CN114433174A - Silicon-aluminum carrier and preparation method and application thereof - Google Patents

Silicon-aluminum carrier and preparation method and application thereof Download PDF

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CN114433174A
CN114433174A CN202011115314.8A CN202011115314A CN114433174A CN 114433174 A CN114433174 A CN 114433174A CN 202011115314 A CN202011115314 A CN 202011115314A CN 114433174 A CN114433174 A CN 114433174A
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molecular sieve
carrier
silicon
alumina
catalyst
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CN114433174B (en
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姜虹
杨占林
王继锋
刘奕
丁思佳
王会刚
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian 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
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—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
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a silicon-aluminum carrier and a preparation method and application thereof. The preparation method of the silicon-aluminum carrier comprises the following steps: (1) dissolving yeast in aqueous solution, and mixing with starch uniformly for later use; (2) adding water into the needed molecular sieve and pulping to form molecular sieve pulp for later use; (3) introducing the molecular sieve slurry obtained in the step (2) into gelling process of amorphous silica-alumina, wherein the addition amount of the molecular sieve is 5-80% of the weight of the final hydrocracking catalyst carrier, and aging, filtering and washing after gelling; (4) kneading, molding, drying and roasting the material obtained in the step (3) to obtain a final hydrocracking catalyst carrier; wherein the material of step (1) is introduced during step (3) or during the kneading of step (4). The silicon-aluminum carrier has high specific surface area and proper acid distribution.

Description

Silicon-aluminum carrier and preparation method and application thereof
Technical Field
The invention relates to a silicon-aluminum carrier and a preparation method and application thereof, in particular to a high-performance silicon-aluminum carrier and a preparation method and application thereof in hydrocracking.
Background
In the field of catalysis, how to prepare a high-efficiency catalyst with high activity, excellent selectivity and long service life has been a topic of attention and importance. For a hydrocracking catalyst, the amorphous silica-alumina carrier not only bears the supporting task, but also has a certain acidic cracking function and plays a role in solid acid catalysis. The proper amorphous silica-alumina carrier is prepared, and the dispersion degree of the loaded active components is high, so that the reaction performance of the catalyst is improved; the surface acidity of the amorphous silica-alumina carrier has a great influence on the activity of the hydrogenation catalyst, and how to weaken the strong interaction between the metal and the carrier and how to make the catalyst have proper acidity becomes the key for preparing the hydrocracking catalyst.
The hydrocracking catalyst is a bifunctional catalyst which has both cracking activity and hydrogenation activity, namely contains both an acidic component and a hydrogenation active component. Wherein the acidity is mainly provided by various molecular sieves and/or refractory inorganic oxides constituting a carrier, and the properties of the acidic component have a very important influence on the activity of the hydrocracking catalyst and the selectivity of the middle distillate. The hydrogenation active component is generally selected from metals, metal oxides and/or metal sulfides of groups VIB and VIII of the periodic Table of the elements. The key component for cracking in the hydrocracking catalyst is the carrier of the catalyst, and the preparation performance of the carrier directly influences the performance of the catalyst and the quality of oil products.
CN1110304A discloses a method for preparing macroporous alumina containing silicon and phosphorus, in the preparation process of the alumina, silicon and phosphorus are added by a step-by-step gelling method, so that most of silicon and phosphorus can be dispersed on the surface of the alumina, the pore diameter and pore volume of the alumina are improved, but the acid content, especially B acid content on the surface of the alumina is greatly reduced due to the addition of more phosphorus, the acid strength is obviously reduced, and the application of the alumina is limited to a certain extent.
CN 201811056468.7 discloses an alumina carrier and a preparation method thereof, wherein a silicon source is added into acid liquor of an organic polymer and is uniformly mixed to obtain a silicon source-organic polymer mixture, the content of the organic polymer in the unit content of an alumina precursor is more than 1.5 times higher than that of the organic polymer in the silicon source-organic polymer mixture, then the silicon source-organic polymer mixture is mixed with the alumina precursor, and the alumina carrier is obtained through extrusion, molding, drying and roasting. The silicon source can be sodium silicate or silicon micropowder.
CN200910236166.2 discloses a preparation method of a petroleum wax hydrofining catalyst. The method comprises the following steps: weighing pseudo-boehmite, adding 6-17% of silicon-containing compound and 2-20% of phosphorus-containing organic compound solution, extruding the mixture on a strip extruder for molding, drying and roasting to obtain gamma-Al containing silicon and phosphorus2O3A carrier; the silicon-containing compound being SiO2Silica sol or nanosilica at a concentration of 30% by weight.
CN201410714768.5 discloses a preparation method of alumina-based carrier containing silicon and magnesium. The method comprises the following steps: and sequentially or simultaneously introducing water-soluble silicone oil and a soluble magnesium-containing compound into the alumina-based carrier, and performing heat treatment to obtain the alumina-based carrier containing silicon and magnesium.
