Control pumping gas in stirring and using is divided extremely to generate without a large amount of bubbles for 2 ~ 5 minutes, standing belt surface again set up to water-soluble by bubble-free Rouge.
Below by embodiment, the present invention will be further described.
Embodiment 1
(1), it prepares and contains SiO2Concentration is the water glass solution 2533ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 1900ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (ammonium hydroxide of 10wt%) is added dropwise under agitation and carries out plastic, The pH value for controlling gel is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g is greater than 2nm secondary pore for 56%) 120g, polypropylene Acid resin 150g, is sufficiently mixed；
(4), system temperature is risen to 120 ± 2 DEG C, controls pH value 8.0 ± 0.1, aging 4 hours, slurries cooled down Filter, the ammonium acetate solution of filter cake pH=8.0, which is washed to sodium content, is less than 0.1m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZA that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Embodiment 2
(1), it prepares and contains SiO2Concentration is the water glass solution 5330ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 4000ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (10% ammonium hydroxide) is added dropwise under agitation and carries out plastic, control The pH value of gel processed is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g is greater than 2nm secondary pore for 56%) 200g, polyacrylic acid Resin 300g, is sufficiently mixed；
(4), system temperature is risen to 130 ± 2 DEG C, controls pH value 7.8 ± 0.1, aging 3 hours, slurries cooled down Filter, the ammonium acetate solution of filter cake pH=8.0, which is washed to sodium content, is less than 0.1m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZB that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Embodiment 3
(1), it prepares and contains SiO2Concentration is the water glass solution 2000ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 1900ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (10% ammonium hydroxide) is added dropwise under agitation and carries out plastic, control The pH value of gel processed is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g is greater than 2nm secondary pore for 56%) 60g, polyacrylic acid Resin 160g, is sufficiently mixed；
(4), system temperature is risen to 115 ± 2 DEG C, controls pH value 8.0 ± 0.1, aging 5 hours, slurries cooled down Filter, the ammonium acetate solution of filter cake pH=8.0, which is washed to sodium content, is less than 0.1m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZC that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Comparative example 1
(1), it prepares and contains SiO2Concentration is the water glass solution 2000ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 1900ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (10% ammonium hydroxide) is added dropwise under agitation and carries out plastic, control The pH value of gel processed is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g is greater than 2nm secondary pore for 56%) 60g, is not added water-soluble Property resin；
(4), system temperature is risen to 115 ± 2 DEG C, controls pH value 8.0 ± 0.1, aging 5 hours, slurries cooled down Filter, the ammonium acetate solution of filter cake pH=8.0, which is washed to sodium content, is less than 0.1m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZD that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Comparative example 2
(1), it prepares and contains SiO2Concentration is the water glass solution 2000ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 1900ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (10% ammonium hydroxide) is added dropwise under agitation and carries out plastic, control The pH value of gel processed is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g is greater than 2nm secondary pore for 56%) 60g, polyacrylic acid Resin 160g, is sufficiently mixed；
(4), system temperature is risen to 80 ± 2 DEG C, controls pH value 8.0 ± 0.1, aging 5 hours, slurries cooled down Filter, the ammonium acetate solution of filter cake pH=8.0, which is washed to sodium content, is less than 0.1m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZE that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Embodiment 4
(1), it prepares and contains SiO2Concentration is the water glass solution 2000ml of 75g/L, contains Al2O3Concentration is the chlorine of 100g/L Change aluminum solutions 1900ml, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up to 60 DEG C, precipitating reagent (10% ammonium hydroxide) is added dropwise under agitation and carries out plastic, control The pH value of gel processed is 8.0；
(3), the modified Y zeolite (SiO for being crushed to 500 mesh is added simultaneously2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, being greater than 2nm secondary pore is that 56%) 60g, water solubility are set Rouge 160g, is sufficiently mixed；
(4), system temperature is risen to 115 ± 2 DEG C, controls pH value 8.0 ± 0.1, aging 5 hours, slurries cooled down Filter, filter cake, which is washed with water purification to sodium content, is equal to 0.4m%；
(5), filter cake is greater than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；Finally roasted at 650 DEG C 3 hours silica-alumina supports finished product ZF that hydrocracking catalyst of the present invention is made are burnt, physico-chemical property is listed in table 1.
Comparative example 3
It is the side described by 103100436 B of Chinese patent CN " preparation method of catalyst carrier dry gel powder " embodiment 1 Method preparation, specific preparation process is as follows: 200g solid aluminum chloride being added in 2 liters of distilled water, while heating and stirring It mixes to dissolution, obtains liquor alumini chloridi (a)；Appropriate distilled water is added in concentrated ammonia liquor and is diluted to about 10% weak aqua ammonia (b)；10g Cetylamine is dissolved in 120ml dehydrated alcohol, and the modified Y type molecular sieve (SiO of 25g is added to the inside under stirring2/Al2O3 Molar ratio is 11.0, lattice constant 24.42, relative crystallinity 95%) in, it is formed solution (c)；Take 10L waterglass (technical grade, modulus 3.0) is diluted in 20L deionized water, is configured to solution (d)；A stainless steel reaction tank is taken, in tank After (a) is added and is heated with stirring to 65 DEG C, the valve for having the container of (b) is opened, by system in tank within control 10 minutes PH=4.5 are added drop-wise to, 250ml solution (c) is added into tank at this time, continue that (b) is added dropwise, by system in tank in control 30 minutes PH=8.0 are added drop-wise to, keeping temperature is 65 DEG C, pH=8.0, stops after twenty minutes, solution (d) is added into system, according to without fixed The amount for the waterglass that the weight ratio that silica/alumina is 45/55 in shape sial calculates adds in 10 minutes.Aging 1 Hour, material in tank is filtered, washing to no chloride ion, filtering is 10 hours dry at 110 DEG C by filter cake, crushed Sieve obtains catalyst carrier dry gel powder ZG.Through roasting 5 hours at 550 DEG C, Main physical chemical property is shown in Table 1.
