CN111468097A - Catalytic cracking catalyst, preparation method and application thereof - Google Patents

Catalytic cracking catalyst, preparation method and application thereof Download PDF

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CN111468097A
CN111468097A CN202010215318.7A CN202010215318A CN111468097A CN 111468097 A CN111468097 A CN 111468097A CN 202010215318 A CN202010215318 A CN 202010215318A CN 111468097 A CN111468097 A CN 111468097A
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catalytic cracking
catalyst
cracking catalyst
modifier
silicon
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CN111468097B (en
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江莉龙
马永德
曹彦宁
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Fuzhou University National Engineering Research Center Of Chemical Fertilizer Catalyst
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Fuzhou University National Engineering Research Center Of Chemical Fertilizer Catalyst
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • 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
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Abstract

The invention discloses a catalytic cracking catalyst and a preparation method and application thereof, wherein the catalyst is an amorphous composite oxide prepared by taking silicon dioxide as a matrix and doping a modifier, and is suitable for a suspension bed hydrocracking process, and the modifier is an oxide of IIIB metal or IVB metal in a periodic table of elements. According to the invention, the silica sol is prepared preferentially, the modifier is deposited on the surface of the silica sol, then crystallization is carried out at a proper temperature by a hydrothermal method, the amorphous composite oxide is prepared by roasting under a set condition, the modifier oxide can be anchored on the silicon dioxide substrate, the amorphous composite oxide is firmly combined by virtue of an M-O-Si bond, the silicon dioxide substrate can be inhibited from agglomerating and growing in the crystallization or roasting process, the composite oxide material maintains nano particles and a high specific surface area, the high dispersion of the catalytic material in a suspended bed is facilitated, and a reaction site is provided for organic macromolecules.

Description

Catalytic cracking catalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of petroleum catalytic cracking, in particular to a catalytic cracking catalyst and a preparation method and application thereof.
Background
In recent years, with increasing heavy and inferior crude oil resources in the world, increasing demand for light oil products and decreasing demand for heavy fuel oil, the deep processing technology of heavy and inferior oil becomes a key and difficult problem to be researched and solved urgently in the oil refining industry, and the efficient utilization of heavy and inferior oil becomes an important direction of the national development strategy of petroleum resources. The suspension bed hydrogenation process is a heavy oil hydrogenation process which takes inferior heavy oil as a raw material and takes the production of light fuel oil as a processing purpose, and is one of ideal methods for realizing the lightening of the inferior heavy oil. The process is suitable for lightening inferior heavy oil with high metal content, high carbon residue and high asphaltene, and has the characteristics of high conversion per pass, high diesel oil fraction yield, high cetane number and the like.
The suspension bed hydrocracking reaction is mainly thermal cracking and accompanied with a hydrogenation reaction, and the reaction mainly proceeds according to a free radical thermal cracking mechanism. At H2In the presence of a catalyst, the catalyst can adsorb and activate hydrogen gas into hydrogen radicals; the free radicals can capture and seal the coke-forming precursor free radicals, and inhibit polymerization coke-forming reaction. The presence of the catalyst mainly inhibits the condensation coking reaction of macromolecular compounds and reduces the wall of the reactorCoking and prolonging the start-up period of the equipment. In order to obtain higher yield of light components, the existing suspension bed process usually increases the reaction temperature and pressure to accelerate the thermal cracking reaction. In this way, while more light components are obtained, the polymerization coking reaction of the coking precursor is accelerated, the generated coke is adsorbed on the surface of the hydrogenation catalyst and in a pore channel to cause inactivation, and the coke adsorbed on the wall of the reactor even can block an equipment pipeline to cause the shutdown of the whole process. The degree of thermal cracking under such high temperature and pressure conditions is severe and the reaction path is not controllable. Therefore, catalytic cracking at lower reaction temperatures and pressures is probably a better choice. Unlike thermal cracking, which proceeds according to a radical reaction mechanism, catalytic cracking proceeds according to a carbonium ion mechanism, and the catalyst promotes cracking, isomerization and aromatization reactions, and the cracked product has higher economic value than thermal cracking.