CN1060977A discloses a method for preparing ultrastable Y-type zeolite containing amorphous silica-alumina, which comprises the steps of introducing silica-alumina gel into NaY zeolite, and then carrying out conventional ammonium ion exchange and hydrothermal roasting processes to obtain USY zeolite containing amorphous silica-alumina. The method has the main defects that amorphous silica-alumina is introduced before the modification of the molecular sieve, so that the modification treatment process of the molecular sieve is limited, and the modification treatment of the molecular sieve has great influence on the properties of the amorphous silica-alumina. In addition, the preparation method is easy to introduce amorphous silica-alumina into the molecular sieve pore channels, block the molecular sieve pore channels, reduce the pore volume of the molecular sieve and influence the catalytic performance of the molecular sieve.
CN106732496A discloses high-activity amorphous silica-alumina, a hydrocracking catalyst using the same as a carrier and a preparation method thereof. The preparation method is characterized in that nickel salt or salt of nickel salt and metal auxiliary agent M is added into mixed aqueous solution of a silicon source and an aluminum source in the preparation method of the amorphous silica-alumina carrier, a coprecipitation method is adopted in the preparation process, the silicon source and the aluminum source exist in the catalyst in the form of amorphous silica-alumina, the activity of the catalyst is higher than that of a common amorphous silica-alumina catalyst, but the pore channel structure is not beneficial to long-period operation.
US4401556 discloses a hydrocracking catalyst for the production of middle distillates. The catalyst takes a dealuminized Y-type molecular sieve as a cracking active component, the molar ratio of silicon to aluminum is 4.5-35, the unit cell parameter is 2.420-2.445 nm, and the BET surface area is not less than 350m2(ii) in terms of/g. When the catalyst uses VGO as a raw material, the activity is poor, and the medium oil selectivity is not high.
CN200910236166.2 discloses a preparation method of a petroleum wax hydrofining catalyst. The method comprises the following steps: weighing pseudo-boehmite, adding 6-17% of silicon-containing compound and 2-20% of phosphorus-containing organic compound solution, extruding the mixture on a strip extruder for molding, drying and roasting to obtain gamma-Al containing silicon and phosphorus2O3A carrier; the silicon-containing compound being SiO2Silica sol or nanosilica at a concentration of 30% by weight.
US5670590 discloses a hydrocracking catalyst for the purpose of increasing the production of naphtha fractions, characterized by the use of a USY molecular sieve. The USY molecular sieve is obtained by exchanging and roasting NaY raw powder with ammonium nitrate, and then exchanging and roasting the NaY raw powder once, wherein the unit cell parameter is 2.438-2.442 nm, and the sodium content is higher and is about 1wt% generally. The catalyst has low activity, the selectivity of heavy naphtha is not very high, and the hydrogen consumption is also larger.
US4672048 discloses a light oil type hydrocracking catalyst, which adopts a Y-type molecular sieve and is characterized in that the molar ratio of silicon to aluminum is 11-15. The preparation method of the Y-type molecular sieve is to treat the ammonia-type Y-type molecular sieve in an acidic buffer solution by ammonium hexafluorosilicate, wherein the sodium content of the obtained molecular sieve is about 0.5wt% generally, and the activity of the catalyst is low.
The hydrocracking catalyst carrier prepared by the method and the performance of the hydrocracking catalyst thereof are improved to a certain extent, but the performance still needs to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silicon-aluminum carrier and a preparation method and application thereof. The silicon-aluminum carrier has higher specific surface area and proper acid distribution; the carrier is used for preparing the hydrocracking catalyst, which is beneficial to the dispersion of active components and improves the catalytic performance. The catalytic performance can be obviously improved.
A preparation method of a silicon-aluminum carrier comprises the following steps:
(1) dissolving yeast in aqueous solution, and mixing with starch uniformly for later use;
(2) adding water into the needed molecular sieve and pulping to form molecular sieve pulp for later use;
(3) introducing the molecular sieve slurry obtained in the step (2) into gelling process of amorphous silica-alumina, wherein the addition amount of the molecular sieve is 5-80% of the weight of the final hydrocracking catalyst carrier, and aging, filtering and washing after gelling;
(4) kneading, molding, drying and roasting the material obtained in the step (3) to obtain a final hydrocracking catalyst carrier;
wherein the material in the step (1) is introduced in the process of the step (3), preferably before the amorphous silica-alumina is aged after gelling or in the process of kneading in the step (4).
In the above method, the yeast in step (1) may be in the form of one of a haploid form, a diploid form, a haploid form, or a mixture thereof, and is dissolved in an aqueous solution at a pH of 3.0 to 7.5, preferably at a pH of 4 to 6.
In the above process, the yeast content of the material of step (1) is 5% to 50%, preferably 15% to 30% by weight.
In the above process, the starch in step (1) may be polyhydroxy aldehyde, polyhydroxy ketone, and organic compounds and polymers thereof which can be hydrolyzed to form polyhydroxy aldehyde and polyhydroxy ketone, and the amount thereof is 0.2-50%, preferably 1-12% by weight of the final catalyst.
In the above method, the aqueous solution in step (1) may further contain one or more acids, which may be inorganic acids or organic acids, preferably acetic acid, formic acid, malic acid, lactic acid, and the like.
