CN106669770A - Silicon-aluminum carrier containing molecular sieve and preparation method thereof - Google Patents
Silicon-aluminum carrier containing molecular sieve and preparation method thereof Download PDFInfo
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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
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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
- 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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Abstract
The invention discloses a silicon-aluminum carrier containing a molecular sieve and a preparation method thereof. The silicon-aluminum carrier is prepared from the following components in percentage by weight: 5 to 30 percent of modified Y zeolite and 70 to 95 percent of amorphous silica-aluminum. The carrier has the properties that the BET surface area is 350 to 650m<2>/g, the pore volume is 0.60 to 1.20ml/g, and pores which are 10 to 20nm in pore diameters account for 15 to 35 percent of the total pore volume. The preparation method of the silicon-aluminum carrier comprises the following steps: (1) preparing a mixed solution containing a silicon source and an aluminum source, and adding a precipitator to obtain a jelly mixture; (2) adding the modified Y zeolite and water-soluble resin into the jelly mixture prepared in the step (1) to perform high-temperature aging; (3) filtering, washing, drying, molding and sintering aged slurry to obtain the silicon-aluminum carrier containing the molecular sieve. The carrier has excellent comprehensive performance, and is suitable for a hydrocracking catalyst for heavy distillate oil secondary machining prolific middle distillate.
Description
Technical field
The present invention relates to a kind of silica-alumina supports containing molecular sieve and preparation method thereof, relate in particular to a kind of silica-alumina supports as hydrocracking catalyst and preparation method thereof, the carrier is suitable for the hydrocracking catalyst of oil secondary operation fecund intermediate oil.
Background technology
Be hydrocracked be heavy raw oil be hydrogenated with the presence of HTHP faces hydrogen and catalyst, desulfurization, denitrogenation, hydrocarbon molecule recurring structure reset and crack etc. reaction a kind of conversion process.Hydrocracking technology has adaptability to raw material strong, good product quality, intermediate oil high income, the advantages of tail oil added value is high.The bifunctional catalyst that hydrocracking catalyst is made up of hydrogenation component and acidic components, acidity of its lytic activity from carrier.The raw material for being hydrocracked processing is mainly vacuum distillate (VGO), and boiling range is generally 350～550 DEG C, and carbon number is usually 22～35, molecular weight substantially 280～450.For the catalytic reaction for having big size molecule 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.The half of VGO is about additionally, due to the carbon number and molecular weight of diesel oil distillate, to voluminous intermediate oil, the second pyrolysis of raw molecule just must be as far as possible reduced, 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 secondary cracking, 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 our carriers for developing and catalyst is conducive to the diffusion of reactant, product to improve reaction rate and avoid excessive fragmentation as far as possible；The acidity of carrier should have beneficial to the activity for improving catalyst and reduce the possibility that second pyrolysis occurs.
The B of CN 103100436 disclose a kind of preparation method of catalyst carrier dry gel powder.The method includes：The mixture of molecular sieve and organic amine is added during amorphous silica-alumina plastic, carries out aging after amorphous silica-alumina cemented into bundles, then Jing is filtered, washing, is dried, and obtains catalyst carrier dry gel powder.The inventive method can make sial in molecular sieve surface aligned orderly, equably deposit, and enhance the adhesion of molecular sieve and sial, avoid amorphous silica-alumina and even block the phenomenon in duct with occurring reuniting between molecular sieve, and sial is mutually communicated with the duct of molecular sieve, make sial and molecular sieve give full play to synergy, improve the performance of catalyst.Pore volume that the inventive embodiments are obtained≤0.75ml/g, i.e. carrier dry gel powder pore volume less, the aperture of carrier dry gel powder is also little.
CN00123131.6 discloses a kind of middle oil type hydrocracking catalyst, and it contains modified Y molecular sieve with amorphous silica-alumina as main carrier, in carrier, and the quality composition of catalyst and physico-chemical property are：WO322.0%, NiO9.0%, ZrO27.0%, SiO233.0%, Al2O329.0%, specific surface area 260m2/ g, pore volume 0.36ml/g.Modified Y molecular sieve accounts for the 7.0% of total catalyst weight, modified molecular screen SiO2/Al2O3Mol ratio is 17, relative crystallinity 93%, specific surface area 800m2/ g,>1.7×10-10The 45% of the hole Zhan Zong holes of m.The catalyst is mainly used in the technical process of voluminous intermediate oil, it is few yet with the molecular sieve consumption, cause the activity of catalyst not high, this requires to improve hydrocracking reaction temperature, so that the thermal cracking trend of molecular sieve strengthens and inhibits hydrogenation reaction, the middle distillates oil selectivity for making catalyst is improved not substantially, and product quality is also impacted.