However, the research on the catalyst in the existing suspension bed hydrogenation process mainly focuses on improving the hydrogenation capacity of the catalyst, and the research on the catalytic cracking capacity of the catalyst is less. For example, chinese patent document CN101543783 discloses a suspension bed hydrocracking catalyst, which adopts a catalytic cracking waste catalyst as a carrier, and a supported transition metal as an active component, wherein the supported transition metal is 0.5-10 wt% in terms of metal oxide; the transition metal is selected from one or more of VIB and VIII group metals, and the catalytic cracking waste catalyst comprises 15-55 wt% of Y-type molecular sieve and 15-45 wt% of alumina; the specific surface area is 50-300 m2The relative crystallinity is 5-15%, and the catalytic cracking capability of the catalyst is improved by introducing the waste cracking catalyst. However, the above catalysts still have significant disadvantages because the catalytic cracking active sites of the conventional cracking catalysts are substantially located in the channels of the molecular sieve, and the reaction molecules enter the channels to contact with the active sites and react with the active sites. However, molecules of the inferior heavy oil are macromolecules, so that the molecules of the inferior heavy oil cannot enter a pore passage to contact with active sites due to the limitation of the diameter of a molecular sieve, and then catalytic cracking reaction occurs. Therefore, the traditional cracking catalyst is not suitable for the catalytic cracking of the poor oil suspension bed.
In view of this, it is urgently needed to develop a catalytic cracking catalyst suitable for the suspension bed of inferior oil, to achieve the catalytic cracking of macromolecules in inferior oil at low temperature, and to change the working conditions of the existing suspension bed for treating inferior oil products by high-temperature thermal cracking and high-pressure hydrogen only.
Disclosure of Invention
The invention aims to solve the problem that the existing hydrogenation process of the inferior oil suspension bed only depends on the working conditions of high-temperature thermal cracking and high-pressure hydrogen, and has low yield of light fractions, thereby providing a catalytic cracking catalyst suitable for the inferior oil suspension bed, a preparation method and application thereof.
The invention adopts the following technical scheme:
the catalytic cracking catalyst is characterized in that the catalyst is an amorphous composite oxide prepared by taking silicon dioxide as a matrix and doping a modifier, wherein the modifier is an oxide of IIIB metal or IVB metal in a periodic table of elements, and the molar ratio of IIIB metal ions or IVB metal ions to silicon ions in the catalyst is 1 (1-100).
The metal element in the modifier is one or more of titanium, zirconium, yttrium, lanthanum and cerium.
The molar ratio of IIIB metal ions or IVB metal ions to silicon ions in the catalyst is 1 (1-50).
The particle size of the catalyst is 1-100 nm, and the specific surface area is 100-800 m2The acid site density is 0.2 to 0.9mmol/g, and the ratio of the acid amount of B to the acid amount of L is 0.1 to 0.4.
The particle size of the catalyst is 1-50 nm.
A preparation method of a catalytic cracking catalyst comprises the following steps:
s1, mixing alcohols and water according to the volume ratio of 1 (0.2-1) to prepare a mixed solution, then adding a silicon-based precursor into the mixed solution, wherein the volume ratio of the silicon-based precursor to the mixed solution is 1:5-50, and stirring at normal temperature to hydrolyze the silicon-based precursor to prepare silica sol;
s2, adding the modifier precursor into the silica sol prepared in the step S1 according to a specific proportion, uniformly mixing, then dropwise adding an alkaline substance to enable the pH value of the sol to be 2-10, then transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction at 60-200 ℃ for 4-24 hours to obtain an intermediate;
s3, cooling the temperature of the intermediate prepared in the step S2 to normal temperature, centrifuging, washing to neutrality, drying, and roasting the product at 300-1000 ℃ for 3-12 hours to obtain the catalytic cracking catalyst.
In the step S1, the alcohol is one of methanol, ethanol, ethylene glycol and isopropanol, and the silicon-based precursor is one of butyl orthosilicate, ethyl orthosilicate, methyl orthosilicate and water glass.
The modifier precursor in the step S2 is soluble salt of IIIB metal or IVB metal in the periodic table of elements; the alkaline substance added dropwise is one of ammonia water, NaOH and KOH.