In the above process, the molecular sieve in the step (2) is any one of known molecular sieves or modified molecular sieves used for hydrocracking catalyst components. The selection of the specific type and properties of the molecular sieve can be determined according to the use requirement, and in the field of petroleum processing, the commonly used molecular sieve can be one or more of Y-type molecular sieve, beta zeolite, ZSM series molecular sieve, SAPO series molecular sieve and the like. To achieve the desired catalytic properties, the various molecular sieves may be subjected to appropriate treatment modifications, which are well known to those skilled in the art, such as hydrothermal modification, acid modification, ion exchange treatment, various solvent treatments, and the like. The molecular sieve required by the petroleum refining catalyst generally needs modification processes such as ion exchange, hydrothermal treatment and the like. The molecular sieve slurry is typically at a concentration of 5% to 40% by weight.
In the above method, the gelling process of amorphous silica-alumina described in step (3) may be performed according to a process well known to those skilled in the art. The gelling process of amorphous silica-alumina is generally a neutralization reaction process of an acidic material and an alkaline material, and the gelling process generally adopts an operation mode of parallel flow gelling of two materials or an operation mode of placing one material in a gelling tank and continuously adding the other material into gelling. In the gelling process of the amorphous silica-alumina, the introduction mode of the molecular sieve slurry can be selected at will, for example, one or a combination of the following modes can be adopted: (1) in the gelling neutralization reaction process, continuously adding the molecular sieve slurry into a gelling tank; (2) adding the molecular sieve slurry into a gelling tank, and then neutralizing an acidic material and an alkaline material to gel; (3) mixing the molecular sieve slurry with one or more of the gelling materials, and then neutralizing the gelling materials to form gel. The materials and gelling conditions used in the gelling process of amorphous silica-alumina are well known to those skilled in the art and can be determined according to the requirements of the application. And after gelling, aging under proper conditions.
In the above method, the aging in step (4) should be a generalized aging process, and pH, temperature and aging time are important control parameters, and generally pH is 7.5-9.5, preferably 8.0-9.0, temperature is 50-70 deg.C, preferably 55-65 deg.C, and time is generally 5-60 min, preferably 15-45 min.
In the above method, the steps of filtering, washing and the like after gelling in step (4) are all processes and conditions well known to those skilled in the art.
In the method, the drying temperature in the step (4) is 100-.
The carrier comprises, by weight, 5-80% of a molecular sieve, 20-95% of amorphous silicon-aluminum and 10-80% of silicon dioxide in the amorphous silicon-aluminum; the properties of the vector are as follows: the specific surface area is 200m2/g~800m2Per g, pore volume of 0.3cm3/g~1.8cm3The amount of the infrared acid at the temperature of not less than 350 ℃ is 0.04-1.10 mmol/g, wherein the B acid accounts for 40-60% of the total acid.
The hydrocracking catalyst comprises 60-86 wt% of the carrier prepared by the method and 14-40 wt% of active metal, wherein the mass content of VIB group metal (calculated by oxide) is 10-30 wt% and the mass content of VIII group metal (calculated by oxide) is 4-10 wt%; wherein the group VIB metal is selected from Mo and/or W, and the group VIII metal is selected from Co and/or Ni; wherein the ratio of VIB/(VIB + VIII) metal atom is 0.30-0.70, preferably 0.45-0.50.
The catalyst of the invention is particularly suitable for treating heavy hydrocarbon materials, the distillation range of the heavy hydrocarbon materials is between 250 ℃ and 600 ℃, and the distillation range of the heavy hydrocarbon materials is generally between 300 ℃ and 550 ℃, and the raw oil with the characteristics is such as gas oil, vacuum distillate oil, deasphalted oil, catalytic cracking cycle oil, shale oil, coal tar and the like. The reaction conditions are that the reaction pressure is 5-25MPa, the hydrogen-oil ratio is 100--1The reaction temperature is 340-450 ℃. When the catalyst of the invention is used for treating the conventional VGO, the reaction condition is generally under the condition of hydrogen, and the reaction pressure is preferably 10-20MPa, hydrogen-oil ratio of 500-2000 and space velocity of 0.5-1.5h-1The reaction temperature is 365-.
According to the preparation method of the silicon-aluminum carrier material, yeast and starch are introduced into the preparation process of the amorphous silicon-aluminum carrier, so that the acidity of the surface of amorphous silicon-aluminum is improved, the pore volume is improved, the dispersion of active metal components is facilitated, and the service performance of the catalyst is improved.
Detailed Description
In the method of the present invention, the gelling process of amorphous silica-alumina can be performed by the methods well known to those skilled in the art.
The gelling material typically comprises a source of aluminum (Al)2（SO4）3、AlCl3、Al（NO3）3And NaAlO2One or more of the above components), silicon source (one or more of water glass, silica sol and organic silicon), and precipitant (NaOH, NH)4OH or CO2Etc.), the conventional operation mode mainly comprises the following steps: (1) acidic aluminum salt (Al)2（SO4）3、AlCl3、Al（NO3）3) With alkaline aluminium salts (NaAlO)2) Or alkaline precipitants (NaOH, NH)4OH) neutralization to form gel, 2 alkaline aluminum salt (NaAlO)2) With acidic precipitants (CO)2) Neutralizing to form gel.
