CN113457668A

CN113457668A - High specific heat capacity matrix material and preparation method and application thereof

Info

Publication number: CN113457668A
Application number: CN202010243109.3A
Authority: CN
Inventors: 刘倩倩; 朱玉霞; 陈振宇; 林伟; 宋海涛; 杨雪
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-03-31
Filing date: 2020-03-31
Publication date: 2021-10-01
Anticipated expiration: 2040-03-31
Also published as: CN113457668B

Abstract

A high specific heat capacity substrate material, a preparation method and an application thereof, wherein the substrate material contains at least 5 weight percent of manganese oxide, and the specific heat capacity is 1.3-2.0J/(g.K). The preparation method of the high specific heat capacity matrix material comprises the following steps: the preparation raw material comprising the manganese source is formed into a mixture, optionally subjected to a step of washing and/or drying and/or calcining. The high specific heat capacity matrix material provided by the invention has excellent metal pollution resistance and can be used as a matrix of a catalytic cracking catalyst or an auxiliary agent.

Description

High specific heat capacity matrix material and preparation method and application thereof

Technical Field

The invention relates to a high specific heat capacity matrix material and a preparation method and application thereof.

Background

With the increasing shortage of petroleum resources and the rising price of crude oil, large refineries can achieve maximum benefit by deeply processing heavy oil and using inferior oil to reduce cost, and catalytic cracking is an important means for processing heavy oil at present.

However, the heavy metal (such as vanadium and nickel) content of the crude oil with poor quality is generally high, and particularly in recent years, the phenomenon of metal poisoning of the catalytic cracking catalyst is increasingly common due to the heavy and inferior degree of the raw oil and the opportunity of processing the crude oil. Many research results show that once metals such as iron and nickel are deposited on the surface, the metals are difficult to migrate and can interact with elements such as silicon, aluminum, vanadium, sodium and the like to form eutectic substances with low melting points, so that the surface of the catalyst is sintered, a dense layer with the thickness of 2-3 mu m is further formed on the surface, the channels for reactants to enter the catalyst and products to diffuse are blocked, and the product distribution is deteriorated. Severe metal contamination can lead to significant problems of poor catalyst fluidization, reduced accessibility of active sites, poor catalyst selectivity, increased dry gas and coke yields, and the risk of equipment shutdown.

Disclosure of Invention

The inventor of the invention has found through long-term research that in the catalytic cracking process, under the high-temperature condition of a regenerator, the temperature of catalytic cracking catalyst particles can be increased sharply, and the temperature of the catalyst particles can be increased instantly even to a degree far higher than the temperature of the atmosphere, so that on one hand, the deposited metal is promoted to be fused and sintered on the surfaces of the particles, on the other hand, the crystal structure of a molecular sieve is collapsed, and the activity and the selectivity of the catalyst are greatly reduced. The inventors of the present invention have studied that the occurrence of this phenomenon is easily caused by the low specific heat capacity of the conventional catalytic cracking catalyst matrix material such as clay, aluminum oxide, alumina sol, etc., and have creatively proposed to improve the metal contamination resistance of the catalyst using a material having a high specific heat capacity.

Therefore, one of the technical problems to be solved by the present invention is to provide a high specific heat capacity matrix material.

The invention also aims to provide a preparation method of the matrix material, and the preparation method can be used for preparing the matrix material with high specific heat capacity.

The third technical problem to be solved by the invention is to provide an application method of the high specific heat capacity matrix material.

The invention provides a high specific heat capacity matrix material, wherein the high specific heat capacity matrix material contains MnO₂At least 5% by weight of manganese oxide, the high specific heat capacity matrix material having a specific heat capacity of 1.3-2.0J/(g.K) at a temperature of 1000K.

The high specific heat capacity matrix material according to the above technical scheme, preferably, the high specific heat capacity matrix material contains MnO₂5-95% by weight, based on the total weight of the material, of manganese oxide, e.g. the high specific heat capacity matrix material containing MnO₂10-70 wt% or 15-66 wt% or 19-66 wt% or 15-80 wt% or 22-72 wt% or 30-72 wt% manganese oxide.

The high specific heat capacity matrix material according to any one of the above technical solutions contains at least 5 wt% of alumina, preferably, the high specific heat capacity matrix material contains Al₂O₃5-95 wt.% of alumina, e.g. the high specific heat capacity matrix material contains 15-80 wt.% or 20-75 wt.% or 20-62 wt.% or 19-74 wt.% or 19-60 wt.% of alumina.

The high specific heat capacity matrix material according to any one of the above embodiments, wherein the high specific heat capacity matrix material may further contain 0 to 40 wt% of a boron compound on a dry basis, for example, the high specific heat capacity matrix material contains 1 to 35 wt% or 3 to 30 wt% or 5 to 26 wt% or 8 to 26 wt% or 0.5 to 10 wt% or 0.8 to 8 wt% or 1 to 5.5 wt% or 2 to 8 wt% of a boron compound on a dry basis.

The matrix material with high specific heat capacity according to any one of the above technical solutions, wherein the boron compound is preferably boron nitride and/or boron oxide.

The high specific heat capacity matrix material according to any one of the above technical solutions, wherein the specific surface area of the high specific heat capacity matrix material is 150-500m²·g^-1E.g. 180-450m²·g^-1Or 200-380m²·g^-1. In one embodiment, the high specific heat capacity matrix material contains a boron compound, the boron compound is boron nitride, and the specific surface area of the high specific heat capacity matrix material is 180-300m²·g^-1E.g., 200-²·g^-1Or 220-245m²·g^-1. In one embodiment, the boron compound contained in the high specific heat capacity host material is boron oxide, and the specific surface area of the high specific heat capacity host material is 300-500m²G 310-²/g or 330-370m²/g。

The high specific heat capacity matrix material according to any one of the above technical solutions, wherein the pore volume of the high specific heat capacity matrix material is 0.3-1.5cm³·g^-1For example, 0.35 to 1.2cm³·g^-1. In one embodiment, the high specific heat capacity matrix material comprises a boron compound, the boron compound is boron nitride, and the pore volume of the high specific heat capacity matrix material is preferably 0.35-0.75cm, such as 0.4-0.65cm³·g^-1. In one embodiment, the boron compound contained in the high specific heat capacity host material is boron oxide, and the pore volume of the high specific heat capacity host material is 0.5-1.5cm³Per g, for example, 0.6 to 1.3cm³G or 0.7-1.2cm³/g。

The high specific heat capacity matrix material according to any one of the above technical solutions, wherein the average pore diameter of the high specific heat capacity matrix material is 3-20nm, such as 4-18nm, or 5-15nm, or 6-13 nm. In one embodiment, the boron compound contained in the high specific heat capacity host material is boron nitride, and the average pore diameter of the high specific heat capacity host material is 5-13nm or 6-11 nm. In one embodiment, the boron compound contained in the high specific heat capacity host material is boron oxide, and the average pore size of the high specific heat capacity host material is 3-20nm, or 5-18nm, or 7-15nm, or 8-14 nm.

In one embodiment of the high specific heat capacity host material according to any of the above embodiments, the high specific heat capacity host material has a specific heat capacity of 1.3 to 1.95J/(g · K), for example, 1.51 to 1.95J/(g · K).

The high specific heat capacity matrix material according to any one of the above technical solutions, preferably, the XRD diffraction pattern of the high specific heat capacity matrix material has characteristic peaks at 2 θ angles of 18 ± 0.5 ° and 2 θ angles of 37 ± 0.5 °, and the ratio of the peak intensity at 2 θ angles of 18 ± 0.5 ° (I1) to the peak intensity at 2 θ angles of 37 ± 0.5 ° (I2) is 1: (3-10).

The invention also provides a preparation method of the matrix material with high specific heat capacity, which comprises the following steps:

(1) mixing an aluminum source and alkali into glue to obtain an aluminum-containing colloid, wherein the pH value of the aluminum-containing colloid is 7-11;

(2) mixing a manganese salt solution with the pH value of 3-7 with urea to obtain a manganese source solution;

(3) forming a mixture of an aluminum-containing colloid, a manganese source solution, and optionally a boron compound; and optionally

(4) Washed and/or dried and/or calcined.