Preferably, the modifier precursor in step S2 is a soluble salt of one or more metals selected from titanium, zirconium, yttrium, lanthanum and cerium.
The soluble salt is one of sulfate, nitrate, chlorate, oxychloronate and organic acid salt.
And S2, dropwise adding alkali liquor to ensure that the pH value in the sol is 2-7 and the reaction temperature of the hydrothermal reaction is 80-150 ℃.
In the step S3, the drying temperature is 80-120 ℃, and the roasting temperature of the product is 400-800 ℃.
An application of a catalytic cracking catalyst in a poor-quality oil suspension bed hydrocracking process comprises the following steps:
placing inferior oil into a suspension bed cracking reactor;
dispersing a catalytic cracking catalyst into the inferior oil, wherein the addition amount of the catalytic cracking catalyst is 1-20 wt% in terms of the weight percentage of the inferior oil;
and step three, the reaction temperature of the inferior oil suspension bed process is 380-420 ℃, and the reaction pressure is 6-15 MPa.
Adding one or more of compound molybdenum, tungsten, iron, cobalt or nickel hydrogenation catalysts in the second step, and dispersing the mixture into the inferior oil.
The addition amount of the catalytic cracking catalyst is 3-15 wt% and the addition amount of the compound hydrogenation catalyst is 0.5-5 wt% based on the weight percentage of the inferior oil.
The technical scheme of the invention has the following advantages:
A. the catalytic cracking catalyst is an amorphous composite oxide prepared by preferentially preparing silica sol, depositing a modifier on the surface of the silica sol, then crystallizing at a proper temperature by a hydrothermal method, and roasting under a set condition. The preparation method provided by the invention can anchor the modifier oxide on the silicon dioxide matrix and firmly bond the modifier oxide by virtue of an M-O-Si bond. On one hand, the agglomeration and growth of the silicon oxide matrix in the crystallization or roasting process can be inhibited, and the composite oxide material maintains nano particles and high specific surface area; on the other hand, the high-dispersion modified oxide can effectively and fully react with the silicon oxide matrix during roasting to generate the composite oxide material. The small particle size and the large specific surface area are beneficial to the high dispersion of the catalytic material in a suspension bed, and provide a reaction site for the reaction of organic macromolecules on the surface of the catalyst.
B. The catalytic cracking catalyst of the invention has extremely weak acidity of the raw materials, but the nano composite oxide material rich in new M-O-Si bonds is prepared by the special preparation process and conditions of the invention. While forming M-O-Si bonds, the bridging oxygen (Si-O-Si) and the terminal oxygen (Si-O) of the silicate bond hydrogen protons (H)+) Abundant surface hydroxyl groups are formed on the surface of the composite material; the modified transition metal ion M + and the silicon ion have different electronegativities, and the modified ion M+The rich B acid sites of the composite catalytic material provide catalytic active sites for catalytic cracking of organic macromolecules, improve the cracking efficiency of the organic macromolecules, and simultaneously, the L acid sites on the surface of the catalyst can stabilize free radicals for cracking the macromolecules and prevent the disordered repolymerization and coking of the free radicalsThe material is suitable for catalytic cracking of poor-quality oil suspension bed catalyst.
C. The catalytic cracking catalyst and the catalytic hydrogenation catalyst provided by the invention are compounded for use, and have a synergistic effect. The catalytic hydrogenation catalyst can activate hydrogen molecules into hydrogen free radicals, and timely hydrogenates and saturates small molecular unsaturated bonds formed by cracking reaction, thereby effectively inhibiting the agglomeration among the free radicals and improving the yield of light fractions. Particularly, the hydrogen free radicals can capture and block coke precursor free radicals, inhibit polymerization coke formation reaction, effectively protect the catalytic cracking catalyst from being inactivated due to carbon deposition, and prolong the service life of the catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings which are needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained from the drawings without inventive labor to those skilled in the art.