CN102553650B discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, it is characterised in that：1. Y and Beta molecular sieves and deionized water are mixed, in being then added to the mixed solution of cetyl trimethylammonium bromide and APES, after stirring, silicon source and silicon source solution is added dropwise, the pH value of adjustment system is 8 ~ 12, material is transferred to 80 ~ 120 DEG C in crystallizing kettle after stable system, 24 ~ 72h of crystallization, suction filtration, drying, roasting obtain again the double microporous-mesoporous composite molecular sieves of Hydrogen Y-Beta/MCM-41 Jing after ammonium exchange；2. double microporous-mesoporous composite molecular sieves, amorphous silica-alumina, macroporous aluminium oxide, adhesive and extrusion aid are well mixed, after extrusion after the wet carrier strip elder generation room temperature 2 ~ 4h of health of gained, in 80 ~ 150 DEG C of 2 ~ 4h of drying, then 4 ~ 8h of roasting obtains described carrier of hydrocracking catalyst at 400 ~ 600 DEG C.The catalyst carrier wishes the macropore of the acid and mesopore molecular sieves of MC M- 41 that Y-Beta micro porous molecular sieves are obtained with reference to micropore, the respective advantage of mesoporous two kinds of molecular sieves.It is known that the reason for be MCM-41 mesopore molecular sieves heat endurance it is bad, so far and be not implemented commercial Application.
CN1253988A discloses a kind of hydrocracking catalyst using oil in the fecund that altogether prepared by glue method, and the catalyst is consisted of containing the modified Y molecular sieve for pressing the preparation of CN96119840.0 methods, its weight：WO323.0%, NiO9.0%, ZrO27.0%, SiO230.0%, Al2O3Surplus, its specific surface area 290m2/ g, pore volume 0.37ml/g.Modified Y molecular sieve acid amount height (C selected by the catalysti=0.9 ~ 1.1mmol/g), good catalyst activity, but middle distillates oil selectivity is bad.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of silica-alumina supports as hydrocracking catalyst and preparation method thereof.The carrier combination property is projected, it is adaptable to the hydrocracking catalyst of heavy distillate secondary operation fecund intermediate oil.
A kind of preparation method of the silica-alumina supports containing molecular sieve, comprises the steps：
（1）Prepare the mixed solution containing silicon source and silicon source and add 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 the silica-alumina supports containing molecular sieve.
The concrete preparation process of silica-alumina supports of the present invention containing molecular sieve is as follows：Mixed solution containing silicon source and silicon source is added in plastic cans, silicon source, the proportioning of silicon source are SiO in mixed solution2/ Al2O3=0.1~1.2；Mixed solution is warming up into 55 ~ 70 DEG C, precipitating reagent is added, the amount for adding precipitating reagent is defined by pH=7.5 ~ 8.5 for controlling slurries, makes gelatinous mixture；Precipitation adds modified Y zeolite and water-soluble resin after terminating, the addition of modified Y zeolite accounts for the 5 ~ 30% of final total weight of carrier, the addition of water-soluble resin is the 1% ~ 8% of sediment slurry quality, it is preferred that 2% ~ 6%, 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, filtration；It is more than 60wt% in 105 ~ 120 DEG C of drying and dehydratings to butt after washing, rolls, extruded moulding is obtained the silica-alumina supports containing molecular sieve in 2 ~ 5 hours in 550 ~ 660 DEG C of roastings.
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.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=8~15（Mol ratio）, Na2O≤0.15wt%, 2.426 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 750 ~ 860m of specific surface area2/ g, 0.42 ~ 0.55ml/g of pore volume, infrared acidity Ci=0.48 ~ 1.3mmol/g, is >=20% more than 2nm secondary pores, water adsorption amount (25 DEG C of P/P0=0.1) it is 2.5 ~ 5.5wt%；It is preferred that SiO2/Al2O3=10~15（Mol ratio）, Na2O≤0.15wt%, lattice constant is 2.426 ~ 2.432nm, 750 ~ 850m of specific surface area2/ g, 0.45 ~ 0.55ml/g of pore volume, infrared acidity Ci=0.48 ~ 0.58mmol/g, is >=50% 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 content and be less than 0.1m%.The meleic acid amount of carrier can be improved using ammonium acetate solution washing, Carriers Active is improved.