According to the preparation method of the matrix material with high specific heat capacity in the technical scheme, in the step (1), the aluminum source and the alkali are mixed to form a colloid, and the mixing of the aluminum source and the alkali to form the colloid can be carried out at room temperature to 85 ℃. In the invention, the temperature of the room temperature is 15-40 ℃.

In one embodiment of the method for preparing a matrix material with high specific heat capacity according to any one of the above embodiments, the mixing an aluminum source and a base into a gel comprises: mixing an aluminum source solution and an alkali solution to form a colloid with the temperature of room temperature to 85 ℃ and the pH value of 7-11; the pH of the colloid has, for example, a pH of 7.5 to 11 or 9 to 10 or 8.5 to 11.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical solutions, wherein the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride and the like, preferably one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and the like.

According to the preparation method of the matrix material with high specific heat capacity in any one of the above technical solutions, the concentration of the alumina in the aluminum source solution is preferably 150-350gAl₂O₃/L。

In the method for preparing a matrix material with high specific heat capacity according to any of the above embodiments, the base is one or more of a water-soluble carbonate, a water-soluble bicarbonate, and a water-soluble hydroxide, such as one or more of an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal hydroxide, ammonium carbonate, ammonium bicarbonate, and ammonia.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical schemes, wherein the concentration of the alkali in the alkali solution is preferably 0.1-1 mol/L. The solution of the base may be selected from the group consisting of CO₃ ^2-、HCO₃ ^-Or OH^-An alkaline aqueous solution of one or more of (a) and (b), the solution of the base being CO₃ ^2-May be in a concentration of 0-0.6mol/L, e.g. 0.3-0.5mol/L, OH^-May be in a concentration of 0-0.5mol/L, e.g. 0.1-0.5mol/L or 0.2-0.35mol/L, HCO₃ ^-The concentration of (B) may be 0 to 1mol/L, for example 0.4 to 1.0 mol/L. Said CO-containing₃ ^2-、HCO₃ ^-Or OH^-The alkaline aqueous solution of one or more of (a) is, for example, an aqueous solution including one or both of ammonium bicarbonate and ammonium carbonate, or a solution including one or both of ammonium bicarbonate and ammonium carbonate and aqueous ammonia.

The method for preparing the matrix material with high specific heat capacity according to any one of the technical schemes, wherein in the step (2), the manganese salt solution is mixed with urea, wherein the molar ratio of the urea to the manganese ions is 1-5:1, such as 2-4: 1. There is no particular requirement on the concentration of the manganese salt solution, e.g. the concentration of the manganese salt in the manganese salt solution is MnO₂The amount can be 50-500 g.L^-1。

The preparation method of the matrix material with high specific heat capacity according to any one of the technical schemes, wherein in the step (2), urea is added into the manganese salt solution, and then the mixture is stirred for 30-60 minutes at room temperature to obtain a manganese source solution.

The method for preparing a high specific heat capacity host material according to any one of the above technical schemes, wherein the boron-containing compound is boron nitride and/or boron oxide and/or a boron oxide precursor. The boron nitride is, for example, at least one selected from hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN), and wurtzite boron nitride (w-BN). The boron oxide precursor is, for example, one or more of ammonium borate, ammonium hydrogen borate, or boric acid.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical schemes, wherein the step (3) further comprises an aging process, preferably, the aging temperature is from room temperature to 120 ℃, such as from 40 ℃ to 100 ℃, and the aging time is from 4 hours to 72 hours. Can be aged under stirring or standing.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical schemes, wherein in one embodiment, the aging is carried out under stirring, the aging temperature is 60-100 ℃, and the aging time is 12-36 h.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical solutions, wherein the aging is performed after the aluminum-containing colloid and the manganese source solution are mixed, for example, the aluminum-containing colloid and the manganese source are added into a mixing container and then aged, and then the aluminum-containing colloid, the manganese source and the boron compound are mixed into the mixing container and then aged.

The method for preparing a high specific heat capacity matrix material according to any one of the above technical solutions, wherein when the boron compound is boron nitride, one embodiment of the step (3) of mixing the aluminum-containing colloid, the manganese source solution and the boron compound is as follows: mixing the aluminum-containing colloid, the manganese source solution and the boron compound, and aging.

The method for preparing a high specific heat capacity base material according to any one of the above, when the boron compound is boron oxide and/or a precursor of boron oxide, the step (3) of mixing an aluminum-containing colloid, a manganese source solution, and a boron compound to form one of the mixturesThe implementation mode is as follows: the aluminium-containing colloid, the manganese source solution, are mixed, aged, optionally washed and then mixed with the boron compound, preferably the resulting mixture is also reacted for a period of time, for example by stirring or standing at room temperature to 90 ℃ for 0.2 to 5 hours, for example 0.5 to 3 hours. Wherein the dosage of the boron compound is B₂O₃The weight ratio on a dry basis of the mixture formed with the aluminum-containing colloid, the manganese source solution and the boron compound is preferably (0.005-0.1): 1.

the method for preparing a matrix material with high specific heat capacity according to any one of the above technical schemes, wherein the washing in steps (3) and (4) has no special requirement, and the washing generally makes the washed solid product neutral. The solid product is neutral, which means that after contacting the solid product with water (for example, mixing and stirring for 1 minute or more in a weight ratio of water to solid product of 3: 1), the water is neutral, and the pH is usually 6.5 to 7.5. The solid precipitate obtained in the step (3) or the solid precipitate obtained by aging can be washed according to the following solid precipitate (dry basis): h₂O is 1: (5-30) mixing and washing one or more times, for example, 1-3 times, each time for 0.5-1 hour at room temperature, preferably, the washing times are such that the water after washing is neutral; the solid precipitate can also be washed with water until the washed water is neutral.

According to the preparation method of the matrix material with high specific heat capacity in any one of the technical schemes, the drying in the step (4) can adopt the existing methods, such as drying, air flow drying, spray drying and flash evaporation drying. In one embodiment, the drying temperature is 100-.

The preparation method of the matrix material with high specific heat capacity according to any one technical scheme, wherein in the step (4), the roasting temperature is 500-900 ℃, and the roasting time is 4-8 hours; the roasting temperature is preferably 550-800 ℃ or 550-750 ℃; the calcination temperature is more preferably from 650 ℃ to 750 ℃.

The method for preparing a matrix material with high specific heat capacity according to any one of the above technical solutions, wherein in one embodiment, the step (4) comprises: and (4) cooling the product obtained in the step (3) to room temperature, filtering, washing with a washing liquid such as deionized water until the washed washing liquid is neutral, drying to obtain a high specific heat capacity matrix material precursor, roasting the high specific heat capacity matrix material precursor, and cooling to room temperature along with a furnace to obtain the matrix material.

The invention further provides a high specific heat capacity matrix material obtained by the preparation method of the high specific heat capacity matrix material according to any one technical scheme. The specific heat capacity of the high specific heat capacity matrix material prepared according to the aforementioned preparation method of the present invention may be 1.3 to 2.0, and preferably, the specific heat capacity of the matrix material prepared according to the preparation method of the high specific heat capacity matrix material of the present invention may be 1.30 to 1.95J/(g.K), for example, 1.51 to 1.95J/(g.K).

The application of the high specific heat capacity matrix material in the technical scheme in the catalyst or the application of the high specific heat capacity matrix material as a heat storage material.

The application of the high specific heat capacity matrix material in any technical scheme as a matrix material in a catalyst or an auxiliary agent.

Further, the invention also provides a catalytic cracking catalyst, which comprises a molecular sieve and a matrix, wherein the matrix comprises the high specific heat capacity matrix material according to any one of the technical schemes.

As an embodiment applied to a catalytic cracking catalyst or promoter, the catalytic cracking catalyst or promoter comprises a molecular sieve and a matrix, wherein the matrix comprises the high specific heat capacity matrix material provided by the invention and other optional matrix materials. The molecular sieve is used for a catalytic cracking catalyst or auxiliary agent, such as a Y-type molecular sieve. Such as one or more of clay, binder, mesoporous material. The addition proportion of the high specific heat capacity matrix material can be properly adjusted according to the properties of raw oil and the change of an operation process, for example, the catalytic cracking catalyst contains 10-85 wt% of the high specific heat capacity matrix material, 15-60 wt% of a molecular sieve and 0-70 wt% of other matrix materials, and the contents are calculated by dry weight.