The silicon source is generally introduced into the colloid forming tank in the colloid forming process, or can be mixed with the aluminum source or the precipitant and then neutralized to form colloid, for example, water glass is added into the alkaline aluminum salt or the alkaline precipitant to neutralize and form colloid, and silica sol is added into the acidic aluminum salt to neutralize and form colloid, etc. The silicon source can also be added into the material after the aluminum source is precipitated. Two or more of the above-described modes may also be used in combination. The above methods are well known to those skilled in the art.
The process of the invention is described below in connection with a specific gelling process.
(a) The yeast is dissolved in an aqueous solution and mixed with starch to form a mixture for use.
(b) Adding water into the required molecular sieve and pulping.
(c) Adding the slurry of step (b), an aluminum salt solution and a precipitant into a reaction gel forming tank with a small amount of deionized water in parallel, or adding an aluminum salt solution and a precipitant into a reaction vessel with the slurry of step (b) in parallel, forming a sol at a pH of 7.0-11.0 and a temperature of 30-90 ℃, and neutralizing for 1-2 hours; or adopting a carbonization method, adding the slurry of the step (b) into the sodium aluminate solution, and then introducing CO with certain concentration and flow rate2Stopping introducing CO when gas reaches proper pH value2A gas.
(d) Adding a silicon compound to the mass of step (c) within 5-10 minutes, or adding the silicon compound to the aluminium salt solution and/or the precipitant before gelling.
(e) Adding the material obtained in the step (a) into the material obtained in the step (d) within 5-10 minutes, or adding the material obtained in the step (d) into the material obtained in the step (a), stirring uniformly, aging at a pH value of 7.5-9.5 and a temperature of 50-70 ℃ for 10-60 minutes or introducing the material obtained in the step (a) in a kneading molding process.
(f) Filtering, washing, kneading, drying and roasting to obtain the final hydrocracking catalyst carrier.
In the preparation process of the silicon-aluminum, the molecular sieve in the step (b) is any known molecular sieve, and the aluminum salt in the step (c) can be Al2（SO4）3、AlCl3、Al（NO3）3、NaAlO2Etc., the precipitant can be NaOH or NH4OH、NaAlO2、CO2And the like. But in industrial applications, due to NaAlO2、Al2（SO4）3Is cheap and is widely used. The silicon compound involved in step (d) may be water glass, silica sol or silicone.
In the process of the present invention, the pH in step (c) is generally from 7.0 to 11, preferably from 7.5 to 8.5, the temperature is preferably from 50 to 70 ℃ and the stabilization time in step (c) is generally from 0 to 60 minutes, preferably from 15 to 45 minutes.
Due to different application purposes, different requirements are required on the acid cracking function of the silicon aluminum, and the properties of the silicon aluminum prepared by the process can be properly changed by adjusting the adding amount of the silicon compound in the step (d).
The process of step (e) should be a generalized aging process, and pH, temperature and aging time are important control parameters, typically pH 7.5-9.5, preferably 8.0-9.0, temperature 50-70, preferably 55-65, for typically 10-60 minutes, preferably 15-45 minutes.
After the aging is finished, in the process (f), the obtained silicon-aluminum product can be washed according to a conventional method to remove impurities such as iron ions, sodium ions, sulfate radicals, chloride ions and the like, and is dried and crushed to obtain the aluminum. The purpose of the impurity removal is that when the silica-alumina of the present invention is used as a component of a catalyst, the impurity level does not affect the activity or stability of the catalyst.
The specific surface area and the pore volume of the product are calculated according to a BET formula by adopting ASAP2400 and low-temperature nitrogen adsorption (77K). The acid amount and acid properties were measured by infrared spectroscopy, and the adsorbent used was pyridine.
The effects and advantages of the present invention will be further described with reference to the following examples and comparative examples, but the following examples are not intended to limit the process of the present invention, and the% are by mass unless otherwise specified in the context of the present invention.
