Phosphorus-containing matrix material and preparation method and application thereof
阅读说明：本技术 一种含磷的基质材料及其制备方法与应用 (Phosphorus-containing matrix material and preparation method and application thereof ) 是由 刘倩倩 陈振宇 朱玉霞 宋海涛 林伟 杨雪 于 2020-03-31 设计创作，主要内容包括：一种含磷的基质材料及其制备方法与应用,所述基质材料含有5-94.5重量％的氧化铝、5-94.5重量％氧化锰以及0.5-10重量％的磷氧化物。其制备方法包括：形成包括锰源、铝源的固体沉淀物,引入磷,任选洗涤和/或干燥和/或焙烧的步骤。该基质材料用于催化剂具有良好的催化反应效果。(A phosphorus-containing matrix material, a preparation method and an application thereof, wherein the matrix material contains 5-94.5 wt% of alumina, 5-94.5 wt% of manganese oxide and 0.5-10 wt% of phosphorus oxide. The preparation method comprises the following steps: a solid precipitate is formed comprising a source of manganese, a source of aluminum, phosphorus is introduced, and optionally steps of washing and/or drying and/or calcining. The matrix material has good catalytic reaction effect when being used for a catalyst.)
1. A high specific heat capacity substrate material, wherein the high specific heat capacity substrate material contains 5-94.5 wt% of alumina as MnO25-94.5% by weight, calculated as P, of manganese oxide2O50.5-10 wt% of phosphorus oxide, wherein the specific heat capacity of the high specific heat capacity matrix material at the temperature of 1000K is 1.3-2.0J/(g.K).
2. The high specific heat capacity matrix material of claim 1, wherein the high specific heat capacity matrix material contains 0-40 wt% or 4-26 wt% boron nitride on a dry basis.
3. The high specific heat capacity matrix material according to claim 1 or 2, wherein the high specific heat capacity matrix material contains Al2O315-80 wt% or 20-60 wt% of alumina.
4. The high specific heat capacity matrix material of claim 1, 2 or 3, wherein MnO is contained in the high specific heat capacity matrix material210-70 wt% or 15-60 wt% manganese oxide.
5. The matrix material with high specific heat capacity according to any one of claims 1 to 4, wherein the matrix material with high specific heat capacity contains P2O50.8-9 wt% or 2-8 wt% calculated phosphorus oxide.
6. High specific heat capacity according to any one of claims 1 to 5A matrix material, wherein the specific surface area of the matrix material with high specific heat capacity is 300-500m2·g-1Or 330 and 400m2·g-1。
7. The high specific heat capacity matrix material of any one of claims 1-6, wherein the high specific heat capacity matrix material has a pore volume of 0.5-1.5cm3/g。
8. The high specific heat capacity matrix material of any one of claims 1-7, wherein the high specific heat capacity matrix material has an average pore diameter of 3-20nm or 9-13 nm.
9. The high specific heat capacity matrix material of claim 1, wherein in the high specific heat capacity matrix material XRD spectrum, the peak intensity ratio at 2 Θ angles of 18 ± 0.5 ° and 2 Θ angles of 37 ± 0.5 ° is 1: (3-10).
10. A preparation method of a high specific heat capacity matrix material 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 boron nitride, and aging;
(4) the aged solid precipitate is contacted with a source of phosphorus, optionally washed and/or dried and/or calcined.
11. The method of claim 10, wherein mixing the aluminum source with the alkali to form 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.
12. The preparation method as claimed in claim 11, 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.
13. The method of claim 10 wherein the aluminum source is selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum phosphate and aluminum chloride, and the base is selected from the group consisting of water-soluble carbonate, water-soluble bicarbonate and water-soluble hydroxide.
14. The process according to claim 11 or 12, 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 -Is 0 to 1 mol/.
15. The production process according to claim 10, wherein, in the step (2), the molar ratio of urea to manganese ions is 1 to 5, preferably 2 to 4; MnO is added into the manganese salt solution2The concentration of manganese salt is preferably 50-500 g.L-1。
16. The production process according to claim 10, wherein, in the step (2), urea is added to the manganese salt solution, followed by stirring at room temperature for 30 to 60 minutes to obtain a manganese source solution.
17. The production process according to claim 10, wherein, in the step (3), the aging temperature is from room temperature to 120 ℃ and the aging time is from 4 to 72 hours.
18. The process according to claim 17, wherein the aging temperature is 60 to 100 ℃ and the aging time is 12 to 36 hours, and stirring and aging are carried out.
19. The method of claim 10, wherein said contacting the aged solid precipitate with a source of phosphorus comprises: mixing the aged solid precipitate with water according to the dry basis of the aged solid precipitate: water 1: (2-5), mixing and pulping, mixing the phosphorus source and the slurry at the temperature of room temperature to 90 ℃, and then stirring or standing for 0.2-5 hours.