The mesoporous matrix material with high specific heat capacity provided by the invention has higher specific heat capacity, and can have at least one of the following beneficial effects, preferably a plurality of or all of the following beneficial effects:

(1) has high-temperature thermal stability.

(2) Has high chemical stability.

(3) Has better abrasion resistance.

(4) Has good metal pollution resistance.

(5) Compared with the conventional matrix materials such as kaolin, sepiolite, aluminum oxide and the like, the composite material has higher specific heat capacity, better high temperature resistance and/or metal pollution resistance. The catalyst can be used as a matrix material of a heavy oil cracking catalyst or an auxiliary agent, can obviously improve the specific heat capacity of catalyst particles, can obviously reduce the particle temperature of the catalyst during regeneration in the high-temperature regeneration process, reduces local rapid temperature rise, improves the metal pollution resistance, especially the iron pollution resistance of the catalyst, has good fluidization performance when the iron pollution amount in the catalytic cracking catalyst is up to 5000ppm, and shows more excellent heavy oil cracking performance while maintaining good coke selectivity.

(6) The catalyst is used for catalytic cracking catalyst, so that the catalyst can have good fluidization performance under the condition of metal pollution.

(7) The catalyst is used for catalytic cracking catalyst, can obviously improve the high-temperature stability of the catalyst, and optimizes the product distribution.

(8) The molecular sieve can be used as a matrix material of a heavy oil cracking catalyst or an auxiliary agent containing the molecular sieve, and can effectively slow down the collapse of the crystal structure of the molecular sieve.

(9) As a matrix material of a heavy oil cracking catalyst or an auxiliary agent containing a molecular sieve, the heavy oil conversion capability of the catalyst is improved, and/or the dry gas selectivity is reduced, and/or the coke selectivity is reduced, and/or the total liquid yield is improved.

The preparation method of the high specific heat capacity matrix material provided by the invention has at least one of the following advantages, preferably a plurality of advantages:

(1) is used for preparing a matrix material with higher specific heat capacity.

(2) The synthesis steps are simple and easy to operate.

(3) The preparation process is economic and environment-friendly.

(4) The wear resistance can be greatly improved when using nitrides, and particularly, the wear resistance can be better when using boron nitrides.

(5) The prepared high specific heat capacity matrix material has mesoporous aperture.

(6) The prepared high specific heat capacity matrix material can have a high mesoporous proportion, and the average pore diameter can be larger than 3 nm.

(7) The prepared high specific heat capacity matrix material has higher chemical stability.

(8) The obtained high specific heat capacity matrix material is used as a matrix for a catalytic cracking catalyst, and can improve the metal pollution resistance of the catalytic cracking catalyst, the heavy oil conversion capacity of the catalytic cracking catalyst and the product distribution.

(9) Materials having characteristic peaks at 18 + -0.5 deg. and 37 + -0.5 deg. of the XRD pattern can be formed below 900 deg.c.

The high specific heat capacity matrix material provided by the invention can be used as a matrix of a catalyst, such as a hydrocarbon oil hydrogenation reaction catalyst, a catalytic cracking reaction catalyst, an alkylation reaction catalyst, an alkyl transfer reaction catalyst, a catalytic cracking catalyst, a catalytic thermal cracking catalyst, a contact cracking catalyst, a flue gas desulfurization and denitrification catalyst, a gasoline desulfurization catalyst and a dehydrogenation hydrogen production catalyst. The high specific heat capacity matrix material provided by the invention can also be used as a heat storage material, such as a heat carrier for coking reaction.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. Wherein:

FIG. 1 is an X-ray diffraction pattern of the high specific heat capacity matrix material of example 1. Diffraction peaks are provided at the 2 theta angles of 18 +/-0.5 degrees, 37 +/-0.5 degrees, 48 +/-0.5 degrees, 59 +/-0.5 degrees and 66 +/-0.5 degrees in the spectrogram.

Detailed Description

The invention provides a high specific heat capacity matrix material, which does not contain boron compound, and the high specific heat capacity matrix material contains Al based on the weight of the high specific heat capacity matrix material₂O₃5-95% by weight, calculated as MnO, of alumina₂5-95 wt% of manganese oxide, for example, the high specific heat capacity matrix material mainly comprises 15-70 wt% or 20-65 wt% or 30-61 wt% of manganese oxide and 30-85 wt% or 35-80 wt% or 39-70 wt% of alumina. The specific surface area of the high specific heat capacity matrix material can be 180-300m²·g^-1E.g., 200-²·g^-1Or 220-245m²·g^-1(ii) a The pore volume of the high specific heat capacity matrix material is in the range of 0.35 to 0.75, such as 0.4 to 0.65cm³·g^-1(ii) a The high specific heat capacity matrix material has an average pore diameter of 5 to 13nm, for example 6 to 11 nm.

The high specific heat capacity matrix material provided by the invention can contain or not contain boron compounds. Preferably, the high specific heat capacity matrix material (the matrix material for short) provided by the invention contains a boron compound, and compared with the high specific heat capacity matrix material without the boron compound, the high specific heat capacity matrix material has better metal pollution resistance.

In a second embodiment of the present invention, the boron compound is boron nitride, and the specific heat capacity is 1.3-2.0J/(g.K), for example, 1.35-1.95J/(g.K) or 1.51-1.95J/(g.K). The anhydrous chemical expression of the high specific heat capacity matrix material in weight ratio can be expressed as (5-94.5) Al₂O₃·(5-94.5)MnO₂0.5-40) BN, for example (20-80) Al₂O₃·(15-75)MnO₂5-30) BN. Preferably, the high specific heat capacity matrix material contains 5 to 94.5 wt% of alumina, in MnO, based on the weight of the high specific heat capacity matrix material₂5-94.5% by weight manganese oxide and more than 0 and not more than 40% by weight, e.g. 0.5-35% by weight boron nitride on a dry basis; more preferably, the high specific heat capacity matrix material contains 15 to 80 weight percent of alumina, 15 to 70 weight percent of manganese oxide and 5 to 30 weight percent of boron nitride; more preferably, the height is higherThe specific heat capacity matrix material contains 19-74 wt% of alumina, 14-66 wt% of manganese oxide and 8-26 wt% of boron nitride. The high specific heat capacity matrix material contains boron nitride, and can greatly improve the wear resistance.

According to the second embodiment of the high specific heat capacity matrix material provided by the invention, the specific surface area of the high specific heat capacity matrix material is 150-350m²·g^-1E.g., 180-²·g^-1Or 200-250m²·g^-1Or 220-245m²·g^-1The pore volume of the high specific heat capacity matrix material is 0.35 to 0.75, such as 0.4 to 0.65cm³·g^-1Or 0.45-0.75 or 0.5-0.7cm³·g^-1The high specific heat capacity matrix material has an average pore diameter of 3 to 20nm, for example 4 to 18nm or 5 to 15nm or 6 to 13nm or 6 to 8.5nm, preferably 5 to 13nm or 6 to 11 nm.

According to the present invention, there is provided a high specific heat capacity matrix material, in a second embodiment, a method for preparing the matrix material, comprising the steps of:

(1) mixing an aluminum source solution and an alkali solution at room temperature to 85 ℃ to form colloid, and controlling the pH value of the colloid formed by the colloid to be 7-11;

(2) preparing a manganese salt solution with the pH value of 3-7, mixing the manganese salt solution with urea, and stirring; the molar ratio of the urea to the manganese ions is 1-5, the temperature for mixing the manganese salt solution and the urea is not specially required, and the mixing is carried out at room temperature, and the stirring time is 30-60 minutes for example;

(3) mixing the product obtained in the step (1), the product obtained in the step (2) and boron nitride, and aging for 4-72 hours at room temperature to 120 ℃; and optionally (c) a second set of instructions,

(4) washing the product obtained in step (3) with water, preferably, the washing is to make the washing liquid after washing neutral (neutral means pH value is 6.5-7.5), for example, washing with deionized water until the deionized water after washing is neutral, drying, and roasting to obtain the high specific heat capacity matrix material.

