TW202211984A - Catalytic cracking catalyst, preparation method therefor, and application thereof - Google Patents

Abstract

A catalytic cracking catalyst, a preparation method therefor, and an application thereof. The catalytic cracking catalyst includes a cracking active component, a high specific heat capacity matrix material, clay, and a binder. The high specific heat capacity matrix material includes at least 5% by weight of manganese oxide, and the specific heat capacity thereof is 1.3-2.0 J/(g.K). The preparation method for the catalytic cracking catalyst comprises: mixing and pulping the cracking active component, the high specific heat capacity matrix material and/or a precursor thereof, the clay, and the binder, and then performing spray drying, roasting, washing, filtering, and drying. The catalytic cracking catalyst has good resistance to metal pollution and good heavy oil conversion ability, is applicable to heavy oil catalytic cracking, and improves light oil yield.

Description

A kind of catalytic cracking catalyst and its preparation method and use

The present invention relates to a catalytic cracking catalyst and its preparation method and application.

With the increasing shortage of petroleum resources and the rising price of crude oil, major refineries reduce costs by deeply processing heavy oil and using inferior oil to maximize benefits. At present, catalytic cracking is an important means of heavy oil processing.

However, the content of heavy metals (such as vanadium and nickel) in inferior crude oil is generally high. Especially in recent years, the phenomenon of metal poisoning of catalytic cracking catalysts has become more and more common due to the heaviness and deterioration of crude oil and the processing of opportunistic crude oil. Numerous research results show that metals such as iron and nickel are difficult to migrate once deposited on the surface, and will interact with elements such as silicon, aluminum, vanadium, and sodium to form a low-melting eutectic, sintering the surface of the catalyst, and then forming a layer on the surface. -3 μm thick dense layer, which blocks the channels for reactants to enter the catalyst and product diffusion, and deteriorate the product distribution. Severe metal contamination can lead to poor catalyst fluidization performance, reduced accessibility of active centers, poor catalyst selectivity, and increased dry gas and coke yields. Some units even face the risk of shutdown.

In order to reduce the impact of metals in the oil on catalytic cracking, metal trapping components are added in the prior art to eliminate or weaken its impact. However, since most of the metal trapping components also affect the activity of the catalyst, Therefore, most of them are introduced into the catalyst system in the form of a separate auxiliary agent. When directly introduced into the catalyst, it may cause some adverse effects on the performance of the catalyst, and the addition is strictly limited.

CN101939095A discloses a molecular sieve catalyst and a preparation method thereof for preparing light olefins by catalytic cracking of naphtha in a harsh environment of high temperature and high humidity. Specifically, the catalyst is prepared by spray-drying and sintering a mixed slurry in which 0.01-5.0 wt % MnO ₂ and 1-15 wt % P ₂ are combined O is _{simultaneously} embedded in a catalyst composed of zeolite, clay, and inorganic composites. According to this invention, the method of simultaneously intercalating manganese and phosphate into zeolite and inorganic composites can be used to improve the thermal stability of the obtained spherical catalyst, and to improve hydrocarbons (eg naphtha) by protecting the acidic sites of the zeolite Olefin yield after cracking. In order to synthesize the desired catalyst, the important steps are the mixing ratio and mixing order of Mn, P, zeolite and inorganic complex. Mixing manganese and phosphorus in the catalyst slurry in a dissolved form has very limited improvement effect on the catalyst, which is mainly used for naphtha conversion, and does not involve how to improve its heavy oil conversion performance.

The technical problem to be solved by the present invention is to provide a new catalytic cracking catalyst with better heavy oil conversion ability and metal pollution resistance ability. Another technical problem to be solved by the present invention is to provide the preparation method of the catalytic cracking catalyst and the application of the catalytic cracking catalyst in the catalytic cracking of heavy oil.

The present invention provides a catalytic cracking catalyst, wherein the catalytic cracking catalyst contains a cracking active component, a high specific heat capacity matrix material, clay and a binder; the high specific heat capacity matrix material contains at least 5% by weight of manganese oxide based on MnO ₂ , The specific heat capacity of the high specific heat capacity matrix material at a temperature of 1000K is 1.3-2.0 J/(g·K), and the cracking active component includes Y-type molecular sieve.