20. The method according to claim 10, wherein the manganese salt is selected from one or more of manganese nitrate, manganese sulfate, manganese phosphate, manganese chloride, and the like, the boron nitride is selected from at least one of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN), and wurtzite boron nitride (w-BN), and the phosphorus source is selected from one or more of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, or phosphoric acid.
21. The production method according to claim 16, wherein the calcination in the step (4) is carried out at a calcination temperature of 500 ℃ to 900 ℃ for 4 to 8 hours.
22. A high specific heat capacity matrix material obtainable by the method of any one of claims 10 to 21.
23. Use of a high specific heat capacity matrix material according to any one of claims 1 to 9 or 22 as a thermal storage material or catalyst support.
24. Use of a high specific heat capacity host material as claimed in any one of claims 1 to 9 or 22 as a host material in a catalytic cracking catalyst or promoter.
25. 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 9 or 22.
Technical Field
The invention relates to a phosphorus-containing matrix material and a preparation method and application thereof.
Background
Refineries typically reduce refinery costs by processing heavy and light crude oils, however, heavy and light crude oils typically have high levels of metals (e.g., vanadium, nickel) and are prone to catalyst metal poisoning. Catalytic cracking is an important means for processing heavy oil, more than 75% of gasoline in China is provided by catalytic cracking, severe metal pollution can cause the fluidization performance of a catalytic cracking catalyst to be deteriorated, the accessibility of an active center to be reduced, the selectivity of the catalyst to be deteriorated, the yield of dry gas and coke to be increased, and sometimes, a device is even exposed to the risk of shutdown. Many research results show that once metals such as iron, nickel and the like are deposited on the surface of the catalyst, the metals are difficult to migrate and can interact with elements such as silicon, aluminum, vanadium, sodium and the like to form low-melting-point eutectic substances, 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 of the catalyst, the reactant is blocked to enter the catalyst and a pore channel for product diffusion, and the product distribution is deteriorated.
In the prior art, one method for reducing the influence of metal pollution is to pretreat raw oil, but the method cannot completely remove metals in oil products and cannot fundamentally improve the metal pollution resistance of a catalytic cracking main agent. In the other method, a metal trapping agent is used in the catalytic cracking process to reduce the deposition of metal on the surface of the catalyst, but the metal trapping agent can only be added in a small proportion and cannot radically improve the metal pollution resistance of the catalytic cracking main agent.
Disclosure of Invention
The inventor of the invention has found through long-term research that the use of proper phosphorus-containing matrix material with high specific heat capacity instead of conventional catalytic cracking catalyst matrix material with low specific heat capacity, such as clay, aluminum oxide, alumina sol and the like, can slow down the sintering deactivation degree of the catalyst surface, is beneficial to gasification and cracking reaction of heavy oil molecules, and simultaneously improves the metal pollution resistance of the catalyst.
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 aims to solve another technical problem of providing a preparation method of a matrix material with excessive heat capacity. The preparation method can prepare 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 substrate material, wherein the high specific heat capacity substrate material contains 5-94.5 wt% of alumina and MnO25-94.5% by weight, calculated as P, of manganese oxide2O50.5-10 wt% of phosphorus oxide, wherein the specific heat capacity of the high specific heat capacity matrix material at the temperature of 1000K is 1.3-2.0J/(g.K).
The high specific heat capacity matrix material according to the above technical aspect, wherein the high specific heat capacity matrix material contains 0 to 40 wt%, such as 0.5 to 35 wt%, or 3 to 30 wt%, or 4 to 26 wt%, or 8 to 25 wt% of boron nitride on a dry basis.
The high specific heat capacity matrix material according to any one of the above technical solutions, wherein preferably, the high specific heat capacity matrix material contains Al2O315-80 wt%, such as 19-71 wt% or 20-60 wt% alumina.
The high specific heat capacity matrix material according to any one of the above technical solutions, wherein preferably, MnO is contained in the high specific heat capacity matrix material210-70 wt%, e.g. 15-60 wt% manganese oxide.
The high specific heat capacity matrix material according to any one of the above technical solutions, wherein preferably, the high specific heat capacity matrix material contains P2O50.8-9 wt%, e.g. 1-8 wt%, or 2-8 wt%, or 3-7.5 wt% calculated phosphorus 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 250-500m2·g-1For example 300-2·g-1Or 300-450m2·g-1Or 330 and 400m2·g-1。
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 0.5-1.5cm3Per g, for example, 0.55 to 1.3cm3G or 0.8-1.3cm3G or 0.9-1.25cm3·g-1。
The high specific heat capacity matrix material according to any one of the above technical schemes, wherein the average pore diameter of the high specific heat capacity matrix material is 3-20nm, or 4-17nm, or 5-15nm, or 9-13 nm.