In the preparation method according to the second embodiment of the present invention, the alkali solution in the step (1) can be selected in a wide range, and preferably, the alkali solution in the step (1)To contain CO₃ ^2-、HCO₃ ^2-And OH^-More preferably, the alkaline aqueous solution is an aqueous solution containing one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide, or a mixed solution of one or more of ammonium carbonate, sodium hydroxide and potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. In one embodiment, the alkali solution is CO₃ ^2-The concentration of (B) is 0 to 0.6mol/L, for example 0.3 to 0.5 mol/L; OH group^-In a concentration of 0 to 0.5mol/L, for example 0.2 to 0.35mol/L, HCO₃ ^2-The concentration of (B) is 0 to 1.0mol/L, for example, 0.4 to 1.0 mol/L. The pH of the gel formed in step (1) is preferably from 8 to 11, for example from 8.5 to 11 or from 9 to 10. And when the ammonia water is selected, assuming that the ammonia water is completely ionized, and calculating the required addition amount of the ammonia water according to the calculated hydroxyl.

According to the preparation method in the case of the second embodiment of the present invention, the kind of the aluminum source can be selected from a wide range, and a water-soluble aluminum source capable of being dissolved in water can be used in the present invention, and for example, the aluminum source can be selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

According to the preparation method of the second embodiment of the present invention, in the step (2), a manganese salt solution having a specific pH value, which is 3 to 7, preferably 5 to 7, is mixed with urea to form a mixture. The conditions for mixing urea with the manganese salt solution can be selected from a wide range, and for the present invention, in one embodiment, the mixing method in step (2) comprises: adding urea into manganese salt solution, and stirring at room temperature for 40-60 min, wherein the molar ratio of urea to manganese ions is preferably 2-4. The manganese salt solution in the step (2) can be selected from water solution of water-soluble manganese salt and/or salt solution formed after manganese oxide and manganese hydroxide contact with acid. The kind of the manganese salt is wide in the optional range, and a water-soluble manganese salt capable of dissolving in water, such as one or more of manganese nitrate, manganese sulfate, manganese chloride, or the like, may be used in the present invention. The manganese salt solution may also be prepared by contacting manganese oxides, such as one or more of manganese monoxide, trimanganese tetroxide, dimanganese trioxide, manganese dioxide, and/or manganese hydroxides, with an acid, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, nitric acid.

According to the production method of the second embodiment of the present invention, the product obtained in the step (1) in the step (3) is Al₂O₃Metering the product obtained in the step (2) with MnO₂The proportion of the boron nitride to the weight of the boron nitride on a dry basis is (5-95) Al₂O₃：(5-95)MnO₂: (0.5-40) BN is, for example, (20-80) Al₂O₃：(15-75)MnO₂: (5-30) BN. Preferably, the product of step (1) in step (3), the product of step (2) and the boron nitride are used in amounts such that the resulting matrix material comprises 5 to 94.5 wt%, e.g. 15 to 80 wt%, or 19 to 74 wt%, or 20 to 80 wt%, or 19 to 60 wt% of alumina, expressed as MnO₂5-94.5 wt% such as 15-75 wt% or 10-70 wt% or 14-66 wt% or 19-66 wt% manganese oxide and more than 0 and not more than 40 wt% such as 0.5-35 wt% or 5-30 wt% or 8-26 wt% boron nitride on a dry basis.

According to the preparation method in the case of the second embodiment of the present invention, the optional range of the aging conditions in the step (3) is wide, and preferably, the aging conditions in the step (3) include: aging at 60-100 deg.C for 12-36 hr under stirring. There is no particular requirement for the manner of stirring, for example, the stirring speed may be from 50 to 300 revolutions per minute.

According to the production method in the case of the second embodiment of the present invention, the boron nitride may be selected from one or more of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN) and wurtzite boron nitride (w-BN).

According to the production method in the case of the second embodiment of the present invention, the optional range of the drying condition and the baking condition in the step (4) is wide. The drying and roasting methods can be carried out according to the prior art, and the invention has no special requirement for the method. For example, the drying conditions in step (4) include: drying at 100-150 deg.C for 6-24 h; the roasting conditions in the step (4) comprise: baking at 550-800 deg.C, such as 550-750 deg.C for 4-8 h.

In a third embodiment of the present invention, the boron compound is boron oxide, the specific heat capacity is 1.3-2.0J/(g.K), such as 1.35-1.95J/(g.K) or 1.51-1.95J/(g.K), and the anhydrous compound composition formula of the high specific heat capacity mesoporous matrix material provided by the present invention is (5-94.5) Al in terms of oxide weight ratio₂O₃·(5-94.5)MnO₂·(0.5-10)B₂O₃For example (20-80) Al₂O₃·(15-75)MnO₂·(0.5-10)B₂O₃Or (20-80) Al₂O₃·(15-75)MnO₂·(1-8)B₂O₃. Preferably, the high specific heat capacity matrix material contains 5-94.5 wt% of alumina, in MnO, based on the weight of the high specific heat capacity matrix material₂5-94.5% by weight, calculated as B, of manganese oxide₂O₃0.5-10% by weight of boron oxide; more preferably, the high specific heat capacity matrix material contains 15-80 wt% of alumina, in MnO₂15-80% by weight of manganese oxide and B₂O₃0.8-8 wt.% of boron oxide or the high specific heat capacity matrix material contains 20-62 wt.% of aluminum oxide in MnO₂34-72% by weight of manganese oxide and B₂O₃2-8% by weight of boron oxide. Preferably, the specific surface area of the high specific heat capacity matrix material is 300-500m²G 310-²/g or 330-370m²Per g, pore volume of 0.5-1.5cm³G is, for example, from 0.7 to 1.4cm³G or 0.6-1.3cm³G or 0.7-1.2cm³(ii) in terms of/g. Preferably, the matrix material is a mesoporous matrix material having an average pore size of 3-20nm, such as 5-18nm or 8-18nm or 7-15nm or 8-14nm or 10-15nm or 10-13 nm.

In the matrix material with high specific heat capacity provided by the third embodiment of the invention, the boron compound is boron oxide, which has higher pore volume and specific surface area, and boron oxide is introduced to modulate matrix acidity and improve matrix pre-cracking capability, so that the boron compound is used as a matrix material of a catalytic cracking catalyst or an auxiliary agent, is applied to heavy oil catalytic cracking, can reduce the particle temperature of the catalytic cracking catalyst during regeneration, slow down molecular sieve collapse, improve the activity, metal pollution resistance and heavy oil conversion capability of the catalyst, reduce the coke selectivity of the catalyst, and ensure good fluidization performance of the catalyst.

According to the high specific heat capacity matrix material of the present invention, in the case of the third embodiment, a method for preparing the high specific heat capacity matrix material includes the steps of:

(1) mixing an aluminum source solution and an alkali solution at room temperature to 85 ℃ to form colloid, and controlling the pH value of the colloid obtained by colloid formation to be 7-11;

(2) preparing a manganese salt solution with the pH value of 3-7, mixing the manganese salt solution with urea, and stirring, for example, stirring at room temperature for 30-60 minutes; wherein the molar ratio of urea to manganese ions is 1-5;

(3) mixing and aging the product obtained in the step (1) and the product obtained in the step (2); the aging is, for example, aging at room temperature to 120 ℃ for 4 to 72 hours; mixing the aged solid product with a boron oxide source or mixing the aged solid product with the boron oxide source after washing, and optionally reacting; wherein with B₂O₃The weight ratio of the boron oxide source feeding amount to the high specific heat capacity matrix material on a dry basis is (0.005-0.1): 1;

(4) directly drying and roasting the solid precipitate (or called solid product) obtained in the step (3) or washing and drying the solid precipitate obtained in the step (3) and roasting; the solid product of step (3) may be washed with water, for example, washed with water, so that the water after washing is neutral.