FIG. 1 is a transmission electron microscope image of a catalytic cracking catalyst prepared by the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a catalytic cracking catalyst, which is an amorphous composite oxide prepared by doping a modifier with silicon dioxide serving as a matrix, wherein the modifier is an oxide of IIIB metal or IVB metal in a periodic table of elements, preferably an oxide of one or more of titanium, zirconium, yttrium, lanthanum and cerium, and the molar ratio of IIIB metal ions or IVB metal ions to silicon ions in the catalyst is 1 (1-100), preferably 1 (1-50). The catalyst has a particle size of 1 to 100nm, preferably 1 to 50nm, in terms of the ratioThe surface area is 100 to 800m2The acid site density is 0.2 to 0.9mmol/g, and the ratio of the acid amount of B to the acid amount of L is 0.1 to 0.4.
The invention also provides a preparation method of the catalytic cracking catalyst, which is characterized by comprising the following steps:
s1, mixing alcohols and water according to the volume ratio of 1 (0.2-1), then adding a silicon-based precursor into the mixed solution, wherein the volume ratio of the silicon-based precursor to the mixed solution is 1:5-50, and stirring at normal temperature to hydrolyze the silicon-based precursor to prepare the silica sol. The alcohol is one of methanol, ethanol, glycol and isopropanol, and the silicon-based precursor is one of n-butyl silicate, ethyl orthosilicate, methyl orthosilicate and water glass.
S2, adding the modifier precursor into the silica sol prepared in the step S1 according to a specific proportion, then dropwise adding an alkaline substance to enable the pH value of the sol to be 2-10, then transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 4-24 hours at the temperature of 60-200 ℃ to obtain an intermediate. The modifier precursor is soluble salt of IIIB metal or IVB metal in the periodic table of elements, preferably soluble salt of one or more of titanium, zirconium, yttrium, lanthanum and cerium, the soluble salt can be one of sulfate, nitrate, chlorate, oxychloridate and organic acid salt, and the molar ratio of the added modifier precursor to silicon in the silica sol is 1 (1-100), preferably 1 (1-50); the pH value is preferably 2-7, and the hydrothermal reaction temperature is preferably 80-150 ℃.
And S3, cooling the temperature of the intermediate prepared in the step S2 to normal temperature, centrifuging, washing and drying the intermediate, and roasting the product at 300-1000 ℃ for 3-12 hours to obtain the catalytic cracking catalyst. The drying temperature is 80-120 ℃, and the roasting temperature of the product is preferably 400-800 ℃.
The catalytic cracking catalyst is an amorphous composite oxide prepared by preferentially preparing silica sol, depositing a modifier on the surface of the silica sol, then crystallizing at a proper temperature by a hydrothermal method, and roasting under a set condition. The preparation method provided by the invention can anchor the modifier oxide on the silicon dioxide matrix and firmly bond the modifier oxide by virtue of an M-O-Si bond. On one hand, the agglomeration and growth of the silicon oxide matrix in the crystallization or roasting process can be inhibited, and the composite oxide material maintains nano particles and high specific surface area; on the other hand, the high-dispersion modified oxide can effectively and fully react with the silicon oxide matrix during roasting to generate the composite oxide material. The small particle size and the large specific surface area are beneficial to the high dispersion of the catalytic material in a suspension bed, and provide a reaction site for the reaction of organic macromolecules on the surface of the catalyst.
The raw materials for preparing the catalytic cracking catalyst of the invention have extremely weak acidity, but the nano composite oxide material rich in new M-O-Si bonds is prepared by special preparation process and conditions. While forming M-O-Si bonds, the bridging oxygen (Si-O-Si) and the terminal oxygen (Si-O) of the silicate bond hydrogen protons (H)+) Abundant surface hydroxyl groups are formed on the surface of the composite material; the modified transition metal ion M + and the silicon ion have different electronegativities, and the modified ion M+The rich B acid sites of the composite catalytic material provide catalytic active sites for the catalytic cracking of organic macromolecules, so that the cracking efficiency of the organic macromolecules is improved, and meanwhile, the L acid sites on the surface of the catalyst can stabilize free radicals for macromolecular cracking and prevent the disordered secondary polymerization and coking of the free radicals.