The high specific heat capacity host material according to any one of the above technical solutions, wherein the specific heat capacity of the high specific heat capacity host material may be 1.32-1.96J/(g · K), for example, 1.4-1.96 or 1.51-1.96J/(g · K).
The high specific heat capacity matrix material according to any one of the above technical solutions, wherein the XRD spectrum of the high specific heat capacity matrix material has peaks at 2 θ angles of 18 ± 0.5 ° and at 2 θ angles of 37 ± 0.5 °, and the ratio of the intensity of the peak at 2 θ angles of 18 ± 0.5 ° to the intensity of the peak at 2 θ angles of 37 ± 0.5 ° 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 boron nitride, and aging;
(4) the aged solid precipitate is contacted with a source of phosphorus, optionally washed and/or dried and/or calcined.
The preparation method according to the above technical scheme, wherein in the step (1), the aluminum source and the alkali are mixed to form a colloid, and the colloid forming temperature for mixing the aluminum source and the alkali into the colloid may be from room temperature to 85 ℃. In the invention, the temperature of the room temperature is 15-40 ℃.
The preparation method according to any one of the above technical solutions, wherein the mixing of the aluminum source and the alkali into the paste may be performed by a method comprising: 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 aluminum-containing colloid is, for example, 8.5 to 11 or 9 to 10 or 10 to 11.
The preparation method according to any one of the above technical solutions, wherein the concentration of the alumina in the aluminum source solution may be 150-350gAl2O3L; the concentration of the base in the solution of the base may be 0.1 to 1 mol/L.
The method according to any one of the preceding claims, wherein the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate and aluminum chloride, preferably one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
The preparation method according to any one of the above technical solutions, wherein the base may be one or more of a carbonate dissolved in water, a bicarbonate dissolved in water, and a hydroxide dissolved in water, for example, the base may be one or more of a carbonate of an alkali metal, a bicarbonate of an alkali metal, a hydroxide of an alkali metal, ammonium carbonate, ammonium bicarbonate, and ammonia water.
The method according to any of the preceding claims, wherein the solution of the base is 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-Preferably in a concentration of 0-0.6mol/L, e.g. 0.3-0.5mol/L, OH-Preferably 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) is preferably 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 preparation method according to any one of the above technical schemes, wherein in the step (2), the molar ratio of the urea to the manganese ions is 1-5:1, such as 2-4: 1. In the manganese salt solution, with MnO2The concentration of manganese salt is preferably 50-500 g.L-1。
The preparation method according to any one of the above technical schemes, wherein in the step (2), urea is added into the manganese salt solution, and then the mixture is stirred at room temperature for 30-60 minutes to obtain a manganese source solution.
The preparation method according to any one of the above technical schemes, wherein the manganese salt may be selected from one or more of manganese nitrate, manganese sulfate, manganese phosphate or manganese chloride, and is preferably selected from one or more of manganese nitrate, manganese sulfate or manganese chloride.
The method according to any one of the above aspects, wherein the boron nitride is 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 process according to any one of the preceding claims, wherein in step (3), the aging temperature is preferably from room temperature to 120 ℃, for example from 40 to 100 ℃, and the aging time is from 4 to 72 hours. Can be aged under stirring or standing.
The preparation method according to any one of the above technical schemes, wherein the aging temperature is preferably 60-100 ℃, the aging time is preferably 12-36h, and the aging is preferably carried out under stirring.
The method according to any one of the preceding claims, wherein the step of contacting the aged solid precipitate with a phosphorus source comprises: on a dry basis of the aged solid precipitate: water 1: (2-5) mixing the aged solid precipitate with water and pulping, mixing a phosphorus source with the obtained slurry at room temperature to 90 ℃, and then stirring or standing for a period of time, for example, 0.2-5 hours, preferably 0.5-3 hours, to perform a reaction.
The preparation method according to any one of the above technical schemes, wherein the phosphorus source is one or more selected from ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphoric acid.
The preparation method according to any one of the above technical solutions, wherein the aged solid precipitate is obtained by filtering and optionally washing the aged product obtained in step (3). The washing is not particularly required, and generally the washing makes the washed solid product neutral. Said solid productNeutral means that the water is neutral, usually at a pH of 6.5 to 7.5, after contacting the solid product with water (for example, the solid product and water may be mixed at a weight ratio of 1: 3, stirred for 1 minute or more, and then the pH is measured). In the washing, an aged solid precipitate (solid precipitate for short) obtained by filtering the aged product obtained in the step (3) may be obtained by mixing the aged 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 aged solid precipitate may also be washed with water until the washed water is neutral.
The method of any one of the preceding claims, wherein the phosphorus source is P2O5The ratio of the amount used to the dry weight of the resulting high specific heat capacity matrix material is preferably (0.005-0.1): 1.
according to any of the above technical solutions, the mixture formed by contacting the aged solid precipitate with the phosphorus source may be further subjected to one or more of washing, drying and roasting, for example, drying and roasting after washing may be performed, or drying and roasting may be performed directly without washing.