Preferably, the high specific heat capacity matrix material contains 5-95 wt % alumina based on Al ₂ O ₃ , 5-95 wt % manganese oxide based on MnO ₂ and 0-40 wt % boron compound based on dry basis.

Preferably, in the high specific heat capacity matrix material, the boron compound is boron nitride and/or boron oxide.

Preferably, the specific surface area of the high specific heat capacity matrix material is 150-500 m ² ·g ^-1 .

Preferably, the pore volume of the high specific heat capacity matrix material is 0.3-1.5 cm ³ ·g ^-1 .

Preferably, the average pore diameter of the high specific heat capacity matrix material is 3-20 nm.

Preferably, in the XRD pattern of the high specific heat capacity matrix material, the intensity ratio of peaks at 2θ angles of 18±0.5° and 2θ angles of 37±0.5° is 1:(3-10).

The high specific heat capacity matrix material can be prepared according to a preparation method comprising the following steps:

(1) mixing aluminum source and alkali to form a gel to obtain aluminum-containing colloid, and the pH value of the obtained aluminum-containing colloid is 7-11;

(2) make the manganese salt solution of pH value 3-7 mix with urea, obtain manganese source solution;

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

(4) Washing and/or drying and/or roasting.

In the preparation step (1) of the high specific heat capacity matrix material, the mixing of the aluminum source and the alkali to form a gel includes: mixing the aluminum source solution and the alkali solution, the forming temperature is from room temperature to 85°C, and the pH value is 7-11 colloid.

The alumina concentration in the aluminum source solution is 150-350 g Al ₂ O ₃ /L, and the alkali concentration in the alkali solution is 0.1-1 mol/L. Described aluminium source is selected from one or more in aluminium nitrate, aluminium sulfate, aluminium phosphate and aluminium chloride etc.; Described alkali is (can be) water-soluble carbonate, (can be) water-soluble bicarbonate One or more of salts, ()water soluble hydroxides.

The alkali solution is selected from an alkaline aqueous solution containing one or more of CO ₃ ^2- , HCO ₃ ^- or OH ^- , and the concentration of CO ₃ ^2- in the alkali solution is 0-0.6 mol/L, OH The concentration of ^- is 0-0.5 mol/L, and the concentration of HCO ₃ ^- is 0-1 mol/L, provided that the sum of the concentration of CO ₃ ^2- , OH ^- and HCO ₃ ^- is not zero. Herein, the concentration of CO ₃ ^2- , the concentration of ^OH- , ^and the concentration of HCO _3- are obtained by dividing the molar amount (mol) of anionic groups in the base used to form the alkaline aqueous solution by the alkaline aqueous solution obtained by the volume (L).

In the described high specific heat capacity matrix material preparation step (2), the molar ratio of urea and manganese ions is 1-5, such as 2-4, and the concentration of manganese salt in the manganese salt solution can be 50-500g in terms of _MnO ·L ^-1 .

Preferably, in step (2), urea is added to the manganese salt solution, and then stirred at room temperature for 30-60 minutes to obtain a manganese source solution.

The boron compound is, for example, boron nitride and/or boron oxide and/or boron oxide precursors. Wherein, the boron nitride can be one or more of hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride and wurtzite boron nitride; the boron oxide precursor can be ammonium borate, boric acid One or more of ammonium hydrogen or boric acid.

In step (3), the process of aging is also included after mixing the aluminum-containing colloid and the manganese source solution, and the aging temperature is from room temperature to 120 ° C, and the aging time is 4-72 hours. Stand for aging; preferably, the aging is performed under stirring, the aging temperature is 60-100° C., and the aging time is 12-36 hours.

In one embodiment, the roasting temperature in step (4) is 500°C-900°C, and the roasting time is 4-8 hours.