Silica-alumina supports containing molecular sieve prepared by a kind of employing said method, in terms of weight content, containing modified Y zeolite 5% ~ 30%, containing amorphous silicon aluminium 70% ~ 95%, described support is as follows：BET surface area is 350 ~ 650m2/ g, pore volume is 0.60 ~ 1.20ml/g, and aperture accounts for the 15% ~ 35% of total pore volume for the hole of 10 ~ 20nm.
The catalyst carrier that the present invention is provided has the advantage that：Carrier is can to carry active material, and active component can be made to be dispersed on carrier surface, improves the catalytic efficiency of unit mass active component, prevents active component from sintering in use, improves the heat resistance of catalyst.For carrier of hydrocracking catalyst, it is both the carrier of hydrogenation metal, is again cracking component donor.The carrier of the present invention adds modified Y zeolite and water-soluble resin to carry out high temperature ageing after co-precipitation, it is possible to obtain larger pore volume, higher specific surface, the concentration pore size distribution of 10 ~ 20nm；Modified Y zeolite component and amorphous silicon aluminium are uniformly dispersed, so as to improve the utilization rate of acidic components.
Specific embodiment
Modified Y molecular sieve used is prepared by the method for the description of example 3 in Chinese patent CN1053429C in the embodiment of the present invention, and specific preparation process is as follows：1. by 2.0kg NaY zeolite (SiO2/Al2O3=5.1, Na2O=11.3% relative crystallinities 93%, lattice constant 2.468nm, butt 50w%) ammonium nitrate solution that 16 liters of concentration are 3M is added to, ion exchange 0.5 hour is stirred at 150 DEG C, coion is exchanged 12 times, obtain Na2O content is 0.17% Y zeolites, drying；2. the dry Y zeolites of above-mentioned drying are put into high-pressure rotary stove, 700 DEG C, 0.01MPa, roasting 4 hours under 100% water vapour pressure；3. the product 400g after water intaking heat treatment, in being put into 4 liters of hydrochloric acid solutions that concentration is 0.4M, is processed 2 hours, is filtered, is washed to neutrality, and drying obtains modified Y zeolite.Its physico-chemical property is：SiO2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56% more than 2nm secondary pores, water adsorption amount (25 DEG C of P/P0=0.1) it is 4w%.
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, again bubble-free obtains final product water-soluble resin to stand belt surface.
Below by embodiment, the present invention will be further described.
Embodiment 1
(1), prepare and contain SiO2Concentration is the water glass solution 2533ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 1900ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent is added dropwise under agitation（The ammoniacal liquor of 10wt%）Plastic is carried out, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 120g, polyacrylic resin 150g more than 2nm secondary pores, is sufficiently mixed；
(4), system temperature is risen into 120 ± 2 DEG C, control ph 8.0 ± 0.1, aging 4 hours, slurries carried 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%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZA that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Embodiment 2
(1), prepare and contain SiO2Concentration is the water glass solution 5330ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 4000ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent (10% ammoniacal liquor) is added dropwise under agitation carries out plastic, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 200g, polyacrylic resin 300g more than 2nm secondary pores, is sufficiently mixed；
(4), system temperature is risen into 130 ± 2 DEG C, control ph 7.8 ± 0.1, aging 3 hours, slurries carried 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%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZB that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Embodiment 3
(1), prepare and contain SiO2Concentration is the water glass solution 2000ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 1900ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent (10% ammoniacal liquor) is added dropwise under agitation carries out plastic, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 60g, polyacrylic resin 160g more than 2nm secondary pores, is sufficiently mixed；
(4), system temperature is risen into 115 ± 2 DEG C, control ph 8.0 ± 0.1, aging 5 hours, slurries carried 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%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZC that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Comparative example 1
(1), prepare and contain SiO2Concentration is the water glass solution 2000ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 1900ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent (10% ammoniacal liquor) is added dropwise under agitation carries out plastic, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 60g more than 2nm secondary pores, is not added with water-soluble resin；
(4), system temperature is risen into 115 ± 2 DEG C, control ph 8.0 ± 0.1, aging 5 hours, slurries carried 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%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZD that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Comparative example 2
(1), prepare and contain SiO2Concentration is the water glass solution 2000ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 1900ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent (10% ammoniacal liquor) is added dropwise under agitation carries out plastic, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 60g, polyacrylic resin 160g more than 2nm secondary pores, is sufficiently mixed；
(4), system temperature is risen into 80 ± 2 DEG C, control ph 8.0 ± 0.1, aging 5 hours, slurries carried 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%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZE that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Embodiment 4
(1), prepare and contain SiO2Concentration is the water glass solution 2000ml of 75g/L, containing Al2O3Concentration is the liquor alumini chloridi 1900ml of 100g/L, under agitation mixes water glass solution and liquor alumini chloridi；
(2), mixed solution is warming up into 60 DEG C, precipitating reagent (10% ammoniacal liquor) is added dropwise under agitation carries out plastic, the pH value for controlling gel is 8.0；
(3), while adding the modified Y zeolite (SiO for being crushed to 500 mesh2/Al2O3=13, Na2O=0.10%, lattice constant 2.428nm, specific surface area 783m2/ g, infrared acidity Ci=0.53mmol/g, is 56%) 60g, water-soluble resin 160g more than 2nm secondary pores, is sufficiently mixed；
(4), system temperature is risen into 115 ± 2 DEG C, control ph 8.0 ± 0.1, aging 5 hours, slurries carried out cooling filtration, and filter cake water purification is washed to sodium content and is equal to 0.4m%；
(5), filter cake is more than 60% in 105 ~ 120 DEG C of drying and dehydratings to butt, rolls, extruded moulding；The last silica-alumina supports finished product ZF that hydrocracking catalyst of the present invention is obtained for 3 hours in 650 DEG C of roastings, its physico-chemical property is listed in table 1.