The preparation method according to any one of the above technical solutions, wherein the drying in step (4) is a drying method in the prior art, and may be drying, pneumatic drying, or flash drying, for example. In one embodiment, the drying temperature may be 100-150 deg.C, and the drying time may be 6-24 hours.
The preparation method according to any one of the above technical schemes, wherein in the step (4), the roasting is carried out at a roasting temperature of 500-900 ℃ for 4-8 hours; the roasting temperature is preferably 550-800 ℃ or 550-750 ℃; the calcination temperature is more preferably from 650 ℃ to 750 ℃.
The invention also provides the high specific heat capacity matrix material obtained by the preparation method in any technical scheme. The specific heat capacity of the high specific heat capacity matrix material prepared according to the preparation method provided by the invention can be 1.3-2.0, for example, the specific heat capacity of the high specific heat capacity matrix material prepared according to the preparation method provided by the invention is 1.32-1.96J/(g.K), or 1.4-1.96J/(g.K), or 1.51-1.96J/(g.K).
The invention also provides application of the high specific heat capacity matrix material in any technical scheme as a catalyst carrier or a heat storage material.
The invention also provides application of the matrix material with high specific heat capacity in any technical scheme as a matrix material in a catalytic cracking catalyst or an auxiliary agent.
The invention also provides a catalytic cracking catalyst, which comprises a molecular sieve and a matrix, and is characterized in that the matrix comprises the high specific heat capacity matrix material in any technical scheme.
As one embodiment applied to a catalytic cracking catalyst or promoter, the catalytic cracking catalyst or promoter comprises a molecular sieve and a matrix comprising the high specific heat capacity matrix material and optionally other matrix materials. The molecular sieve is used in a cracking catalyst or an auxiliary agent, such as a Y-type molecular sieve. Such as one or more of clay, binder, mesoporous material. The addition ratio of the high specific heat capacity matrix material can be properly adjusted according to the properties of raw oil and the change of operation process, for example, the catalytic cracking catalyst contains 10-85 wt% of the high specific heat capacity matrix material, 15-60 wt% of molecular sieve and 0-70 wt% of other matrix materials, 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 also has at least one of the following beneficial effects, preferably a plurality of or all of the following beneficial effects:
(1) has good metal pollution resistance, especially iron pollution resistance; (2) the chemical stability is higher; (3) the wear resistance is better; (4) has higher high-temperature thermal stability; (5) compared with the conventional matrix materials such as kaolin, sepiolite, aluminum oxide and the like, the composite material has higher specific heat capacity and better high temperature resistance and/or metal pollution resistance; (6) the catalyst is used as a matrix material of a heavy oil cracking catalyst or an auxiliary agent, so that the specific heat capacity of catalyst particles can be fundamentally improved, and the metal pollution resistance, especially the iron pollution resistance, of the catalyst is improved; (7) the catalyst is used for a catalytic cracking catalyst, so that the catalyst can have good fluidization performance under the condition of metal pollution; (8) the catalyst is used for catalytic cracking catalyst, can obviously improve the high-temperature stability of the catalyst, and optimizes the product distribution; (9) the material can be used as a matrix material of a heavy oil cracking catalyst or an auxiliary agent containing a molecular sieve, and can effectively slow down the collapse of the crystal structure of the molecular sieve; (10) 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. (11) Phosphorus is introduced into the high specific heat capacity matrix material, and is matched with aluminum and manganese, so that the acidity is improved, and the pre-cracking capability is enhanced.
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) for preparing a matrix material having a high 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 is good; (5) the high specific heat capacity matrix material with a mesoporous structure can be prepared, and the average pore diameter of the prepared matrix material can be larger than 3nm and even more than 7 nm; (6) can prepare a high specific heat capacity matrix material with a higher mesoporous ratio; (7) a high specific heat capacity matrix material with a high specific surface area can be prepared; (8) a high specific heat capacity matrix material with higher pore volume can be obtained; (9) the prepared high specific heat capacity matrix material has higher chemical stability; (10) the prepared 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. (11) Compared with the matrix material prepared by other preparation methods in the range, the prepared matrix material with high specific heat capacity in the range has better high-temperature stability and metal pollution resistance.
The high specific heat capacity matrix material provided by the invention can be used as a matrix of a catalytic cracking catalyst or an auxiliary agent and a carrier of a hydrogenation catalyst.
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. As can be seen from FIG. 1, the said spectrum has diffraction peaks at 2 θ angles of 18. + -. 0.5 °, 37. + -. 0.5 °, 48. + -. 0.5 °, 59. + -. 0.5 °, 66. + -. 0.5 °.