The present invention also provides a method for preparing the catalytic cracking catalyst, which comprises mixing and beating the cracking active component, a matrix material with high specific heat capacity and/or its precursor, clay and a binder, spray drying, washing, filtering and drying . The precursor of the high specific heat capacity matrix material refers to the high specific heat capacity matrix material obtained without calcination in step (4); thus in the present invention, "high specific heat capacity matrix material" may refer to the calcination in step (4) and the The general term for the obtained high specific heat capacity matrix material and the high specific heat capacity matrix material obtained without the calcination in step (4), or only refers to the high specific heat capacity matrix material obtained through the calcination in step (4).

The invention also provides the application of the catalytic cracking catalyst in the catalytic cracking of heavy oil.

The catalytic cracking catalyst provided by the invention can improve the specific heat capacity of the catalytic cracking catalyst by using a specific high specific heat capacity material in combination with a cracking active component, clay and a binder, which is beneficial to the atomization and cracking of heavy oil macromolecules in the reactor. The catalyst provided by the invention has better wear resistance performance. The catalytic cracking catalyst provided by the invention is used for the catalytic cracking of heavy oil, has higher conversion rate of heavy oil, higher yield of light oil, and higher yield of liquid. The catalyst provided by the invention has the ability to resist pollution of various metals, and can have higher total liquid yield, higher light oil yield and higher gasoline yield under the condition of iron, vanadium and nickel pollution. .

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

In the present invention, the high specific heat capacity matrix material refers to a material whose specific heat capacity at 1000K is not less than 1.3 J/(g·K).

In the present invention, when it comes to the content of the components of the catalyst, the sum of the content of the components of the catalyst is 100% by weight; when it is related to the content of the components of the high specific heat capacity matrix material, The sum of the content is 100% by weight; when referring to the anhydrous chemical expression of the high specific heat capacity matrix material, the coefficients of each component in the anhydrous chemical expression are based on weight, and the sum of the coefficients of each component is 100.

The catalytic cracking catalyst provided by the present invention, wherein, based on the total weight of the catalytic cracking catalyst, on a dry basis, the catalytic cracking catalyst contains 1-60 wt % of cracking active components, 1-50 wt % of High specific heat capacity matrix material, 1-70 wt % clay and 1-70 wt % binder; the high specific heat capacity matrix material contains at least 5 wt % manganese oxide, and when the temperature is 1000K, the high specific heat capacity matrix material has a The specific heat capacity is 1.3-2.0 J/(g·K).

The dry basis refers to the solid product after the substance is calcined at 800°C for 1 hour.

The room temperature in the present invention is 15-40°C, for example, 15°C.

According to the catalytic cracking catalyst provided by the present invention, preferably, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 10-50% by weight of cracking active components on a dry basis, 5% by weight on a dry basis - 40% by weight of high specific heat capacity matrix material, 10-60% by weight of clay on a dry basis and 10-60% by weight of binder on a dry basis. Controlling the content of the above components within the preferred range can make the obtained catalytic cracking catalyst have better physicochemical properties and reaction performance.

According to the catalytic cracking catalyst provided by the present invention, when the catalyst exists in the form of particles (one particle or discrete particle), the cracking active components and the high specific heat capacity matrix material are in the same particle, that is, in the same catalytic cracking catalyst The granules contain the pyrolysis active component, high specific heat capacity matrix material, clay and binder.

According to the first embodiment of the catalytic cracking catalyst provided by the present invention, the high specific heat capacity matrix material does not contain boron compounds. Based on the weight of the high specific heat capacity matrix material, the high specific heat capacity matrix material contains 5-95 wt % alumina calculated as Al ₂ O ₃ and 5-95 wt % manganese _oxide calculated as MnO , such as the The high specific heat capacity matrix material is mainly composed of 15-70% by weight or 20-65% by weight or 30-61% by weight of manganese oxide and 30-85% by weight or 35-80% by weight or 39-70% by weight of alumina . The specific surface area of the high specific heat capacity matrix material can be 180-300 m ² ·g ^-1 , such as 200-250 m ² ·g ^-1 or 220-245 m ² ·g ^-1 ; the pores of the high specific heat capacity matrix material The volume is 0.35-0.75, such as 0.4-0.65 cm ³ ·g ^-1 ; the average pore diameter of the high specific heat capacity matrix material is 5-13 nm, such as 6-11 nm.