In addition, the invention also provides an application of the catalytic cracking catalyst in the poor-quality oil suspension bed process, wherein the catalytic cracking catalyst can be used alone as the poor-quality oil suspension bed catalytic cracking catalyst, and can also be compounded with one or more of molybdenum, tungsten, iron, cobalt or nickel hydrogenation catalysts for simultaneous use. The amount of the catalytic cracking catalyst is 1-20 wt%, preferably 3-15 wt%, based on the weight percentage of the poor oil.
The catalytic cracking catalyst and the catalytic hydrogenation catalyst provided by the invention are compounded for use, and have a synergistic effect. The catalytic hydrogenation catalyst can activate hydrogen molecules into hydrogen free radicals, and timely hydrogenates and saturates small molecular unsaturated bonds formed by cracking reaction, thereby effectively inhibiting the agglomeration among the free radicals and improving the yield of light fractions. Particularly, the hydrogen free radicals can capture and block coke precursor free radicals, inhibit polymerization coke formation reaction, effectively protect the catalytic cracking catalyst from being inactivated due to carbon deposition, and prolong the service life of the catalyst.
The present invention will be described in detail below by way of specific examples.
Example 1:
this example is used to illustrate the preparation method of the catalytic cracking catalyst and the catalytic cracking catalyst provided by the present invention, and specifically includes the following steps:
s1, mixing isopropanol and water according to the volume ratio of 1:1 to prepare a mixed solution, then adding tetraethoxysilane into the mixed solution, wherein the volume ratio of tetraethoxysilane to the mixed solution is 1:5, and stirring for 2 hours at normal temperature to hydrolyze the silicon-based precursor tetraethoxysilane to prepare the silica sol.
S2, adding titanium isopropoxide into the silica sol according to the molar ratio of Ti to Si of 1:50, stirring for 0.5 hour at normal temperature, dropwise adding ammonia water, adjusting the pH to 7.0, transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 20 hours at 150 ℃ to obtain an intermediate.
S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate at 800 ℃ for 8 hours to obtain a sample A.
Example 2
This example is used to illustrate the preparation method of the catalytic cracking catalyst and the catalytic cracking catalyst provided by the present invention, and specifically includes the following steps:
s1, mixing ethanol and water according to the volume ratio of 1:1 to prepare a mixed solution, then adding n-butyl silicate into the mixed solution, wherein the volume ratio of the n-butyl silicate to the mixed solution is 1:50, stirring for 2 hours at normal temperature, and hydrolyzing the silicon-based precursor n-butyl silicate to prepare the silica sol.
S2, adding zirconyl nitrate into the silica sol according to the Zr-Si molar ratio of 1:20, stirring for 0.5 hour at normal temperature, dropwise adding ammonia water, adjusting the pH to 2.0, transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 24 hours at 80 ℃ to obtain an intermediate.
And S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate at the temperature of 400 ℃ for 12 hours to prepare a sample B.
Example 3
This example is used to illustrate the preparation method of the catalytic cracking catalyst and the catalytic cracking catalyst provided by the present invention, and specifically includes the following steps:
and S1, mixing ethanol and water according to the volume ratio of 1:0.2 to prepare a mixed solution, then adding water glass into the mixed solution, wherein the volume ratio of the water glass to the mixed solution is 1:5, stirring at normal temperature for 2 hours, and hydrolyzing the silicon-based precursor water glass to prepare the silica sol.
S2, adding cerium chloride into the silica sol according to the molar ratio of Ce to Si of 1:10, stirring for 0.5 hour at normal temperature, dropwise adding ammonia water, adjusting the pH to 4.0, transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 4 hours at 110 ℃ to obtain an intermediate.
And S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate for 3 hours at the temperature of 550 ℃ to obtain a sample C.
Example 4
This example is used to illustrate the preparation method of the catalytic cracking catalyst and the catalytic cracking catalyst provided by the present invention, and specifically includes the following steps:
s1, mixing methanol and water according to the volume ratio of 1:0.5 to prepare a mixed solution, then adding methyl orthosilicate into the mixed solution, wherein the volume ratio of the methyl orthosilicate to the mixed solution is 1:25, stirring for 2 hours at normal temperature, and hydrolyzing the silicon-based precursor methyl orthosilicate to prepare the silica sol.