According to the preparation method of the third embodiment, the prepared matrix material not only has higher specific heat capacity, but also has higher average pore diameter, higher specific surface area and higher pore volume compared with the matrix material with high specific heat capacity obtained by other methods in the range of the invention, and has higher liquid product yield, lower dry gas and coke yield when being used for the catalytic cracking of heavy oil with high metal content, especially high iron content.

According to a third embodiment of the inventionThe preparation method has wide optional range of the alkali solution in the step (1), and preferably, the alkali solution in the step (1) contains HCO₃ ^2-、CO₃ ^2-And OH^-Preferably, the alkaline aqueous solution is an aqueous solution containing one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide, or a mixed solution containing one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. Preferably, in said alkaline solution, CO₃ ^2-The concentration of (B) is 0 to 0.6mol/L, for example 0.3 to 0.5 mol/L; OH group^-Preferably 0 to 0.5mol/L, for example 0.2 to 0.35mol/L, HCO₃ ^2-The concentration of (B) is 0 to 1.0mol/L, for example, 0.4 to 1.0 mol/L. When the ammonia water is selected, assuming that the ammonia water is completely ionized, and calculating the required addition amount of the ammonia water according to the calculated hydroxyl. The pH of the colloid obtained in the gelling is preferably from 9 to 11 or from 10 to 11.

According to the production method of the third embodiment of the present invention, the kind of the aluminum source can be selected from a wide range, and a water-soluble aluminum source capable of being dissolved in water can be used in the present invention, for example, the soluble aluminum salt can be one or more selected from aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, and the like, preferably one or more selected from aluminum nitrate, aluminum sulfate, aluminum chloride, and the like.

According to the preparation method of the third embodiment of the present invention, the manganese salt solution in the step (2) may be selected from an aqueous solution of a water-soluble manganese salt and/or a salt solution formed after contacting a manganese oxide, a manganese hydroxide and an acid; the pH value of the manganese salt solution is 3-7, preferably 5-7. Preferably, after the manganese salt solution and the urea are mixed in the step (2), the mixture is stirred for 40 to 60 minutes at room temperature, and the molar ratio of the urea to the manganese ions is between 2 and 4. The manganese salt solution in the step (2) can be selected from water solution of water-soluble manganese salt and/or salt solution formed after manganese oxide and manganese hydroxide contact with acid. The kind of the manganese salt is wide in the optional range, and a water-soluble manganese salt capable of dissolving in water, such as one or more of manganese nitrate, manganese sulfate, manganese phosphate, manganese chloride, or the like, may be used in the present invention. The manganese salt solution may also be prepared by contacting manganese oxides, such as one or more of manganese monoxide, trimanganese tetroxide, dimanganese trioxide, manganese dioxide, and/or manganese hydroxides, with an acid, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, nitric acid.

According to the production process of the third embodiment of the present invention, the aging conditions in step (3) can be selected in a wide range, and preferably, the aging conditions in step (3) include: the aging temperature is 60-100 ℃, the stirring and the aging are carried out, and the aging time is 12-36 h. The stirring method is the existing method, for example, the stirring speed is 50-300 r/min. Filtering or washing the aged product to obtain an aged solid product. In one embodiment, the washing is carried out on an aged solid product (dry basis): h₂O is 1: (5-30) weight ratio the aged solid product (also called precipitate) obtained by aging is contacted with water at room temperature for 1-3 times, each for 0.5-1 hour, until the washing liquid after washing is neutral, usually at pH 6.5-7.5.

According to the production method of the third embodiment of the present invention, the aged solid product is subjected to a contact treatment with a boron source, and the contact treatment may be carried out by various methods. The aged product can be filtered to obtain a filter cake, namely the aged solid product is directly mixed with the boron source, or the aged solid product obtained after the filter cake obtained by filtering is washed is mixed with the boron source; preferably, the resulting mixture is also subjected to a reaction for a period of time, for example, stirring or standing at room temperature to 90 ℃ for 0.2 to 5 hours. In one embodiment, the aged solid product is slurried in water, wherein the aged solid product (on a dry basis): h₂The weight ratio of O is 1: (5-20), adding a boron source into the slurry, standing or stirring at room temperature to 90 ℃ for 0.2-5 hours, preferably 0.5-3 hours, and filtering to obtain a solid precipitate. Or mixing the aged solid product or the washed aged solid product with a boron source in proportion, and uniformly grinding to obtain a solid precipitate.

According to the production method of the third embodiment of the present invention, the boron oxide source is preferably a substance capable of yielding boron oxide after calcination, and may be, for example, one or more of ammonium borate, ammonium hydrogen borate, or boric acid.

According to the production method of the third embodiment of the present invention, the product obtained in the step (1) in the step (3) is Al₂O₃Metering the product obtained in the step (2) with MnO₂Metering and mixing boron source with B₂O₃Calculated weight and dosage ratio is (5-94.5) Al₂O₃：(5-94.5)MnO₂：(0.5-10)B₂O₃For example, (20-80) Al₂O₃：(15-75)MnO₂：(1-8)B₂O₃. Preferably, the resulting high specific heat capacity matrix material contains 5 to 94.5 wt%, such as 15 to 80 wt%, or 20 to 75 wt%, or 20 to 62 wt% of alumina, 5 to 94.5 wt%, such as 15 to 80 wt%, or 22 to 72 wt%, or 30 to 72 wt% in MnO₂Manganese oxide and 0.5-10 wt% or 0.8-8 wt% or 2-8 wt% of B₂O₃Boron oxide (calculated).

According to the preparation method of the third embodiment of the present invention, the step (4) is to directly dry and calcine the solid precipitate obtained in the step (3), or to dry and calcine the solid precipitate after washing. Wherein the washing may be carried out by washing with water, for example, by mixing with water and washing with water, and usually, the solid precipitate after washing is neutral, i.e., the pH of water after contacting with water is from 6.5 to 7.5. The drying and roasting methods can be carried out according to the prior art, the optional range is wide, and the invention has no special requirement. For example, the drying may be performed at 100-150 ℃ for 12-24 h; the roasting can be carried out at 550-800 ℃, for example, 550-750 ℃ for 4-8 h.

The high specific heat capacity matrix material provided by the invention is used for preparing a catalytic cracking catalyst by matching with a Y-type molecular sieve, clay such as kaolin, a binder and the like, and the catalyst is used for catalytic cracking reaction, can keep good coke selectivity, simultaneously shows more excellent heavy oil cracking performance, particularly has good cracking reaction performance under the condition of metal pollution, can keep good coke selectivity, simultaneously enables the catalytic cracking catalyst to have more excellent heavy oil cracking performance, optimizes product distribution, for example, has higher cracking activity, obviously reduces the heavy oil yield, improves the gasoline yield and improves the liquid yield.

The invention is further illustrated by the following examples, which are not intended to be limiting thereof.

In the present invention, the catalyst-to-oil ratio refers to the mass ratio of the catalyst to the feedstock oil.

In the present invention, ppm is ppm by weight unless otherwise specified.

BN used is hexagonal boron nitride.

In each of examples and comparative examples, Al in the sample₂O₃、MnO₂The content of B, N, Fe was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP), eds of Yangroi, published by scientific Press, 1990). The sample phase was determined by X-ray diffraction. The specific surface area, pore volume and average pore diameter of the sample are measured by a low-temperature nitrogen adsorption-desorption method and a BJH method to obtain the pore diameter distribution.

Example 1

This example illustrates the preparation of a high specific heat capacity matrix material provided by the present invention.

The concentration of 300gAl₂O₃Al of/L₂(SO₄)₃Solution with CO^3-Ammonium carbonate solution with a concentration of 0.10mol/L was mixed to a gel at 20 ℃ and the resulting gel pH was 7.5 to give slurry a. To a concentration of 450gMnO₂MnCl of/L₂Hydrochloric acid was added to the solution, the pH was controlled to 3.5, urea was then added to the solution at a molar ratio of urea to manganese ions of 2, and the mixture was stirred at room temperature for 30 minutes to obtain solution B. And adding the solution B into the slurry A, stirring and aging for 4h at 80 ℃, cooling the system to room temperature, washing with deionized water until the washed water is neutral, drying for 12h at 120 ℃ to obtain a matrix material precursor, roasting for 6h at 550 ℃, and cooling to room temperature along with a furnace to obtain the high specific heat capacity matrix material, which is marked as AM-1. The compounding ratio of AM-1, preparation condition parameters, specific heat capacity, specific surface area, pore volume and average pore diameter are shown in Table 1.