According to the catalytic cracking catalyst provided by the present invention, the high specific heat capacity matrix material may or may not contain boron compounds. Preferably, the high specific heat capacity matrix material provided by the present invention (referred to as the matrix material) contains a boron compound, which can have better anti-metal pollution performance than the high specific heat capacity matrix material without boron compound.

According to the catalytic cracking catalyst provided by the present invention, in the second embodiment, in the high specific heat capacity matrix material, the boron compound is boron nitride, and its specific heat capacity is 1.3-2.0 J/(g·K), such as 1.35-1.95 J/(g·K) or 1.51-1.95 J/(g·K). The anhydrous chemical expression of the high specific heat capacity matrix material in terms of weight ratio can be expressed as (5-94.5)Al ₂ O ₃ ·(5-94.5)MnO ₂ ·(0.5-40)BN, for example, it can be (20-80 )Al ₂ O ₃ ·(15-75)MnO ₂ ·(5-30)BN. Preferably, based on the weight of the high specific heat capacity matrix material, the high specific heat capacity matrix material contains 5-94.5 wt % alumina, 5-94.5 wt % manganese oxide calculated as MnO ₂ and 5-94.5 wt % based on the dry basis More than 0 and not more than 40% by weight such as 0.5-35% by weight of boron nitride; more preferably, the high specific heat capacity matrix material contains 15-80% by weight of alumina, 15-70% by weight of manganese oxide and 5- 30 wt% boron nitride; more preferably, the high specific heat capacity matrix material contains 19-74 wt% alumina, 14-66 wt% manganese oxide and 8-26 wt% boron nitride. The high specific heat capacity matrix material contains boron nitride, which can improve the wear resistance of the catalyst.

In the second embodiment of the catalytic cracking catalyst of the present invention, the specific surface area of the high specific heat capacity matrix material is 150-350 m ² ·g ^-1 , for example, 180-300 m ² ·g ^-1 or 200-250 m ² ·g ^-1 or 220-245 m ² ·g ^-1 , the high specific heat capacity matrix material has a pore volume of 0.35-0.75 such as 0.4-0.65 cm ³ ·g ^-1 or 0.45-0.75 or 0.5-0.7 cm ³ ·g ^-1 , the average pore diameter of the high specific heat capacity host material is 3-20 nm, such as 4-18 nm or 5-15 nm or 6-13 nm or 6-8.5 nm, preferably 5-13 nm or 6-11 nm.

The second embodiment of the catalytic cracking catalyst of the present invention, a preparation method of the matrix material, comprises the following steps:

(1) Mix the aluminum source solution and the alkaline solution to form a gel at room temperature to 85°C, and control the pH value of the gel formed by the gel to be 7-11;

(2) Configure a manganese salt solution with a pH value of 3-7, mix the manganese salt solution with urea, and stir; the molar ratio of urea and manganese ions is 1-5, and the temperature at which the manganese salt solution and urea are mixed has no special requirements. It can be carried out at room temperature, and the stirring time is for example 30-60 minutes;

(3) mixing the product obtained in step (1), the product obtained in step (2), and boron nitride, and aging at room temperature to 120° C. for 4-72 hours; and optionally,

(4) Washing the product obtained in step (3) with water, preferably, the washing makes the washed washing solution neutral (neutrality refers to a pH value of 6.5-7.5), for example, with deionized water until after washing The deionized water is neutralized, dried, and calcined to obtain a matrix material with high specific heat capacity.

In the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the alkaline solution in step (1) is wide. The alkaline solution is an alkaline aqueous solution containing at least one of CO ₃ ^2- , HCO ₃ ^2- and ^OH- , more preferably, the alkaline aqueous solution includes ammonium bicarbonate, ammonium carbonate, sodium hydroxide, hydroxide An aqueous solution of one or more of potassium, or a mixed solution of one or more of ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. In one embodiment, in the alkaline solution, the concentration of CO ₃ ^2- is 0-0.6 mol/L, such as 0.3-0.5 mol/L; the concentration of ^OH- is 0-0.5 mol/L, such as 0.2 -0.35 mol/L, the concentration of HCO ₃ ^2- is 0-1.0 mol/L, for example, 0.4-1.0 mol/L. The pH value of step (1) gel formation is preferably 8-11, such as 8.5-11 or 9-10. When selecting ammonia water, it is assumed that the ammonia water is completely ionized, and the required addition amount of ammonia water is calculated according to the calculated hydroxide radicals.