Comparative example 3
It is prepared by the method described by the B of Chinese patent CN 103100436 " preparation method of catalyst carrier dry gel powder " embodiment 1, specific preparation process is as follows：200g solid aluminum chlorides are added in 2 liters of distilled water, while heating and stirring to dissolving, liquor alumini chloridi (a) is obtained；Concentrated ammonia liquor is added into appropriate distilled water diluting into about 10% weak aqua ammonia (b)；10g cetylamines are dissolved in 120ml absolute ethyl alcohols, and the modified Y type molecular sieve (SiO of 25g are added to the inside under stirring2/Al2O3Mol ratio is 11.0, and lattice constant is 24.42, relative crystallinity be 95%) in, formed solution (c)；(technical grade, modulus is 3.0) to be diluted in 20L deionized waters, is configured to solution (d) to take 10L waterglass；Take a stainless steel reaction tank, (a) is added in tank and after being heated with stirring to 65 DEG C, opening has the valve of the container of (b), system in tank is added drop-wise to pH=4.5 by control within 10 minutes, 250ml solution (c) is now added in tank, continue that (b) is added dropwise, system in tank is added drop-wise to pH=8.0 by control in 30 minutes, keeping temperature is 65 DEG C, pH=8.0, after stopping 20 minutes, solution (d) is added in system, the amount of the waterglass calculated according to the part by weight that silica/alumina in amorphous silica-alumina is 45/55 was added in 10 minutes.Aging 1 hour, material in tank is filtered, washed to without chlorion, filtered, filter cake is dried 10 hours at 110 DEG C, pulverized and sieved and obtain catalyst carrier dry gel powder ZG.Roasting 5 hours at 550 DEG C of Jing, its Main physical chemical property is shown in Table 1.
The physico-chemical property of the embodiment of table 1 and comparative example carrier
Carrier ZA, ZB, ZC, ZF are the carrier of hydrocracking catalyst prepared by the inventive method in table, ZD is not added with water-soluble resin in preparation process, ZE does not carry out high temperature ageing in preparation process, and ZF is not less than 0.1m% in preparation process with the sodium content in ammonium acetate solution wash vehicle.Data from table can be seen that：The specific surface area of carrier of the present invention is big, pore volume is also big, aperture accounts for more than the 25% of total pore volume for the hole of 10 ~ 20nm, the silica-alumina supports of hydrocracking catalyst of the present invention contain modified Y molecular sieve, its infrared acidity is also higher, is suitable for preparing hydrocracking catalyst to obtain high lytic activity and purpose product selectivity.
Claims (14)
1. a kind of preparation method of the silica-alumina supports containing molecular sieve, its feature：Comprise the steps：
（1）Prepare the mixed solution containing silicon source and silicon source and add 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 the silica-alumina supports containing molecular sieve.
2. method according to claim 1, it is characterised in that：Mixed solution containing silicon source and silicon source is added in plastic cans, silicon source, the proportioning of silicon source are SiO in mixed solution2/ Al2O3=0.1~1.2。
3. method according to claim 1, it is characterised in that：Mixed solution is warming up into 55 ~ 70 DEG C, precipitating reagent is added, the amount for adding precipitating reagent is defined by pH=7.5 ~ 8.5 for controlling slurries, makes gelatinous mixture.