The X-ray diffraction spectrum of AM-1 is shown in FIG. 1, wherein the characteristic peaks are present at 2 theta angles of 18 + -0.5 deg. and 2 theta angles of 37 + -0.5 deg., and the intensity ratio (I1/I2) is 1: 5.2; the expression of the elemental analysis chemical composition (by weight) is 60.5MnO₂·39.5Al₂O₃(ii) a Specific heat capacity of 1.36J/(g.K), specific surface area of 238m²G, pore volume 0.38cm³G, average pore diameter 6.4 nm.

Examples 2 to 4

Examples 2-4 are provided to illustrate the preparation of the high specific heat capacity matrix material provided by the present invention.

High specific heat capacity matrix materials AM-2 to AM-4 were prepared according to the method of example 1 except that the raw material ratio, preparation condition parameters, element composition of the product, specific heat capacity, specific surface area, pore volume and average pore diameter were as shown in table 1, wherein solution B was added to slurry a, followed by addition of boron nitride and then said aging.

Example 5

Example 5 is used to illustrate the preparation of the high specific heat capacity matrix material provided by the present invention.

The concentration of 350gAl₂O₃Al (NO)/L₃)₃Solution with CO^3-The concentration of (ammonium carbonate) and OH is 0.1mol/L^-The solution with the concentration of 0.1mol/L (ammonia water) is mixed into glue at the temperature of 25 ℃, and the pH value is controlled to be 10.5, so that slurry A is obtained. Adding Mn₃O₄Mixing with hydrochloric acid and water to obtain a mixture with a concentration of 116.5g MnO₂And (3) adding urea into the solution of manganese chloride solution at a pH value of 6, wherein the molar ratio of the urea to manganese ions is 3, and stirring the solution at room temperature for 40 minutes to obtain solution B. Adding the solution B and 145.6gBN (with the solid content of 80 wt%) into the slurry A, stirring and aging for 24h at 60 ℃, cooling the system to room temperature, washing with deionized water until the washed water is neutral, drying for 12h at 120 ℃ to obtain a matrix material precursor, then roasting for 4h at 650 ℃, and cooling to room temperature along with the furnace to obtain the high specific heat capacity matrix material, which is marked as AM-5. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore diameter of AM-5 are listed in Table 1.

X-ray diffraction spectrum of AM-5The graph is the same as that of FIG. 1, wherein characteristic peaks exist at the 2 theta angle of 18 +/-0.5 degrees and the 2 theta angle of 37 +/-0.5 degrees, and the intensity ratio of the characteristic peaks to the 2 theta angle is 1: 6.6; chemical composition expression of AM-5 as 20.6MnO by weight₂·59.4Al₂O₃19.4 BN; specific heat capacity of 1.48J/(g.K), specific surface area of 243m²G, pore volume 0.46cm³G, average pore diameter 7.6 nm.

Example 6

Example 6 is provided to illustrate the preparation of the high specific heat capacity matrix material provided by the present invention.

The matrix material AM-6 was prepared according to the method of example 5, with the different raw material ratios, preparation conditions parameters, composition, specific heat capacity, specific surface area, pore volume and mean pore diameter listed in Table 1, wherein CO was present in the alkaline solution used for gelling^3-Concentration of 0.2mol/L, OH^-The concentration was 0.15 mol/L.

The X-ray diffraction patterns of AM-2 to AM-6 are shown in FIG. 1, and have peaks at an angle of 2. theta. of 18. + -. 0.5 ℃ and an angle of 2. theta. of 37. + -. 0.5 ℃.

Comparative example 1

Deionized water is used for respectively preparing 350gAl₂O₃Al (NO)/L₃)₃Solution and concentration of 525gMnO₂And mixing the manganese nitrate solution/L uniformly to obtain a solution A. And preparing an ammonium bicarbonate solution, and marking as a solution B by controlling the pH value to be 10.0. And mixing the solution A and the solution B under continuous stirring to obtain mother liquor C, wherein the PH value of the mother liquor C is controlled to be 8-9 by controlling the adding amount of the solution B in the mixing process. And after the mixing is finished, aging is carried out for 20h at 180 ℃, when the temperature of the system is reduced to room temperature, the system is washed to be neutral by deionized water, and is dried for 12h at 120 ℃ to obtain a manganese-aluminum matrix precursor, and then the manganese-aluminum matrix precursor is roasted for 4h at 1000 ℃, and is cooled to room temperature along with a furnace to obtain a contrast matrix material, which is marked as DB-1.

An X-ray diffraction pattern of DB-1, wherein characteristic peaks are provided at an angle of 2 theta of 18 +/-0.5 degrees and an angle of 2 theta of 37 +/-0.5 degrees, and the intensity ratio of the characteristic peaks is 1: 1.9; the expression of the elemental analysis chemical composition of DB-1 is 60.6MnO₂·39.4Al₂O₃(ii) a Specific heat capacity of 0.62J/(g.K), specific surface area of 224m²G, pore volume 0.31cm³G, average pore diameter 5.5 nm.

Comparative example 2

The concentration of 350gAl₂O₃Al of/L₂(SO₄)₃The solution was mixed with ammonium carbonate to give a gel, and the pH was controlled to 10.0 to give slurry a. The concentration of 209.7gMnO₂MnSO of/L₄The solution was added to slurry A and stirred at room temperature for 30 minutes to give slurry B. And adding the solution B and 95.4g of boron nitride (with the solid content of 80 weight percent) into the slurry A, aging for 24h at the temperature of 80 ℃, cooling the system to room temperature, washing the system to be neutral by deionized water, drying the system for 12h at the temperature of 120 ℃ to obtain a manganese-aluminum matrix precursor, roasting the precursor for 6h at the temperature of 900 ℃, and cooling the precursor to room temperature along with a furnace to obtain a sample of a comparative matrix material, which is recorded as DB-2.

The expression of the elemental analytical chemical composition of DB-2 is 33.3MnO by weight₂·54.7Al₂O₃11.7 BN; specific heat capacity of 0.85J/(g.K), specific surface area of 219m²G, pore volume 0.25cm³G, average pore diameter 4.6 nm.

Example 7

This example illustrates the cracking activity of the high specific heat capacity matrix material provided in examples 1-6 of the present invention as applied to a heavy oil cracking process.

The high specific heat capacity matrix materials prepared in examples 1-6 were separately mixed with REY molecular sieves (RE)₂O₃16.5 wt.% Na₂O1.4 wt%, produced by Changling catalyst factory of China petrochemical catalyst Co., Ltd.) in a weight ratio of 2:8, taking samples as C-1 to C-6, dipping 4000ppm of contaminated iron, 2000ppm of nickel and 2000ppm of vanadium by a Mitchell method, tabletting after grinding uniformly, screening into 20-40 mesh particles, aging at 780 ℃ for 12 hours under the condition of 100% steam, carrying out cracking performance evaluation on a heavy oil micro-reaction device, carrying out three reaction-regeneration cycles in the evaluation process of each sample, namely continuously carrying out three raw oil reactions and regeneration processes under the condition that the same catalyst is not unloaded, and taking the result of the last reaction as the evaluation result of the cracking performance of the catalyst. The evaluation conditions of the heavy oil micro-reaction are as follows: the weight ratio of the agent to the oil is 1.56, the sample loading is 2g, the reaction temperature is 500 ℃, the reaction time is 70 seconds, the regeneration temperature is 700 ℃, and the raw oil is vacuum gas oil. The properties of the feed oil are shown in Table 2. The evaluation results are shown in Table 3。

Comparative example 3

This example illustrates the cracking activity of comparative sample materials obtained in comparative examples 1 and 2, respectively, applied to a heavy oil cracking process.