The physico-chemical property of 1 embodiment and comparative example carrier of table
Carrier ZA, ZB, ZC, ZF are the carrier of hydrocracking catalyst prepared by the method for the present invention in table, prepared by ZD Cheng Bujia water-soluble resin, ZE do not carry out high temperature ageing in preparation process, and ZF is not washed with ammonium acetate solution in preparation process The sodium content washed in carrier is less than 0.1m%.From the data in table it can be seen that the large specific surface area of carrier of the present invention, Kong Rong Greatly, aperture is that the hole of 10 ~ 20nm accounts for 25% of total pore volume or more, and the silica-alumina supports of hydrocracking catalyst of the present invention contain modified Y Molecular sieve, infrared acidity is also higher, and high lytic activity and purpose are obtained suitable for hydrocracking catalyst is prepared and is produced Product selectivity.

Claims (12)

1. a kind of preparation method of the silica-alumina supports containing molecular sieve, feature: includes the following steps:
(1) it prepares the mixed solution containing silicon source and silicon source and precipitating reagent is added and gelatinous mixture is made；
(2) modified Y molecular sieve is added in the gelatinous mixture prepared to step (1) and water-soluble resin carries out high temperature ageing；
(3) slurries after aging are filtered, wash, drying, forming, roasting the obtained silica-alumina supports containing molecular sieve；
The high temperature ageing be 110 ~ 150 DEG C aging 1 ~ 6 hour；
The modified Y molecular sieve is by being made conventional Y molecular sieve progress hydrothermal dealumination and chemical dealuminization, modified Y molecule It is as follows to sieve property: SiO2And Al2O3Molar ratio is 8 ~ 15, Na2O≤0.15wt%, 2.426 ~ 2.445nm of lattice constant are opposite to tie Brilliant degree 92 ~ 99%, 750 ~ 860m of specific surface area2/ g, Kong Rong 0.42 ~ 0.55ml/g, infrared acidity Ci=0.48 ~ 1.3mmol/g, greatly In 2nm secondary pore be >=20%, 25 DEG C of P/P0=0.1 water adsorption amount is 2.5 ~ 5.5wt%；
The water-soluble resin is water-soluble polypropylene acid resin, water soluble polyurethane resin, water-soluble epoxy resin, water-soluble One or more of property phenolic resin.
2. according to the method described in claim 1, it is characterized by: by plastic cans is added containing the mixed solution of silicon source and silicon source In, silicon source, the proportion of silicon source are SiO in mixed solution2/ Al2O3=0.1~1.2。
3. according to the method described in claim 1, precipitating reagent is added it is characterized by: mixed solution is warming up to 55 ~ 70 DEG C, The amount that precipitating reagent is added is subject to pH=7.5 ~ 8.5 for controlling slurries, and gelatinous mixture is made.
4. according to the method described in claim 1, it is characterized by: modified Y molecular sieve and water-soluble tree are added after precipitating Rouge, the additional amount of modified Y molecular sieve account for the 5 ~ 30% of final total weight of carrier, and the additional amount of water-soluble resin is sediment slurry matter The 1% ~ 8% of amount.
5. according to the method described in claim 1, it is characterized by: aging pH value 7.5 ~ 8.5, ageing time are 1.0 ~ 6.0 small When.
6. according to the method described in claim 1, it is characterized by: the slurries after aging cool down, filter；After washing 105 ~ 120 DEG C of drying and dehydratings to butt is greater than 60wt%, rolls, extruded moulding is roasted 2 ~ 5 hours at 550 ~ 660 DEG C and is made containing molecular sieve Silica-alumina supports.
7. according to the method described in claim 1, it is characterized by: the silicon source is silica solution, one in waterglass, white carbon black Kind is a variety of.
8. according to the method described in claim 1, it is characterized by: the silicon source is sodium aluminate, aluminum sulfate, aluminium chloride, nitre One of sour aluminium is a variety of.
9. according to the method described in claim 1, it is characterized by: the precipitating reagent is NaOH aqueous solution, ammonia spirit, carbon At least one of sour aqueous ammonium.
10. according to the method described in claim 1, it is characterized by: SiO2And Al2O3Molar ratio is 10 ~ 15, Na2O≤ 0.15wt%, lattice constant are 2.426 ~ 2.432nm, 750 ~ 850m of specific surface area20.45 ~ 0.55ml/g of/g, Kong Rong, meleic acid Spend Ci=0.48 ~ 0.58mmol/g, being greater than 2nm secondary pore is >=50%.
11. according to the method described in claim 1, it is characterized by: use pH for the ammonium acetate solution of 7.5-8.5 to filtering after Material washed, washing to sodium mass content less than 0.1%.
12. the silica-alumina supports containing molecular sieve of claim 1 to 11 either method preparation, it is characterised in that: in terms of weight content, Containing modified Y molecular sieve 5% ~ 30%, containing amorphous silicon aluminium 70% ~ 95%, the support is as follows: BET specific surface area is 350 ~ 650m2/ g, Kong Rong are 0.60 ~ 1.20ml/g, and aperture is that the hole of 10 ~ 20nm accounts for the 15% ~ 35% of total pore volume.
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