In the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the types of the aluminum sources is wide, and the water-soluble aluminum sources that can dissolve in water can be used for In the present invention, for example, the aluminum source may be selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

In the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, in step (2), a manganese salt solution with a specific pH value is mixed with urea to form a mixture, and the manganese salt solution is mixed with urea to form a mixture. The pH value is 3-7, preferably 5-7. The optional range of the conditions for mixing urea and manganese salt solution is wider, for the present invention, in one embodiment, the method for mixing described in step (2) comprises: adding urea to the manganese salt solution, stirring at room temperature for 40- For 60 minutes, the molar ratio of urea and manganese ions is preferably between 2-4. In step (2), the manganese salt solution can be selected from an aqueous solution of a water-soluble manganese salt, and/or a salt solution formed by contacting a water-soluble manganese salt, manganese oxide, and/or manganese hydroxide with an acid. The types of the manganese salts can be selected in a wide range, and all water-soluble manganese salts that can dissolve in water can be used in the present invention, such as one or more of manganese nitrate, manganese sulfate or manganese chloride. Manganese salt solutions can also be prepared by contacting manganese oxides and/or manganese hydroxides and/or water-soluble manganese salts, such as manganese monoxide, manganese tetroxide, manganese One or more of manganese oxide, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.

In the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the product obtained in the step (1) in the step (3) is calculated as Al ₂ O ₃ , and the step (2) The obtained product is calculated as MnO ₂ and the ratio of boron nitride by weight on a dry basis is (5-95) Al ₂ O ₃ : (5-95) MnO ₂ : (0.5-40) BN, for example, (20-80 ) Al ₂ O ₃ : (15-75) MnO ₂ : (5-30) BN. Preferably, the amount of the product obtained in step (1), the product obtained in step (2) and the boron nitride in step (3) is such that the prepared matrix material contains 5-94.5% by weight, such as 15-80% by weight or 19-74 wt % or 20-80 wt % or 19-60 wt % alumina, 5-94.5 wt % as MnO ₂ for example 15-75 wt % or 10-70 wt % or 14-66 wt % or 19 - 66% by weight of manganese oxide and, on a dry basis, more than 0 and not more than 40% by weight, eg, 0.5-35% by weight or 5-30% by weight or 8-26% by weight of boron nitride.

In the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the aging conditions in step (3) is wide (for example, the aging temperature is room temperature). Warm to 120 ° C, aging time is 4-72 hours), preferably, the aging conditions described in step (3) include: aging temperature is 60-100 ° C, aging time 12-36 hours, aging under stirring change. There is no special requirement for the stirring method, for example, the stirring speed can be 50-300 rpm.

According to the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the boron nitride can be selected from hexagonal boron nitride (h-BN), cubic boron nitride (c -BN), one or more of rhombohedral boron nitride (r-BN) and wurtzite boron nitride (w-BN).

According to the second embodiment of the catalytic cracking catalyst of the present invention, in the preparation method of the high specific heat capacity matrix material, the optional ranges of the drying conditions and calcination conditions in step (4) are wide. The drying and roasting methods can be carried out with reference to the prior art, and the present invention has no special requirements for this. For example, the drying conditions in step (4) include: drying at 100-150°C for 6-24 hours; the roasting conditions in step (4) include: roasting at 550-800°C, such as 550-750°C for 4- 8 hours.