S2, adding lanthanum chloride into the silica sol according to the molar ratio of L a to Si of 1:5, stirring for 0.5 hour at normal temperature, dropwise adding sodium hydroxide, adjusting the pH to 3.0, transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 12 hours at 100 ℃ to obtain an intermediate.
S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate at the temperature of 450 ℃ for 6 hours to prepare a sample D.
Example 5
This example is used to illustrate the application of the catalytic cracking catalyst provided by the present invention in the poor oil suspension bed process, and specifically includes the following steps:
the method comprises the steps of selecting atmospheric residuum as inferior oil, dispersing 5 wt% (based on the mass percent of the atmospheric residuum) of oil-soluble molybdenum isooctanoate hydrogenation catalyst into the inferior oil, adding 5 wt% (based on the mass percent of the atmospheric residuum) of the catalytic cracking catalyst sample D prepared in example 4, taking solid sublimed sulfur powder as a vulcanizing agent, and adding the solid sublimed sulfur powder and the vulcanizing agent into a suspension bed hydrocracking reactor. The specific reaction conditions are as follows: in a 300ml high-pressure reaction kettle, the initial pressure is 10.0MPa, the reaction temperature is 400 ℃, and the reaction time is 4 hours.
Example 6
The example is used to illustrate the application of the catalytic cracking catalyst provided by the present invention in the poor oil suspension bed hydrocracking process, and specifically includes the following steps:
the atmospheric residue oil is selected as the poor oil, 5 wt% (based on the mass percent of the atmospheric residue oil) of the catalytic cracking catalyst sample D prepared in the example 4 is added, and the specific reaction conditions are as follows: in a 300ml high-pressure reaction kettle, the initial pressure is 10.0MPa, the reaction temperature is 400 ℃, and the reaction time is 4 hours.
Comparative example 1
The comparative example is used to illustrate a reference catalytic cracking catalyst preparation method and a catalytic cracking catalyst, and specifically includes the following:
s1, mixing methanol and water according to the volume ratio of 1:0.5 to prepare a mixed solution, then adding methyl orthosilicate into the mixed solution, wherein the volume ratio of the methyl orthosilicate to the mixed solution is 1:25, stirring for 2 hours at normal temperature, and hydrolyzing the silicon-based precursor methyl orthosilicate to prepare the silica sol.
S2, adding lanthanum chloride into the silica sol according to the molar ratio of L a to Si of 1:5, stirring for 0.5 hour at normal temperature, dropwise adding sodium hydroxide, adjusting the pH to 3.0, transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction for 12 hours at 250 ℃ to obtain an intermediate.
S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate at 1200 ℃ for 6 hours to prepare a sample E.
Comparative example 2
The comparative example is used to illustrate a reference catalytic cracking catalyst preparation method and a catalytic cracking catalyst, and specifically includes the following:
s1, mixing methanol and water according to the volume ratio of 1:0.5 to prepare a mixed solution, then adding methyl orthosilicate into the mixed solution, wherein the volume ratio of the methyl orthosilicate to the mixed solution is 1:25, stirring for 2 hours at normal temperature, and hydrolyzing the silicon-based precursor methyl orthosilicate to prepare the silica sol.
S2, adding aluminum sulfate into the silica sol according to the molar ratio of Al to Si of 1:5, stirring at normal temperature for 0.5 hour, then dropwise adding sodium hydroxide, adjusting the pH to 3.0, then transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction at 100 ℃ for 12 hours to obtain an intermediate.
S3, cooling the temperature of the prepared intermediate to normal temperature, centrifuging and washing the intermediate to be neutral, drying the intermediate, and roasting the intermediate at the temperature of 450 ℃ for 6 hours to prepare a sample F.
Comparative example 3
The method comprises the steps of selecting normal pressure residual oil as inferior oil, dispersing an oil-soluble molybdenum isooctanoate hydrogenation catalyst in the inferior oil, adding 5 wt% (based on the mass percent of the normal pressure residual oil) of a sample F prepared in the comparative example 2, and adding solid sublimed sulfur powder serving as a vulcanizing agent into a suspension bed hydrocracking reactor together. The specific reaction conditions are as follows: in a 300ml high-pressure reaction kettle, the initial pressure is 10.0MPa, the reaction temperature is 400 ℃, and the reaction time is 4 hours.