Example 1
42.1g of yeast was dissolved in 220mL of water, and then 19.3g of glucose was added to the solution, and after completely dissolving the mixture by stirring, the mixture was kept at 20 ℃ for 2 hours to obtain a mixture A1. 150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3(molecular ratio, the same below), unit cell constant 24.50 and relative crystallinity 90%) was added to 2 liters of distilled water, stirred and beaten to form a slurry (a), 4000g of solid aluminum sulfate was added to distilled water while heating and stirring to dissolve to give aluminum sulfate solution (b), and Al was added to the solution2O3The concentration was about 4g/100 ml. Adding a proper amount of distilled water into the concentrated ammonia water to dilute the concentrated ammonia water to obtain dilute ammonia water (c) with the concentration of about 10 percent. 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Get oneAdding 2 liters of distilled water into a 50 liter steel reaction tank, stirring and heating to 70 ℃, simultaneously opening valves of containers respectively containing aluminum sulfate and ammonia water, slowly adding (a) into the reaction tank, setting the flow rate of (b) according to 750g of prepared silicon-aluminum products so as to lead the neutralization reaction time to be one hour, simultaneously adjusting the adding speed of (a), ensuring that (a) is also added when (b) is added, rapidly adjusting the flow rate of (c) so as to lead the pH value of the system to be kept between 7 and 8, and controlling the temperature of the system to be about 65 ℃. Stopping adding ammonia water after the aluminum sulfate reaction is finished, stabilizing the generated alumina sol for 15 minutes, and finally obtaining the product containing SiO2The amount was started and the amount (d) 3.3 l was metered in over 10 minutes. The mixture A1 was added with stirring, the addition was completed within 10 minutes, the aging process of the system was started, and the temperature was maintained at 60-65 ℃. After aging for 45 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). Drying at 120 ℃ for 4h to obtain the carrier S-1.
153.7g of S-1 carrier related by the invention is weighed, 250g of jelly-like adhesive which is formed by adding nitric acid peptization to small-pore alumina with pore volume of 0.42ml/g is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the catalyst C-1 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Example 2
100.3g of yeast was dissolved in 220mL of water, 125.6g of glucose was added to the solution, and after completely dissolving the mixture by stirring, the mixture was kept at 30 ℃ for 3 hours to obtain a mixture A2. 150g of modified beta (SiO) in hydrogen form2/Al2O328 having a unit cell constant of 11.98 a and a relative crystallinity of 87%) was added to 2 liters of distilled water and stirred and beaten to form slurry (a), 4000g of solid aluminum sulfate was added to distilled water while heating and stirring to dissolve to give aluminum sulfate solution (b), Al2O3The concentration was about 4g/100 ml. Diluting the concentrated ammonia water with appropriate amount of distilled water to obtain diluted ammonia water (10%)c) In that respect 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Taking a 50-liter steel reaction tank, adding 2 liters of distilled water into the tank, stirring and heating the tank to 70 ℃, simultaneously opening valves of containers respectively containing aluminum sulfate and ammonia water, slowly adding (a) into the reaction tank, setting the flow rate of (b) according to 750g of prepared silicon-aluminum products so as to ensure that the neutralization reaction time is one hour, simultaneously adjusting the adding speed of (a), ensuring that the (a) is also added when the (b) is added, quickly adjusting the flow rate of (c) so as to ensure that the pH value of the system is kept between 7 and 8, and controlling the temperature of the system to be about 65 ℃. Stopping adding ammonia water after the aluminum sulfate reaction is finished, stabilizing the generated alumina sol for 15 minutes, and finally obtaining the product containing SiO2The amount was started and the amount (d) 3.3 l was metered in over 10 minutes. The mixture A2 was added with stirring over 10 minutes, the aging process of the system was started, the pH was maintained at 8.0 and the temperature was 60-65 ℃. After aging for 45 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). Drying at 120 deg.C for 4h to obtain carrier S-2.
153.7g of S-2 carrier related by the invention is weighed, 250g of jelly-like adhesive which is formed by adding small-hole alumina with the pore volume of 0.42ml/g and nitric acid peptization is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the catalyst C-2 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Example 3
193.7g of yeast was dissolved in 220mL of water, and then 232g of glucose was added to the solution, and after completely dissolving the mixture by stirring, the mixture was kept at 30 ℃ for 4 hours to obtain a mixture A3. 150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3Unit cell constant 24.50 a, relative crystallinity 90%) was added to 2 liters of distilled water, stirred and beaten to form slurry (a), 4000g of solid aluminum sulfate was added to 7.5 liters of distilled water while heating and stirring to dissolve,obtaining aluminum sulfate solution (b), Al2O3The concentration was about 4g/100 ml. Mixing (a) and (b) to form (b'). Adding a proper amount of distilled water into the concentrated ammonia water to dilute the concentrated ammonia water to obtain dilute ammonia water (c) with the concentration of about 10 percent. 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Taking a 50-liter steel reaction tank, adding 2 liters of distilled water into the tank, stirring and heating to 70 ℃, simultaneously opening valves of containers respectively storing aluminum sulfate (containing molecular sieve slurry) and ammonia water, setting the flow rate of (b') according to 750g of prepared silicon-aluminum products so as to lead the neutralization reaction time to be one hour, adjusting the flow rate of (c) to lead the pH value of the system to be kept between 7 and 8, and controlling the temperature of the system to be about 65 ℃. Stopping adding ammonia water after the aluminum sulfate reaction is finished, stabilizing the generated alumina sol for 15 minutes, and finally obtaining the product containing SiO23.3 l of (d) were initially metered in, the addition being completed within 10 minutes, the mixture A3 was added with stirring and the addition being completed within 10 minutes, the aging process of the system was started and the temperature was maintained at 60-65 ℃. After aging for 40 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). Pulping the (e) again, adding 17.6ml of phosphoric acid, continuously stirring for 30 minutes, filtering to obtain a filter cake (f), and drying at 120 ℃ for 4 hours to obtain the carrier S-3.