Detailed Description
The high specific heat capacity matrix material provided by the invention contains Al2O35-94.5% by weight of alumina and in MnO25-94.5% by weight manganese oxide, 0-40% by weight boron nitride on a dry basis and P2O50.5-10 wt% phosphorus oxide, for example, the high specific heat capacity matrix material comprises 15-70 wt%, or 20-65 wt%, or 30-61 wt% manganese oxide and 29-84 wt%, or 35-80 wt%, or 39-70 wt% alumina, 5-35 wt% boron nitride and 1-8 wt% phosphorus oxide.
The high specific heat capacity matrix material provided by the invention has the specific heat capacity of 1.3-2.0J/(g.K). The high specific heat capacity matrix material (for short, matrix material) may or may not contain boron nitride, and preferably, the high specific heat capacity matrix provided by the invention contains boron nitride, and compared with the high specific heat capacity matrix material without boron nitride, the high specific heat capacity matrix material has better metal contamination resistance.
The invention provides a high specific heat capacity matrix material, a first embodiment, which contains Al2O35-94.5% by weight of alumina, expressed as MnO25-94.5% by weight calculated as oxides of manganese and in P2O50.5-10 wt% calculated phosphorus oxide, and no boron nitride. For example, the high specific heat capacity matrix material comprises 15-70 wt%, or 20-65 wt%, or 25-60 wt% manganese oxide, 29-84 wt%, or 35-80 wt%, or 39-74 wt% alumina, and 0.8-8 wt% phosphorus oxide.
The invention providesA high specific heat capacity matrix material, in the first embodiment, the specific surface area of the high specific heat capacity matrix material is 250-400m2·g-1E.g., 280-350m2·g-1. The pore volume of the high specific heat capacity matrix material is 0.5-1.0cm3Per g, for example, 0.55 to 0.8cm3(ii) in terms of/g. The high specific heat capacity matrix material has an average pore diameter of 3 to 12nm, for example 6 to 10 nm.
The second embodiment of the high specific heat capacity matrix material provided by the invention contains boron nitride, and the specific heat capacity of the boron nitride is 1.3-2.0J/(g.K), for example, 1.4-1.96J/(g.K) or 1.51-1.96J/(g.K). The anhydrous chemical expression of the high specific heat capacity matrix material in weight ratio can be expressed as (5-94) Al2O3·(5-94)MnO2·(0.5-40)BN·(0.5-10)P2O5For example, it may be (20-80) Al2O3·(15-75)MnO2·(5-30)BN·(1-8)P2O5. Preferably, the high specific heat capacity matrix material contains 5 to 94 wt.% of alumina, 5 to 94 wt.% of manganese oxide, 0.5 to 10 wt.% of phosphorus oxide, and more than 0 and not more than 40 wt.%, e.g., 0.5 to 35 wt.% of boron nitride on a dry basis, based on the weight of the high specific heat capacity matrix material. For example, the high specific heat capacity matrix material contains 15 to 80 wt% of alumina, 15 to 70 wt% of manganese oxide, 0.8 to 9 wt% of phosphorus oxide, and 5 to 30 wt% of boron nitride; further, the high specific heat capacity matrix material contains 19 to 74 wt% of alumina, 0.8 to 8 wt% of phosphorus oxide, 15 to 60 wt% of manganese oxide, and 8 to 26 wt% of boron nitride. The matrix material contains boron nitride, so that the abrasion resistance of the catalyst can be greatly improved.
According to a 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 300-500m2·g-1For example, 320-450m2·g-1Or 330 and 400m2·g-1The pore volume of the high specific heat capacity matrix material is 0.5-1.5cm3·g-1For example 0.8-1.3cm3·g-1Or 0.9-1.25cm3·g-1The high specific heat capacity matrix material is flatThe average pore diameter is from 3 to 20nm, for example from 5 to 18nm or from 7 to 15nm or from 9 to 13nm or from 11 to 13 nm.
The preparation method of the high specific heat capacity matrix material provided by the invention comprises the following steps:
(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 urea to manganese ions is 1-5; the temperature at which the manganese salt solution is mixed with the urea is not particularly critical, for example the mixing is carried out at room temperature, the stirring time being for example 30 to 60 minutes;
(3) mixing the product obtained in the step (1), the product obtained in the step (2) and optional boron nitride, and aging at room temperature to 120 ℃ for 4-72 hours; and
(4) and (4) filtering the aged product obtained in the step (3), optionally carrying out first washing to obtain an aged solid precipitate, contacting the aged solid precipitate with a phosphorus source, optionally carrying out second washing, drying and roasting to obtain the high specific heat capacity matrix material.
According to the specific embodiment of the method for preparing the matrix material with high specific heat capacity of the present invention, wherein the alkali solution in the step (1) has a wide selection range, it is preferable that the alkali solution in the step (1) contains 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. 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. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. The pH of the colloid obtained by gelling in step (1) is preferably from 7.5 to 11, for example from 8.5 to 11 or from 9 to 10. When ammonia water is selectedAnd calculating the required addition amount of the ammonia water according to the calculated hydroxyl radical on the assumption that the ammonia water is completely ionized.