The matrix materials obtained in comparative examples 1 and 2 were mixed with REY molecular sieves (RE)₂O₃16.5 wt.% Na₂O1.4 wt%, produced by chang catalyst factory) were mixed in a weight ratio of 2:8, and the samples were designated as C-DB-1 and C-DB-2, and immersed in 4000ppm contaminated iron, 2000ppm nickel, and 2000ppm vanadium by Mitchell method, ground uniformly, tabletted, and sieved into 20-40 mesh particles, aged at 780 ℃ for 12 hours under 100% steam, and subjected to cracking performance evaluation on a heavy oil microreaction device in the same manner as in example 7. The evaluation results are shown in Table 3.

TABLE 1

Note: in tables 1 and 4, I1/I2 is the ratio of the intensity of the peak at the 2 theta angle of 18 +/-0.5 DEG to the intensity of the peak at the 2 theta angle of 37 +/-0.5 DEG in the XRD pattern

TABLE 2

TABLE 3

Sample numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-DB-1	C-DB-2
									Fe/ppm	4250	4230	4220	4260	4270	4260	4230	4280
Ni/ppm	2030	2035	2009	1997	2011	2013	2021	2100
									V/ppm	2025	2015	2012	2008	2020	2007	2016	2130
Material balance/mass%
									Dry gas	2.71	2.56	2.74	2.75	2.78	2.55	3.24	3.12
Liquefied gas	15	15.52	15.4	15.27	15.32	15.35	13.86	14.55
									C5+ gasoline	40.85	42.43	42.25	40.77	41.85	41.83	38.57	39.76
Diesel oil	16.94	16.75	16.63	17.08	16.67	16.76	17.34	16.47
									Heavy oil	11.22	9.57	9.72	10.92	10.3	10.53	12.42	12.45
Coke	13.28	13.17	13.24	13.21	13.08	12.98	14.57	13.65
									Total of	100	100	100	100	100	100	100	100
Conversion/mass%	71.84	73.68	73.65	72	73.03	72.71	70.24	71.08
									Total liquid/mass%	72.79	74.7	74.28	73.12	73.84	73.94	69.77	70.78
Coke selectivity	0.1849	0.1787	0.1798	0.1834	0.1791	0.1785	0.2074	0.1920
									Selectivity of dry gas	0.0377	0.0347	0.0372	0.0382	0.0381	0.0351	0.0461	0.0439

In the present invention, the conversion rate is gasoline yield + liquefied gas yield + dry gas yield + coke yield, the total liquid yield (also referred to as total liquid product yield) is gasoline yield + diesel oil yield + liquefied gas yield, the coke selectivity is coke yield/conversion rate, and the dry gas selectivity is dry gas yield/conversion rate.

Example B1

This example illustrates the preparation of the mesoporous matrix material with high specific heat capacity provided by the present invention.

The concentration of 350gAl₂O₃Al of/L₂(SO₄)₃Solution with CO^3-Ammonium carbonate solution with a concentration of 0.10mol/L was mixed at 30 ℃ to prepare a gel, and the pH was controlled to 7.5 to obtain slurry BA. To a concentration of 145gMnO₂MnCl of/L₂Adding urea into the solution, wherein the molar ratio of the urea to the manganese ions is 2, and stirring for 30 minutes at room temperature to obtain a solution BB. Adding the solution BB into the slurry BA, aging for 24h at 80 ℃ under stirring, and cooling the system to room temperatureThe solid precipitate obtained by filtration was then separated into solid precipitates (dry basis): h₂O is 1: 10 is mixed with water for beating according to the weight ratio of B₂O₃: adding ammonium borate in a weight ratio of 0.01:1 on a dry basis to the high specific heat capacity matrix material, stirring at 50 ℃ for 2 hours, filtering, and precipitating the solid precipitate as a precipitate (dry basis): h₂O is 1: and exchanging for 3 times at room temperature according to the weight ratio of 8, wherein each exchange is carried out for 0.5 hour, the obtained washed solid precipitate is neutral, then drying is carried out for 12 hours at 120 ℃ to obtain a matrix material precursor, then roasting is carried out for 6 hours at 550 ℃, and furnace cooling is carried out to room temperature to obtain the high specific heat capacity matrix material, which is marked as BAM-1. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore diameter of BAM-1 are listed in Table 4.

The elemental analytical chemical composition expression of BAM-1 is 29.7MnO by weight₂·69.2Al₂O₃·1.1B₂O₃(ii) a Specific heat capacity of 1.3J/(g.K), specific surface area of 310m²Per g, pore volume 0.65cm³G, average pore diameter 8.4 nm.

Examples B2-B4

Examples B2-B4 are provided to illustrate the preparation of the mesoporous matrix material with high specific heat capacity provided by the present invention.

Mesoporous matrix materials BAM-2 to BAM-4 of high specific heat capacity were prepared according to the method of example B1, except for the formulation, preparation parameters, the elemental composition, specific heat capacity, specific surface area, pore volume and average pore diameter, which are listed in Table 4.

Example B5

Example B5 is provided to illustrate the preparation of a mesoporous host material with high specific heat capacity according to the present invention.

The concentration of 350gAl₂O₃Al (NO)/L₃)₃Solution with CO^3-Ammonium carbonate and OH with the concentration of 0.30mol/L^-An aqueous ammonia solution having a concentration of 0.1mol/L was mixed to prepare a gel, and the pH was controlled to 10.5 to obtain slurry BA. Adding Mn₃O₄Mixing with hydrochloric acid and water to obtain 201.7gMnO₂Controlling the pH value of a/L manganese chloride solution to be 6, adding urea into the solution, wherein the molar ratio of the urea to manganese ions is 3, and stirring the solution for 40 minutes at room temperature to obtain the manganese chloride/L manganese chloride solutionTo solution BB. Adding the solution BB into the slurry BA, stirring and aging at 60 ℃ for 24h, cooling the system to room temperature, and then filtering to obtain a solid precipitate, wherein the solid precipitate is prepared from the following components in percentage by weight: h₂O is 1: 10 is mixed with water for beating according to the weight ratio of B₂O₃: the resulting high specific heat capacity matrix material was 0.01:1, stirring for 2 hours at 50 ℃, filtering, washing with water (namely washing with water), drying for 12 hours at 120 ℃ to obtain a matrix material precursor, roasting for 4 hours at 650 ℃, and cooling to room temperature along with a furnace to obtain the matrix material, which is marked as BAM-5. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore diameter of BAM-5 are listed in Table 4.

BAM-5 has an elemental analytical chemical composition expression of 34.8MnO by weight₂·60.4Al₂O₃·4.8B₂O₃(ii) a Specific heat capacity of 1.43J/(g.K), specific surface area of 338m²G, pore volume 0.94cm³G, average pore diameter 11.1 nm.

Example B6

Example B6 is provided to illustrate the preparation of a mesoporous host material with high specific heat capacity according to the present invention.

A matrix material BAM-6 was prepared according to the method of example B5, except for the formulation, preparation parameters, the elemental composition, the specific surface area, the pore volume and the average pore diameter, which are listed in Table 4.

Example B7

This example illustrates the cracking activity of the mesoporous matrix material with high specific heat capacity applied in the heavy oil cracking process.

The matrix material of each example was mixed with REY molecular sieves (RE)₂O₃ 16.5％，Na₂O1.4% and produced by Changling catalyst factory of China petrochemical catalyst Co., Ltd.) in a weight ratio of 2:8, wherein the samples are recorded as BC-1 to BC-6, 4000ppm of contaminated iron, 2000ppm of nickel and 2000ppm of vanadium are dipped by a Mitchell method, uniformly ground, tabletted and sieved into 20-40 mesh particles, aged at 780 ℃ for 12 hours under the condition of 100% water vapor, subjected to cracking performance evaluation on a heavy oil microreaction device, and subjected to three reactions in the evaluation process, and then subjected to cracking performance evaluationAnd (4) generating a cycle, and taking the last result as the evaluation result of the cracking performance of the catalyst. The evaluation conditions of the heavy oil micro-reaction are as follows: the weight ratio of the agent to the oil is 1.56, the sample loading is 2g, the reaction temperature is 500 ℃, the reaction time is 70 seconds, the regeneration temperature is 600 ℃, and the raw oil is vacuum gas oil. The properties of the feed oil are shown in Table 2. The evaluation results are shown in Table 5.