153.7g of S-3 carrier related by the invention is weighed, 250g of jelly-like adhesive which is formed by adding small-hole alumina with the pore volume of 0.42ml/g and nitric acid peptization is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the catalyst C-3 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Example 4
150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3Unit cell constant 24.50 a, relative crystallinity 90%) was added to 2 liters of distilled water, stirred and beaten to form slurry (a), 4000g of solid aluminum sulfate was added to distilled water while heating and stirring to dissolve to giveAluminum sulfate solution (b), Al2O3The concentration was about 4g/100 ml. Mixing (a) and (b) to form (b'). Adding a proper amount of distilled water into the concentrated ammonia water to dilute the concentrated ammonia water to obtain dilute ammonia water (c) with the concentration of about 10 percent. 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Taking a 15L steel reaction tank, adding 2L distilled water into the tank, stirring and heating to 70 ℃, simultaneously opening valves of containers respectively storing aluminum sulfate (containing molecular sieve slurry) and ammonia water, setting the flow rate of (b') according to 750g of prepared silicon-aluminum product so as to lead the neutralization reaction time to be one hour, adjusting the flow rate of (c) to lead the pH value of the system to be kept between 7 and 8, and controlling the temperature of the system to be about 65 ℃. Stopping adding ammonia water after the aluminum sulfate reaction is finished, stabilizing the generated alumina sol for 15 minutes, and finally obtaining the product containing SiO23.3 liters of (d) were initially metered in, the addition was completed within 10 minutes, the aging process of the system was started and the temperature was maintained at 60-65 ℃. After aging for 50 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). Pulping the (e) again, adding 17.6ml of phosphoric acid, continuously stirring for 30 minutes, filtering to obtain a filter cake (f), and drying at 120 ℃ for 4 hours to obtain the carrier S-4.
29.9g of yeast was dissolved in 100mL of water, and then 20.5g of glucose was added to the solution, and after completely dissolving the mixture by stirring, the mixture was kept at 30 ℃ for 4 hours to obtain a mixture A4. 153.7g of S-4 carrier is weighed, 150g of jelly-shaped adhesive which is formed by adding small-hole alumina with the pore volume of 0.42ml/g and nitric acid peptization is added, the mixture is rolled into a cluster, the cluster is placed into a strip extruding machine to be extruded into a cylindrical strip shape, the cylindrical strip shape is dried for 10 hours at the temperature of 110 ℃, and the cylindrical strip shape is activated for 4 hours at the temperature of 500 ℃ to obtain the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the catalyst C-4 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Example 5
49.5g of yeast was dissolved in 220mL of water, 56.3g of glucose was added to the solution, and after completely dissolving the mixture by stirring, the mixture was kept at 30 ℃ for 3 hours to obtain a mixture A5. 150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3Unit cell constant 24.50 a, relative crystallinity 90%) was added to 2 liters of distilled water, slurried with stirring to form slurry (a), and solid sodium aluminate was formulated to a concentration of 200g Al2O3/l concentrated sodium aluminate solution, and then diluted into Al with the concentration of 20g2O3Taking SiO-containing sodium aluminate working solution228wt% sodium silicate solution, and then diluted to 100g SiO2L sodium silicate working solution. 10L of sodium aluminate working solution is taken and placed in a gel forming tank, then 0.3L of sodium silicate working solution is added, and then 0.2L of slurry (a) is added. The mixture A5 was added with stirring over 10 minutes, the reaction temperature was controlled at 24 ℃ and the flow rate was 6Nm3CO at a concentration of 50 v%/h2Gas, CO introduction is stopped when the pH value reaches 10.020.6L of sodium silicate working solution was added and then stabilized for 10 minutes, and the slurry was filtered and washed to neutrality with deionized water at 75 ℃. The carrier dried at 120 ℃ for 4 hours is marked as a silicon-aluminum product S-5.
153.7g of S-5 carrier related by the invention is weighed, 250g of jelly-like adhesive which is formed by adding small-hole alumina with the pore volume of 0.42ml/g and nitric acid peptization is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the catalyst C-5 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Comparative example 1
150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3(molecular ratio, the same below), unit cell constant 24.50 and relative crystallinity 90%) was added to 2 liters of distilled water, stirred and beaten to form a slurry (a), 4000g of solid aluminum sulfate was added to distilled water while heating and stirring to dissolve to give aluminum sulfate solution (b), and Al was added to the solution2O3The concentration was about 4g/100 ml. Adding a proper amount of distilled water into the concentrated ammonia water to dilute the concentrated ammonia water to obtain dilute ammonia water (c) with the concentration of about 10 percent. 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Get one 502 liters of distilled water is added into a steel reaction tank, stirred and heated to 70 ℃, valves of containers respectively storing aluminum sulfate and ammonia water are opened at the same time, the (a) is slowly added into the reaction tank, the flow rate of the (b) is set according to the preparation of 750g of silicon-aluminum products so as to lead the neutralization reaction time to be one hour, the adding speed of the (a) is adjusted at the same time, the (a) is ensured to be added when the (b) is added, the flow rate of the (c) is quickly adjusted so as to lead the pH value of the system to be kept between 7 and 8, and the temperature of the system is controlled to be about 65 ℃. Stopping adding ammonia water after the aluminum sulfate reaction is finished, stabilizing the generated alumina sol for 15 minutes, and finally obtaining the product containing SiO2The amount was initially metered in (d) 3.3 l, which was completed in 10 minutes. The aging process of the system is started, and the temperature is kept between 60 and 65 ℃. After aging for 45 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). The carrier was obtained as D-1 by drying at 120 ℃ for 4 h.