According to the specific embodiment of the method for preparing the high specific heat capacity matrix material provided by the invention, the variety of the aluminum source can be widely selected, and a water-soluble aluminum source capable of being dissolved in water can be used in the invention, for example, the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate and aluminum chloride, preferably one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
According to the specific embodiment of the preparation method of the high specific heat capacity matrix material, the manganese salt solution with a specific pH value is mixed with urea to form a mixture in the step (2), and the pH value of the manganese salt solution is 3-7, preferably 5-7. 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 the manganese salt solution, and stirring at room temperature for 40-60 minutes, 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 phosphate, manganese chloride, or the like, preferably 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 specific embodiment of the preparation method of the high specific heat capacity matrix material provided by the 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: (0-40) BN, e.g.Is (20-80) Al2O3：(15-75)MnO2: (5-30) BN or (20-70) Al2O3：(15-60)MnO2：(8-25)BN。
According to the specific embodiment of the method for preparing the matrix material with high specific heat capacity provided by the invention, the aging conditions in the step (3) are wide in optional range, and preferably, the aging conditions in the step (3) comprise: 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 a specific embodiment of the method for preparing a high specific heat capacity matrix material provided by the present invention, the boron nitride is 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 specific embodiment of the preparation method of the high specific heat capacity matrix material provided by the invention, in the step (4), the aged product obtained in the step (3) is filtered, and optionally subjected to first washing to obtain an aged solid precipitate, and then the aged solid precipitate is contacted with a phosphorus source, and optionally subjected to second washing. Wherein said phosphorus source is P2O5The weight ratio of the material feeding amount to the dry basis of the high specific heat capacity matrix material is (0.005-0.1): 1. preferably, the product of step (1) in step (3), the product of step (2), the boron nitride and the phosphorus source are used in amounts such that the resulting matrix material comprises 5 to 94% by weight, for example 15 to 80% by weight or 19 to 74% by weight or 20 to 80% by weight, of alumina in MnO25-94% by weight, for example 15-75% by weight or 15-70% by weight or 14-66% by weight, manganese oxide, more than 0 and not more than 40% by weight, for example 0.5-35% by weight or 5-30% by weight or 8-26% by weight, boron nitride and boron nitride in P on a dry basis2O50.5-10% by weight of phosphorus oxide. The first wash or the second wash may be washed with water, preferably the wash renders the wash solution neutral (neutral means a pH of 6.5-7.5) after washing, e.g. by rinsing with deionized water until the deionized water after washing is neutral. Preferably, the first and second washes are performed at least once, preferably at least the first wash is performedAnd (6) washing.
According to the specific embodiment of the preparation method of the high specific heat capacity matrix material provided by the invention, in the step (4), the aged solid precipitate is contacted with a phosphorus source, and the preferable process comprises the following steps of: h2O is 1: (2-5) mixing with water according to the weight ratio, pulping, adding a phosphorus source into the slurry, carrying out contact treatment (for example, stirring) at room temperature to 90 ℃ for 0.2-5 hours, preferably 0.5-3 hours, optionally filtering, and optionally carrying out secondary washing; alternatively, the obtained aged solid precipitate can be directly mixed with a phosphorus source in proportion and uniformly ground. Wherein with P2O5The weight ratio of the phosphorus source to the aged solid precipitate on a dry basis may be 0.005-0.1: 0.9-0.995.
According to a particular embodiment of the method of preparation provided by the present invention, the source of phosphorus comprises a phosphorus-containing compound, which may be one or more of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or phosphoric acid.
According to the specific embodiment of the preparation method of the high specific heat capacity matrix material provided by the invention, the optional range of the drying condition and the roasting 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.
The application method of the high specific heat capacity matrix material provided by the invention is characterized in that the high specific heat capacity matrix material is matched with a Y-type molecular sieve, clay such as kaolin, a binder and the like to prepare a catalytic cracking catalyst, the catalyst is used for catalytic cracking reaction, the catalyst can show more excellent heavy oil cracking performance while maintaining good coke selectivity, particularly has good cracking reaction performance under the condition of metal pollution, and has optimized product distribution, such as higher cracking activity, remarkably reduced heavy oil yield, remarkably improved gasoline yield and remarkably improved total 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 contents of B, N, Fe and P were measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP test method)", eds Yang Cui et al, ed. by scientific Press, 1990). The sample phase was determined by X-ray diffraction. The specific surface area, the pore volume and the average pore diameter of the sample are measured by a low-temperature nitrogen adsorption-desorption method, and the pore distribution is calculated by a BJH method.
Example 1
This example illustrates the preparation of a high specific heat capacity matrix material provided by the present invention.