TABLE 4

TABLE 5

Sample numbering	BC-1	BC-2	BC-3	BC-4	BC-5	BC-6
							Fe/ppm	4250	4230	4220	4260	4270	4260
Ni/ppm	2030	2035	2009	1997	2011	2013
							V/ppm	2025	2015	2012	2008	2020	2007
Material balance/m%
							Dry gas	2.61	2.58	2.71	2.59	2.73	2.68
Liquefied gas	15.21	15.33	15.45	15.48	15.36	15.35
							C5+ gasoline	41.23	42.36	42.76	43.43	42.25	41.32
Diesel oil	17.09	16.87	16.67	16.33	16.71	17.18
							Heavy oil	10.74	9.99	9.17	9.02	9.87	10.31
Coke	13.12	12.87	13.24	13.15	13.08	13.16
							Total of	100	100	100	100	100	100
Conversion/mass%	72.17	73.14	74.16	74.65	73.42	72.51
							Total liquid/mass%	73.53	74.56	74.88	75.24	74.32	73.85
Coke selectivity	0.1818	0.1760	0.1785	0.1762	0.1782	0.1815
							Selectivity of dry gas	0.0362	0.0353	0.0365	0.0347	0.0372	0.0370

As can be seen from the heavy oil evaluation results in tables 3 and 5, compared with the comparative sample, the sample containing the matrix material with high specific heat capacity provided by the invention has the advantages that the catalyst shows more excellent heavy oil cracking performance while maintaining good coke selectivity, the conversion rate is higher, the heavy oil yield is remarkably reduced, the gasoline yield is improved, the total liquid yield is remarkably higher, and the product distribution is optimized.

Claims

1. A high specific heat capacity host material, wherein the high specific heat capacity host material contains at least 5 wt% manganese oxide, and the high specific heat capacity host material has a specific heat capacity of 1.3-2.0J/(g · K) at a temperature of 1000K.

2. The high specific heat capacity host material of claim 1, wherein the high specific heat capacity host material comprises Al₂O₃5-95% by weight, calculated as MnO, of alumina₂5-95% by weight manganese oxide and 0-40% by weight boron compound on a dry basis.

3. The high specific heat capacity matrix material according to claim 2, wherein the boron compound is boron nitride and/or boron oxide.

4. The high specific heat capacity host material of claim 3, wherein the high specific heat capacity host material comprises Al₂O₃15-80% or 19-60% by weight of alumina, calculated as MnO₂10-70 wt% or 19-66 wt% manganese oxide, 3-30 wt% or 8-26 wt% boron nitride on a dry basis.

5. According to the rightThe high specific heat capacity matrix material according to claim 3, wherein the high specific heat capacity matrix material contains Al₂O₃15-80% by weight or 20-62% by weight of alumina, in terms of MnO₂15-80% by weight or 30-72% by weight of manganese oxide and B₂O₃0.5-10 wt% or 2-8 wt% of boron oxide.

6. The high specific heat capacity matrix material according to claim 1 or 2, wherein the specific surface area of the high specific heat capacity matrix material is 150-500m²·g^-1。

7. The matrix material with high specific heat capacity as defined in claim 4 or 6, wherein the matrix material with high specific heat capacity has a specific surface area of 180-300m²·g^-1。

8. The matrix material with high specific heat capacity as claimed in claim 5 or 6, wherein the specific surface area of the matrix material is 300-500m²/g。

9. The high specific heat capacity matrix material of claim 2 or 6, wherein the high specific heat capacity matrix material has a pore volume of 0.3 to 1.5cm³·g^-1。

10. The high specific heat capacity host material of claim 4 or 7 or 9, wherein the high specific heat capacity host material has a pore volume of 0.35 to 0.75cm³/g。

11. The high specific heat capacity host material of claim 5 or 8 or 9, wherein the high specific heat capacity host material has a pore volume of 0.5-1.5cm³/g。

12. The high specific heat capacity matrix material of claim 2, 6 or 9, wherein the high specific heat capacity matrix material has an average pore diameter of 3 to 20 nm.

13. The high specific heat capacity matrix material of claim 4, 7, 10 or 12, wherein the high specific heat capacity matrix material has an average pore diameter of 5-13 nm.

14. The high specific heat capacity host material of claim 5, 8, 11 or 12, wherein the high specific heat capacity host material has an average pore size of 5-18 nm.

15. The high specific heat capacity matrix material of claim 1, wherein an XRD pattern of the high specific heat capacity matrix material has an intensity ratio of peaks at 18 ± 0.5 ° 2 theta and 37 ± 0.5 ° 2 theta of 1: (3-10).

16. A preparation method of a high specific heat capacity matrix material comprises the following steps:

(4) Washed and/or dried and/or calcined.

17. The method of claim 16 wherein mixing the aluminum source and the alkali into the gel comprises: mixing the aluminum source solution and the alkali solution to form colloid with the temperature of room temperature to 85 ℃ and the pH value of 7-11.

18. The preparation process as claimed in claim 17, wherein the concentration of alumina in the aluminum source solution is 150-350gAl₂O₃and/L, wherein the concentration of the alkali in the alkali solution is 0.1-1 mol/L.

19. The production method according to any one of claims 16 to 18, wherein the aluminum source is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride and the like; the alkali is one or more of carbonate dissolved in water, bicarbonate dissolved in water and hydroxide dissolved in water.

20. The process according to claim 17 or 18, wherein the solution of the base is selected from the group consisting of solutions containing CO₃ ^2-、HCO₃ ^-Or OH^-An alkaline aqueous solution of one or more of (a) and (b), the solution of the base being CO₃ ^2-Has a concentration of 0-0.6mol/L, OH^-The concentration of (A) is 0-0.5mol/L, HCO₃ ^-The concentration of (b) is 0 to 1 mol/L.

21. The process according to claim 16, wherein in the step (2), the molar ratio of urea to manganese ions is 1 to 5, for example 2 to 4, and the concentration of manganese salt in the manganese salt solution is MnO₂The amount can be 50-500 g.L^-1。

22. The production process according to claim 16, wherein the step (2) comprises adding urea to the manganese salt solution, followed by stirring at room temperature for 30 to 60 minutes to obtain a manganese source solution.

23. The method according to claim 16, wherein the boron-containing compound is boron nitride and/or boron oxide and/or a boron oxide precursor.

24. The production method according to claim 23, wherein the boron nitride is at least one selected from the group consisting of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN) and wurtzite boron nitride (w-BN); the boron oxide precursor is one or more of ammonium borate, ammonium hydrogen borate or boric acid.

25. The preparation method according to claim 16, wherein the step (3) further comprises an aging process after mixing the aluminum-containing colloid and the manganese source solution, wherein the aging temperature is from room temperature to 120 ℃, the aging time is from 4 to 72 hours, and the aging process is performed under stirring or standing aging; preferably, the ageing is carried out under stirring, at an ageing temperature of 60-100 ℃ and for an ageing time of 12-36 h.

26. The production method according to claim 16 or 25, wherein the boron compound is boron nitride; the method for forming the mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in the step (3) is as follows: mixing the aluminum-containing colloid, the manganese source solution and the boron compound, and aging.

27. The method according to claim 16 or 25, wherein the boron compound is boron oxide and/or a precursor of boron oxide, and the method of mixing the aluminum-containing colloid, the manganese source solution, and the boron compound in the step (3) is as follows: the aluminum-containing colloid and the manganese source solution are mixed, aged, optionally washed, and then mixed with the boron compound.

28. The production method according to claim 16, wherein the calcination temperature in the step (4) is 500 ℃ to 900 ℃ and the calcination time is 4 to 8 hours.

29. A high specific heat capacity matrix material obtained by the method of making a high specific heat capacity matrix material of any one of claims 16-28.

30. Use of a high specific heat capacity matrix material according to any one of claims 1 to 15 or 29 in a catalyst or as a thermal storage material.

31. Use of a high specific heat capacity matrix material according to any one of claims 1 to 15 or 29 as a matrix material in a catalytic cracking catalyst or promoter.

32. A catalytic cracking catalyst comprising a molecular sieve and a matrix, characterised in that the matrix comprises a high specific heat capacity matrix material according to any one of claims 1 to 15 or claim 29.