153.7g of the D-1 carrier related by the invention is weighed, 250g of jelly-like adhesive which is formed by adding the pore volume of 0.42ml/g of small-pore alumina and nitric acid peptization is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the comparative catalyst DC-1 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Comparative example 2
150g of modified beta (SiO) in hydrogen form2/Al2O3(ii) 28 a molecular sieve having a unit cell constant of 11.98 and a relative crystallinity of 87%) was added to 2 liters of distilled water, stirred and beaten to form a slurry (a), 4000g of solid aluminum sulfate was added to distilled water while heating and stirring to dissolve to obtain an aluminum sulfate solution (b), Al2O3The concentration was about 4g/100 ml. Adding a proper amount of distilled water into the concentrated ammonia water to dilute the concentrated ammonia water to obtain dilute ammonia water (c) with the concentration of about 10 percent. 10l of distilled water were added to 4.8 l of a technical grade concentrated water glass having a modulus of 3.0 to give a dilute water glass solution (d). Taking a 50L steel reaction tank, adding 2L distilled water and 50 percent of the slurry (a)And after stirring and heating to 70 ℃, simultaneously opening valves of containers respectively storing aluminum sulfate, ammonia water and water glass, setting the flow rate of (b) according to 750g of prepared silicon-aluminum product so as to lead the neutralization reaction time to be within one hour, simultaneously adjusting the adding speed of (a) to ensure that the residual slurry (a) is also added when the addition of (b) and (d) is finished, rapidly adjusting the flow rate of (c) to lead the pH value of the system to be kept between 7 and 8, and controlling the temperature of the system to be about 65 ℃. Then aging, keeping pH at 8.0 and temperature at 60-65 deg.C. After aging for 45 minutes, the colloidal solution was filtered to obtain a wet cake, the wet cake was again slurried with distilled water and washed with water, and then filtered to obtain a cake (e). The support dried at 120 ℃ for 4h is designated D-2.
153.7g of the D-2 carrier related by the invention is weighed, 250g of jelly-shaped adhesive which is prepared by adding nitric acid peptization into small-pore alumina with pore volume of 0.42ml/g, the mixture is rolled into a cluster, the cluster is placed into a strip extruding machine to be extruded and molded, the cluster is dried for 10 hours at 110 ℃, and the cluster is activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the comparative catalyst DC-2 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
Comparative example 3
150g of modified Y molecular Sieve (SiO) in hydrogen form2/Al2O3Unit cell constant 24.50 a, relative crystallinity 90%) was added to 2 liters of distilled water, slurried with stirring to form slurry (a), and solid sodium aluminate was formulated to a concentration of 200g Al2O3/l concentrated sodium aluminate solution, and then diluted into Al with the concentration of 20g2O3Taking SiO-containing sodium aluminate working solution228wt% sodium silicate solution, and then diluted to 100g SiO2L sodium silicate working solution. Placing 10L of sodium aluminate working solution in a colloid forming tank, adding 0.3L of sodium silicate working solution, adding 0.2L of slurry (a), controlling the reaction temperature at 24 deg.C, and introducing the slurry at 6Nm3CO at a concentration of 50 v%/h2Gas, CO introduction is stopped when the pH value reaches 10.02Adding 0.6L of sodium silicate working solution, stabilizing for 10 min, filtering the slurry and washing with deionized water at 75 deg.CAnd (4) the product is neutral. And marking the carrier dried at 120 ℃ for 4 hours as a silicon-aluminum product D-3.
153.7g of the D-3 carrier related by the invention is weighed, 250g of jelly-like adhesive which is prepared by adding the pore volume of 0.42ml/g of small-pore alumina and nitric acid peptization is added, rolled into a cluster, put into a strip extruding machine for extruding and forming, dried for 10 hours at 110 ℃, and activated for 4 hours at 500 ℃ to prepare the carrier. 40.9g of ammonium metatungstate and 45g of nickel nitrate were dissolved and calibrated to 85ml, to obtain a W-Ni co-immersion liquid. Then the carrier is loaded with active metal by W-Ni co-impregnation liquid, and the comparative catalyst DC-3 is obtained after drying for 12 hours at 110 ℃ and activating for 3 hours at 500 ℃.
The above samples were calcined at 600 ℃ for 6h and analyzed, the results are shown in Table 1. As can be seen from the results in Table 1, in SiO2When the contents are relative, the specific surface and the pore volume of the comparative sample are lower than those of the sample of the invention, the infrared acidity is increased, the proportion of B acid is also increased, and the performance of the catalyst is improved.