4. method according to claim 1, it is characterised in that：Precipitation adds modified Y zeolite and water-soluble resin, the addition of modified Y zeolite to account for the 5 ~ 30% of final total weight of carrier after terminating, the addition of water-soluble resin is the 1% ~ 8% of sediment slurry quality.
5. method according to claim 1, it is characterised in that：Temperature rises to 110 ~ 150 DEG C of aging 1 ~ 6 hour, aging pH value 7.5 ~ 8.5, and ageing time is 1.0 ~ 6.0 hours.
6. method according to claim 1, it is characterised in that：Slurries cooling after aging, filtration；It is more than 60wt% in 105 ~ 120 DEG C of drying and dehydratings to butt after washing, rolls, extruded moulding is obtained the silica-alumina supports containing molecular sieve in 2 ~ 5 hours in 550 ~ 660 DEG C of roastings.
7. method according to claim 1, it is characterised in that：Described silicon source is one or more in Ludox, waterglass, white carbon.
8. method according to claim 1, it is characterised in that：Described silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate.
9. method according to claim 1, it is characterised in that：Described precipitating reagent is the NaOH aqueous solution, ammonia spirit, at least one of ammonium carbonate solution.
10. method according to claim 1, 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.
11. methods according to claim 1, 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=8~15（Mol ratio）, Na2O≤0.15wt%, 2.426 ~ 2.445nm of lattice constant, relative crystallinity 92 ~ 99%, 750 ~ 860m of specific surface area2/ g, 0.42 ~ 0.55ml/g of pore volume, infrared acidity Ci=0.48 ~ 1.3mmol/g, is >=20% more than 2nm secondary pores, water adsorption amount (25 DEG C of P/P0=0.1) it is 2.5 ~ 5.5wt%.
12. methods according to claim 11, it is characterised in that：SiO2/Al2O3=10~15（Mol ratio）, Na2O≤0.15wt%, lattice constant is 2.426 ~ 2.432nm, 750 ~ 850m of specific surface area2/ g, 0.45 ~ 0.55ml/g of pore volume, infrared acidity Ci=0.48 ~ 0.58mmol/g, is >=50% more than 2nm secondary pores.
13. methods according to claim 1, 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%.
Silica-alumina supports containing molecular sieve prepared by 14. claim 1 to 13 either method, it is characterised in that：In terms of weight content, containing modified Y zeolite 5% ~ 30%, containing amorphous silicon aluminium 70% ~ 95%, described support is as follows：BET surface area is 350 ~ 650m2/ g, pore volume is 0.60 ~ 1.20ml/g, and aperture accounts for the 15% ~ 35% of total pore volume for the hole of 10 ~ 20nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824111A (en) * | 2019-02-28 | 2019-05-31 | 长沙埃比林环保科技有限公司 | A kind of preparation method of sewage adsorbent material |
| CN109824110A (en) * | 2019-02-28 | 2019-05-31 | 长沙埃比林环保科技有限公司 | A kind of preparation method of heavy metal containing sewage adsorbent material |
| CN115041219A (en) * | 2022-07-18 | 2022-09-13 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalyst for converting waste into oil product |
| CN116059987A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of amorphous silicon aluminum |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253988A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN102755903A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Preparation method of acidic molecular sieve and resin composite catalyst |
| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
| US20140331601A1 (en) * | 2013-05-09 | 2014-11-13 | H.B. Fuller Company | Thermoplastic compositions that include sorbent particles, and methods of using the same |
-
2015
- 2015-11-09 CN CN201510750641.3A patent/CN106669770B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253988A (en) * | 1998-11-18 | 2000-05-24 | 中国石油化工集团公司 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
| CN102755903A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Preparation method of acidic molecular sieve and resin composite catalyst |
| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
| US20140331601A1 (en) * | 2013-05-09 | 2014-11-13 | H.B. Fuller Company | Thermoplastic compositions that include sorbent particles, and methods of using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824111A (en) * | 2019-02-28 | 2019-05-31 | 长沙埃比林环保科技有限公司 | A kind of preparation method of sewage adsorbent material |
| CN109824110A (en) * | 2019-02-28 | 2019-05-31 | 长沙埃比林环保科技有限公司 | A kind of preparation method of heavy metal containing sewage adsorbent material |
| CN116059987A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of amorphous silicon aluminum |
| CN115041219A (en) * | 2022-07-18 | 2022-09-13 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalyst for converting waste into oil product |
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