Examples of the experiments
1. Specific surface area and acidity test of samples
This experimental example tests were carried out on samples prepared in examples 1 to 4 and comparative examples 1 to 2, wherein the specific surface area of the prepared samples was measured on a full-automatic analyzer, model ASAP 2020, Micromeritics, usa. Before testing, the samples were first evacuated (less than 10 ℃) at 300 ℃-5Torr) for 4 hours, and then nitrogen adsorption measurement was performed under liquid nitrogen. The total acid content of the sample is NH3(ii) determination of temperature programmed desorption by chemisorption model AutoChem 2920 from Micromeritics, USAThe method is carried out on the instrument. The sample is firstly pretreated by heat preservation for 60 minutes at 500 ℃ under He atmosphere, and then is reduced to 50 ℃ to adsorb NH3Purging with He after adsorption saturation, and then heating to 600 deg.C (heating rate of 10 deg.C/min) under He atmosphere to obtain NH3The desorption amount of (c) was determined by MS (m/e-17) the relative content of B acid/L acid of the sample was determined by pyridine-infrared spectroscopy, by calculating 1450cm-1And 1540cm-1The relative ratio of peak areas was obtained.
TABLE 1 specific surface area and acidity test results for the samples
Figure BDA0002424201400000111
Figure BDA0002424201400000121
As is apparent from the experimental data given in Table 1, the specific surface area, the total amount of acids, and the ratio of B acid/L acid of the samples prepared in examples 1 to 4 satisfy the catalytic cracking catalyst, and are larger than those of the samples prepared in comparative examples 1 to 2.
2. Sample hydrocracking reaction performance test
The catalytic cracking catalyst provided by the invention is applied to the inferior oil suspension bed process, and the hydrocracking reaction performance of the catalytic cracking catalyst is characterized in that the conversion rate of raw oil and the yield of distillate oil are calculated according to the following formulas and are used as the evaluation indexes of the reaction effect:
conversion rate of below 520 deg.C component mass (gas)/raw material oil mass × raw material oil mass
Gas yield (raw oil-liquid product mass)/raw oil mass × raw oil mass
Yield of distillate oil below 520 deg.C liquid component/raw oil × raw oil quality
The corresponding test results are shown in table 2 below:
TABLE 2 test results of hydrocracking reaction performance of samples
Gas yield/wt% Yield of distillate oil/wt% Conversion/wt.%
Example 5 4.0 92.3 96.3
Example 6 6.5 89.7 96.2
Comparative example 3 9.8 78.4 88.2
From the experimental data given in table 2, it can be seen that the distillate yield and the conversion rate of the catalytic cracking catalyst sample D prepared in example 4 added in the hydrocracking reaction are both greater than those of the sample F prepared in comparative example 2, and respectively reach 92.3% and 96.3%, and the gas yield is significantly lower than that of the sample F prepared in comparative example 2, and is 4.0%, which indicates that the catalytic cracking catalyst prepared in the present invention is used in combination with the catalytic hydrogenation catalyst, and the catalytic cracking effect on poor oil is very good. In example 6, no compound hydrogenation catalyst is used, and compared with example 5, the gas yield is increased and the distillate yield is reduced.
3. Sample morphology and particle size testing
The morphology and particle size measurements of the samples were observed on a Tecnai G2F 20 type high resolution Transmission Electron microscope (HR-TEM). Before testing, firstly, grinding a sample, dispersing the sample in ethanol, ultrasonically oscillating, then, dripping the dispersed suspension into a carbon-coated copper net, naturally airing, and observing the appearance and the particle size of the sample under a 200KV electron beam. FIG. 1 is a TEM image of a sample of example 3, from which it can be seen that both the silica and the modifier oxide are in an amorphous state with no significant lattice striations. Meanwhile, the crystal grains of the two are small, and no obvious agglomeration phenomenon exists.