In the third embodiment of the catalytic cracking catalyst provided by the present invention, in the high specific heat capacity matrix material, the boron compound is boron oxide, and its specific heat capacity is 1.3-2.0 J/(g·K), for example, 1.35-1.95 J /(g·K) or 1.51-1.95 J/(g·K), the composition formula of the anhydrous compound of the high specific heat capacity mesoporous matrix material provided by the present invention is (5-94.5) Al ₂ O ₃ in terms of the weight ratio of oxides · (5-94.5) MnO ₂ · (0.5-10) B ₂ O ₃ , for example (20-80) Al ₂ O ₃ · (15-75) MnO ₂ · (0.5-10) B ₂ O ₃ or (20-80)Al ₂ O ₃ ·(15-75)MnO ₂ ·(1-8)B ₂ O ₃ . Preferably, based on the weight of the high specific heat capacity matrix material, the high specific heat capacity matrix material contains 5-94.5 wt % alumina, 5-94.5 wt % manganese oxide calculated as MnO ₂ and B ₂ 0.5-10 wt% boron oxide based on _O3 ; more preferably, the high specific heat capacity matrix material contains 15-80 wt% alumina, 15-80 wt% manganese _oxide based on _MnO2 and B2O ₃ based on 0.8-8% by weight of boron oxide or the high specific heat capacity matrix material containing 20-62% by weight of aluminum oxide, 34-72% by weight of manganese oxide based on MnO ₂ and 2-8 based on B ₂ O ₃ wt % boron oxide. Preferably, the high specific heat capacity matrix material has a specific surface area of 300-500 m ² /g such as 310-370 m ² /g or 330-370 m ² /g, and a pore volume of 0.5-1.5 cm ³ /g such as 0.7-1.4 cm ³ /g or 0.6-1.3 cm ³ /g or 0.7-1.2 cm ³ /g. Preferably, the matrix material is a mesoporous matrix material with an average pore size of 3-20 nm, such as 5-18 nm or 8-18 nm or 7-15 nm or 8-14 nm or 10-15 nm or 10-13 nm nm.

In the third embodiment of the catalytic cracking catalyst provided by the present invention, in the high specific heat capacity matrix material, the boron compound is boron oxide, which can have higher pore volume and specific surface area, and the introduction of boron oxide modulates the matrix Acidity, improve the pre-cracking ability of the matrix, as the matrix material of catalytic cracking catalyst or auxiliary agent, used in the catalytic cracking of heavy oil, can reduce the particle temperature during the regeneration of catalytic cracking catalyst, slow down the collapse of molecular sieve, improve the activity of the catalyst and the ability to resist metal pollution And heavy oil conversion ability, reduce the coke selectivity of the catalyst, so that the catalyst fluidization performance is good.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, a preparation method of the high specific heat capacity matrix material comprises the following steps:

(1) Mix the aluminum source solution and the alkali solution at room temperature to 85°C to form a gel, and control the pH value of the gel obtained by forming the gel to be 7-11;

(2) configure the manganese salt solution with pH value of 3-7, mix the manganese salt solution with urea, and stir for example at room temperature for 30-60 minutes; wherein urea and manganese ion molar ratio are 1-5;

(3) Mix the product obtained in step (1) and the product obtained in step (2), and age; for example, age at room temperature to 120° C. for 4-72 hours; mix the ageing solid product with oxidized Mixing the boron source or mixing the aged solid product with the boron oxide source after washing, optionally also reacting; wherein the boron oxide source charging amount in terms of B ₂ O ₃ and the weight ratio of the high specific heat capacity matrix material in terms of dry basis is (0.005-0.1): 1;