TABLE 1 Main Properties of the support Material
Figure 300747DEST_PATH_IMAGE001
The physicochemical properties of the catalyst samples obtained in the examples and comparative examples are shown in Table 2.
TABLE 2 physicochemical Properties of catalysts of examples and comparative examples
Figure 195014DEST_PATH_IMAGE002
Example 6
The catalysts of the invention and comparative catalysts described above were evaluated. The raw oil for evaluation is victory VGO, the reaction pressure is 14MPa, the volume ratio of hydrogen to oil is 1500, and the airspeed is 1.5h-1. The main properties are shown in table 3. Evaluation the activity of the hydrocracking catalyst was assessed by comparing the reaction temperature at which the same conversion per pass was achieved and the selectivity of the catalyst was assessed as a function of the product distribution at a given conversion, the medium oil selectivity being calculated as "middle distillate yield<Product yield at 370 ℃In (1).
Figure 17477DEST_PATH_IMAGE004
Table 4 comparative evaluation results of catalysts of the invention
Figure 346827DEST_PATH_IMAGE006
As can be seen from the physicochemical properties of the catalyst in Table 2, the use of the carrier of the present invention is more favorable for the loading of active metals, and the pore volume and the specific surface area are both superior to those of the comparative examples, and as can be seen from the evaluation results in Table 4, the use of the carrier of the present invention can obtain higher yield of middle distillate oil at the same reaction temperature, and the product properties are also improved.

Claims (14)

1. A preparation method of a silicon-aluminum carrier is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving yeast in aqueous solution, and mixing with starch uniformly for later use;
(2) adding water into the needed molecular sieve and pulping to form molecular sieve pulp for later use;
(3) introducing the molecular sieve slurry obtained in the step (2) into gelling process of amorphous silica-alumina, wherein the addition amount of the molecular sieve is 5-80% of the weight of the final hydrocracking catalyst carrier, and aging, filtering and washing after gelling;
(4) kneading, molding, drying and roasting the material obtained in the step (3) to obtain a silicon-aluminum carrier;
wherein the material in step (1) is introduced during step (3) or during the kneading in step (4).
2. The method of claim 1, wherein: and (3) introducing the material in the step (1) before aging after gelling the amorphous silica-alumina in the step (3).
3. The method of claim 1, wherein: in the step (1), the yeast is one of a haplotype, a doublet and a haplotype and doublet or a mixture thereof, and is dissolved in an aqueous solution to have a pH value of 3.0-7.5, preferably a pH value of 4-6.
4. The method of claim 1, wherein: the yeast content of the material of step (1) is 5-50% by weight, preferably 15-30% by weight.
5. The method of claim 1, wherein: in the step (2), the molecular sieve is one or more of Y-type molecular sieve, beta zeolite, ZSM series molecular sieve, SAPO series molecular sieve and the like, and the weight concentration of the molecular sieve slurry is 5-40%.
6. The method of claim 1, wherein: the gelling process of the amorphous silica-alumina in the step (3) is a neutralization reaction process of an acidic material and an alkaline material, and the gelling process adopts an operation mode of parallel flow gelling of two materials or an operation mode of continuously adding one material into another material in a gelling tank.
7. The method of claim 1, wherein: in the step (4), the aging pH value is 7.5-9.5, the aging temperature is 50-70 ℃, and the aging time is 5-60.
8. The method of claim 1, wherein: the drying temperature in the step (4) is 100-140 ℃, and the drying time is 2-6 h.
9. A silica-alumina carrier characterized by: prepared by the process of any one of claims 1 to 8.
10. The silica alumina carrier of claim 9, wherein: the carrier comprises, by weight, 5-80% of molecular sieve, 20-95% of amorphous silicon-aluminum, and the content of silicon dioxide in the amorphous silicon-aluminum is10wt% -80 wt%; the properties of the vector are as follows: the specific surface area is 200m2/g~800m2Per g, pore volume of 0.3cm3/g~1.8cm3The amount of the infrared acid at the temperature of not less than 350 ℃ is 0.04-1.10 mmol/g, wherein the B acid accounts for 40-60% of the total acid.
11. A hydrocracking catalyst characterized by: the hydrocracking catalyst contains the silica-alumina carrier according to claim 9.
12. The catalyst of claim 11, wherein: the catalyst comprises 60-86% of a carrier and 14-40% of active metal by weight.
13. The catalyst of claim 12, wherein: the active metal is a VIB group metal and/or a VIB group metal, the mass content of the VIII group metal calculated by oxide is 10-30%, and the mass content of the VIII group metal calculated by oxide is 4-10%; wherein the group VIB metal is selected from Mo and/or W, and the group VIII metal is selected from Co and/or Ni.
14. Use of a catalyst according to any of claims 11-13 in a hydrocracking reaction, characterized in that: the reaction conditions were as follows: the reaction pressure is 5-25MPa, the hydrogen-oil ratio is 100--1The reaction temperature is 340-450 ℃.
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