The invention is applicable to the prior art.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

Claims (15)

1. The catalytic cracking catalyst is characterized in that the catalyst is an amorphous composite oxide prepared by taking silicon dioxide as a matrix and doping a modifier, wherein the modifier is an oxide of IIIB metal or IVB metal in a periodic table of elements, and the molar ratio of IIIB metal ions or IVB metal ions to silicon ions in the catalyst is 1 (1-100).
2. The catalytic cracking catalyst of claim 1, wherein the metal element in the modifier is one or more of titanium, zirconium, yttrium, lanthanum and cerium.
3. The catalytic cracking catalyst of claim 1, wherein the molar ratio of IIIB metal ions or IVB metal ions to silicon ions in the catalyst is 1 (1-50).
4. Catalytic cracking according to claim 1The catalyst is characterized in that the particle size of the catalyst is 1-100 nm, and the specific surface area is 100-800 m2The acid site density is 0.2 to 0.9mmol/g, and the ratio of the acid amount of B to the acid amount of L is 0.1 to 0.4.
5. The catalytic cracking catalyst according to claim 4, wherein the catalyst has a particle size of 1 to 50 nm.
6. A process for preparing a catalytic cracking catalyst according to any of claims 1 to 5, characterized by comprising the steps of:
s1, mixing alcohols and water according to the volume ratio of 1 (0.2-1) to prepare a mixed solution, then adding a silicon-based precursor into the mixed solution, wherein the volume ratio of the silicon-based precursor to the mixed solution is 1:5-50, and stirring at normal temperature to hydrolyze the silicon-based precursor to prepare silica sol;
s2, adding the modifier precursor into the silica sol prepared in the step S1 according to a specific proportion, uniformly mixing, then dropwise adding an alkaline substance to enable the pH value of the sol to be 2-10, then transferring the sol into a hydrothermal kettle, and carrying out hydrothermal reaction at 60-200 ℃ for 4-24 hours to obtain an intermediate;
s3, cooling the temperature of the intermediate prepared in the step S2 to normal temperature, centrifuging, washing to neutrality, drying, and roasting the product at 300-1000 ℃ for 3-12 hours to obtain the catalytic cracking catalyst.
7. The method of claim 6, wherein the alcohol in step S1 is one of methanol, ethanol, ethylene glycol and isopropanol, and the silicon-based precursor is one of butyl orthosilicate, ethyl orthosilicate, methyl orthosilicate and water glass.
8. The method of claim 6, wherein the modifier precursor in step S2 is a soluble salt of IIIB or IVB metal of the periodic Table.
9. The method of claim 8, wherein the modifier precursor in step S2 is a soluble salt of one or more metals selected from titanium, zirconium, yttrium, lanthanum and cerium.
10. The method of claim 9, wherein the soluble salt is one of sulfate, nitrate, chlorate, oxychloronate, and organic acid salt.
11. The method for preparing the catalytic cracking catalyst according to claim 6, wherein the step S2 is performed by dropping alkali liquor so that the pH value of the sol is 2-7, and the reaction temperature of the hydrothermal reaction is 80-150 ℃.
12. The preparation method of the catalytic cracking catalyst according to claim 6, wherein the drying temperature in the step S3 is 80-120 ℃, and the calcination temperature of the product is 400-800 ℃.
13. An application of a catalytic cracking catalyst in a poor-quality oil suspension bed hydrocracking process is characterized in that,
placing inferior oil into a suspension bed cracking reactor;
dispersing the catalytic cracking catalyst of any one of claims 6 to 12 into the inferior oil, wherein the amount of the catalytic cracking catalyst is 1 to 20 wt% in terms of the weight percentage of the inferior oil;
and step three, the reaction temperature of the inferior oil suspension bed process is 380-420 ℃, and the reaction pressure is 6-15 MPa.
14. The use of claim 13, wherein one or more of molybdenum, tungsten, iron, cobalt or nickel complex hydrogenation catalysts are added in the second step and dispersed into the low-quality oil.
15. The application of the catalyst as claimed in claim 14, wherein the amount of the catalytic cracking catalyst is 3-15 wt% and the amount of the compounded hydrogenation catalyst is 0.5-5 wt% based on the weight percentage of the low-quality oil.
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