The concentration of 350gAl2O3Al of/L2(SO4)3Solution with CO3-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 145gMnO2MnCl of/L2Hydrochloric acid (concentration: 36 wt%) was added to the solution, and the pH was controlled to 3.5, then urea was 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. Adding the solution B into the slurry A, stirring and aging for 24h at 80 ℃, cooling the system to room temperature, filtering, washing with deionized water until the washed water is neutral to obtain an aged solid precipitate, and then aging the aged solid precipitate (dry basis): h2O is 1: 2, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: high specific heat capacity matrix material dry basis 0.01: 1, stirring for 2 hours at 50 ℃, drying for 12 hours at 120 ℃ to obtain a matrix material precursor, roasting for 6 hours at 550 ℃, and cooling to room temperature along with the furnace to obtain the high specific heat capacity matrix material, which is marked as AM-1. Formulation, preparation parameters and ratio of AM-1The 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, in which 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 of them is 1: 4.1; the elemental analysis weight chemical composition of the composition is 28.9 percent MnO2、70.2％Al2O3、0.9％P2O5(ii) a Specific heat capacity of 1.33J/(g.K), specific surface area of 308m2Per g, pore volume 0.59cm3G, average pore diameter 7.7 nm.
Examples 2 to 4
Examples 2-4 are provided to illustrate the preparation of high specific heat capacity matrix materials 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 for the raw material ratio, preparation condition parameters, in which solution B and boron nitride were added to slurry a, followed by the aging. The raw material ratios, preparation condition parameters, elemental composition of the product, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in table 1.
Example 5
At 25 ℃ and room temperature, the concentration of 350gAl2O3Al (NO)/L3)3Solution with CO3-The concentration of ammonium carbonate and OH is 0.1mol/L-A solution of 0.15mol/L aqueous ammonia was mixed, stirred for 1 hour, and the pH was controlled to 10.5 to obtain slurry A. Adding Mn3O4Mixing with hydrochloric acid and water to obtain MnO with a concentration of 87.5g2Controlling the pH value of a/L manganese chloride solution to be 6, then adding urea into the solution, wherein the molar concentration ratio of the urea to manganese ions is 3, and stirring for 40 minutes at room temperature to obtain a solution B. Adding the solution B and 145.6gBN (solid content is 80 weight percent) into the slurry A, aging for 24h under stirring at 60 ℃, cooling the system to room temperature, washing with deionized water until the washed water is neutral, filtering, and mixing the obtained aged solid precipitate with the aged solid precipitate (dry basis): h2O is 1: 4 is mixed with water and beaten according to the weight ratio of P2O5: dry basis of high specific heat capacity material is 0.05: 1, reacting at 50 deg.C for 2 hr, and drying at 120 deg.C for 12 hr to obtain matrix materialAnd (3) driving the body, then roasting for 4 hours at 650 ℃, and cooling to room temperature along with the furnace to obtain the 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.
AM-5 elemental analytical chemical composition in weight percent 15.6% MnO2、59.4％Al2O3、19.5％BN、5.5％P2O5(ii) a Specific heat capacity of 1.45J/(g.K), specific surface area of 380m2G, pore volume 1.12cm3G, average pore diameter 11.8 nm.
Example 6
Example 6 is used to illustrate the preparation process of the mesoporous matrix material with high specific heat capacity provided by the present invention.
The matrix material AM-6 was prepared according to the method of example 5, except that the formulation, preparation parameters, elemental composition, specific surface area, pore volume and average pore diameter were as listed in table 1. CO in alkali solution3-The concentration is 0.15mol/L and OH-The concentration was 0.25 mol/L.
The XRD patterns of AM-2 to AM-6 are shown in FIG. 1.
Comparative example 1
Deionized water is used for respectively preparing 350gAl2O3Al (NO)/L3)3Solution and concentration of 145gMnO2And mixing the manganese nitrate solution/L uniformly to obtain a solution A. And preparing an ammonium bicarbonate solution, controlling the pH to be 10.0, and marking as a solution B. 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. After mixing, aging at 180 ℃ for 20h, when the temperature of the system is reduced to room temperature, washing the system to be neutral by deionized water to obtain an aged solid precipitate, and then, mixing the aged solid precipitate (dry basis): h2O is 1: 3, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: the resulting matrix material was 0.01: 1, adding phosphoric acid, stirring for 2 hours at 50 ℃, drying for 12 hours at 120 ℃ to obtain a manganese-aluminum matrix precursor, roasting for 4 hours at 1000 ℃, and cooling to room temperature along with a furnace to obtain a matrix material, wherein the matrix material is marked as DB-1.
The DB-1 has the characteristics of figure 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 characteristic peaks is 1: 1.5; the elemental analytical chemical composition of DB-1 was 30.2 wt.% MnO268.9% by weight of Al2O3、0.9％P2O5(ii) a Specific heat capacity of 0.58J/(g.K), specific surface area of 284m2G, pore volume 0.41cm3G, average pore diameter 5.8 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. Adding the solution B and 95.4g of boron nitride (with the solid content of 80 weight percent) into the slurry A, aging at 80 ℃ for 24h, respectively washing with deionized water to be neutral after the system temperature is reduced to room temperature to obtain an aged solid precipitate, and then adding the aged solid precipitate (dry basis): h2O is 1: 4, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: the resulting matrix material was 0.03 dry basis: 1, adding phosphoric acid, stirring for 2 hours at 50 ℃, drying for 12 hours at 120 ℃ to obtain a manganese-aluminum matrix precursor, then roasting for 6 hours at 900 ℃, and cooling to room temperature along with the furnace to obtain a matrix material, which is recorded as DB-2.
The elemental analytical chemical composition of DB-2 was 33.3 wt.% MnO254.7% by weight of Al2O39.1% by weight of BN and 2.9% by weight of P2O5(ii) a Specific heat capacity of 0.89J/(g.K), specific surface area of 249m2G, pore volume 0.35cm3G, average pore diameter 5.6 nm.
Example 7
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)2O316.5 wt.% Na2O1.4% by weight, produced by Changling catalyst works) in a weight ratio of 2:8Mixing the components in proportion, recording samples as C-1 to C-6, dipping 4000ppm of polluted iron, 2000ppm of nickel and 2000ppm of vanadium by a Mitchell method, uniformly grinding, tabletting, screening into particles of 20-40 meshes, aging for 12 hours under the conditions of 780 ℃ and 100% steam, and evaluating the cracking performance on a heavy oil micro-reaction device. And (3) carrying out three reaction-regeneration cycles on each sample, namely, carrying out the reaction and then regeneration on the raw oil under the condition that the same catalyst is not discharged, and taking the reaction result of the last time as the cracking performance evaluation result of the catalyst. The evaluation conditions of the heavy oil micro-reaction are as follows: the catalyst-oil ratio is 1.56, the sample loading is 2g, the reaction temperature is 500 ℃, the reaction time is 70s, 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 materials obtained in comparative examples 1 and 2 were mixed with REY molecular sieves (RE)2O3 16.5％，Na2O1.4% by weight, produced by chang catalyst factory) were mixed at a weight ratio of 2:8, samples were designated as C-DB-1 and C-DB-2, 4000ppm contaminated iron, 2000ppm nickel and 2000ppm vanadium were dipped by Mitchell method, ground uniformly, tabletted and sieved into 20-40 mesh particles, aged at 780 ℃ under 100% steam for 12 hours, and cracking performance was evaluated on a heavy oil microreaction device in the same manner as in example 7. The evaluation results are shown in Table 3.
TABLE 1
In I1/I2 in Table 1, I1 is the intensity of the peak at an angle of 18. + -. 0.5 ℃ in terms of 2. theta. in the XRD spectrum, I2 is the intensity of the peak at an angle of 37. + -. 0.5 ℃ in terms of 2. theta.
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
4240
4220
4210
4230
4285
4245
4220
4250
Ni/ppm
2020
2005
2019
1990
2022
2007
2014
2050
V/ppm
2015
2025
2022
2018
2013
2017
2009
2030
Material balance/m%
Dry gas
2.75
2.81
2.63
2.63
2.66
2.59
3.21
3.04
Liquefied gas
15.23
15.39
15.36
15.17
15.44
15.48
13.94
14.38
C5+ gasoline
41.77
42.65
43.11
42.21
42.73
43.55
38.93
40.57
Diesel oil
16.86
16.57
16.71
17.03
16.63
16.69
16.93
16.37
Heavy oil
10.18
9.41
9.03
9.85
9.5
8.57
12.36
12.13
Coke
13.21
13.17
13.16
13.11
13.04
13.12
14.63
13.51
Total of
100
100
100
100
100
100
100
100
Conversion/mass%
72.96
74.02
74.26
73.12
73.87
74.74
70.71
71.5
Total liquid/mass%
73.86
74.61
75.18
74.41
74.8
75.72
69.8
71.32
Coke selectivity
0.1811
0.1779
0.1772
0.1793
0.1765
0.1755
0.2069
0.1890
Selectivity of dry gas
0.0377
0.0380
0.0354
0.0360
0.0360
0.0347
0.0454
0.0425
In the invention, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield,
total liquid yield (also called total liquid product yield) is gasoline yield, diesel oil yield and liquefied gas yield,
coke selectivity is the coke yield/conversion, dry gas selectivity is the dry gas yield/conversion.
As can be seen from the heavy oil evaluation results in table 3, the catalyst shows more excellent heavy oil cracking performance, higher cracking activity, significantly reduced heavy oil yield, significantly increased gasoline yield, and significantly increased total liquid yield while maintaining good coke selectivity for the sample containing the high specific heat capacity matrix material provided by the present invention.