(4) the solid precipitate obtained in step (3) (or called solid product) is directly dried, calcined or dried and calcined after the solid precipitate of step (3) is washed; described washing, can be used for step (3) The solid product is washed, for example, it can be washed with water to make the washed water neutral.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the method for preparing the high specific heat capacity matrix material, the prepared matrix material not only has a higher specific heat capacity than other methods to obtain the high specific heat capacity matrix material within the scope of the present invention It can also have a higher average pore size, a higher specific surface area, and a higher pore volume. It can be used for catalytic cracking of heavy oil with high metal content, especially high iron content, with higher liquid product yield and lower dryness. Gas and coke yields. Compared with the catalyst using the high specific heat capacity matrix material without boron oxide, it can have higher heavy oil conversion activity and can have higher gasoline yield.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the alkaline solution in step (1) is wide, preferably, in step (1) The alkaline solution is an alkaline aqueous solution containing at least one of HCO ₃ ^2- , CO ₃ ^2- and ^OH- , and the alkaline aqueous solution preferably includes ammonium bicarbonate, ammonium carbonate, sodium hydroxide, and potassium hydroxide. One or more aqueous solutions, or a mixed solution comprising one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. Preferably, in the alkaline solution, the concentration of CO ₃ ^2- is 0-0.6 mol/L, such as 0.3-0.5 mol/L; the concentration of ^OH- is preferably 0-0.5 mol/L, such as 0.2-0.35 mol /L, the concentration of HCO ₃ ^2- is 0-1.0 mol/L, for example, 0.4-1.0 mol/L. When selecting ammonia water, it is assumed that the ammonia water is completely ionized, and the required addition amount of ammonia water can be calculated according to the calculated hydroxide radicals. The pH value of the gel obtained by gel formation is preferably 9-11 or 10-11.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the types of the aluminum sources is wide, and the water-soluble aluminum sources that can be dissolved in water can be used for In the present invention, for example, the soluble aluminum salt can be selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, and aluminum chloride, etc., preferably one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the manganese salt solution in step (2) can be selected from an aqueous solution of a water-soluble manganese salt, and/or a water-soluble manganese salt, manganese oxide, and/or manganese hydroxide in contact with acid; the pH value of the manganese salt solution is 3-7, preferably 5-7. Preferably, in step (2), after the manganese salt solution is mixed with urea, the mixture is stirred at room temperature for 40-60 minutes, and the molar ratio of urea and manganese ions is between 2-4. The manganese salt solution in step (2) can be selected from the aqueous solution of water-soluble manganese salt and/or the salt solution formed by manganese oxide, manganese hydroxide and/or water-soluble manganese salt in contact with acid. The optional range of the type of the manganese salt is wide, and all water-soluble manganese salts that can be dissolved in water can be used in the present invention, such as manganese nitrate, manganese sulfate, manganese phosphate or manganese chloride. one or more. The manganese salt solution can also be prepared by contacting water-soluble manganese salts, manganese oxides and/or manganese hydroxides, such as manganese monoxide, manganese tetraoxide, manganese One or more of manganese oxide, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the optional range of the aging conditions in step (3) is wide (for example, the aging temperature is room temperature) Warm to 120 ° C, the aging time is 4-72 hours), preferably, the aging conditions described in step (3) include: the aging temperature is 60-100 ° C, stirring and aging, and the aging time is 12-36 Hour. The stirring method is the existing method, for example, the stirring speed is 50-300 rev/min. The aged product is filtered or washed after filtration to obtain aged solid product. In one embodiment, in the washing, the aged solid product (also called precipitate) obtained by aging is mixed with water at room temperature according to the weight ratio of aged solid product (dry basis):H ₂ O=1:(5-30). Contact 1-3 times, each contact for 0.5-1 hour, until the washing solution after washing is neutral, usually pH is 6.5-7.5.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the aged solid product is contacted with a boron source, and the contact treatment method can be various. The ageing product can be filtered to obtain a filter cake, that is, the ageing solid product is directly mixed with the boron source or the ageing solid product obtained after washing the filter cake obtained by filtration is mixed with the boron source; preferably, the formed mixture is also carried out for a period of time. For example, stirring or standing for 0.2-5 hours at room temperature to 90 °C. One embodiment, mixing and beating the aged solid product with water, wherein the weight ratio of the aged solid product (on a dry basis):H ₂ O is 1:(5-20), and then adding the boron source to the above-mentioned slurry , stand or stir at room temperature to 90° C. for 0.2-5 hours, preferably 0.5-3 hours, and filter to obtain a solid precipitate. It is also possible to mix the aged solid product or the washed aged solid product with the boron source in proportion, and grind uniformly to obtain a solid precipitate.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the boron oxide source is preferably a material that can obtain boron oxide after calcination, such as ammonium borate, ammonium hydrogen borate or one or more of boric acid.

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, the product obtained in the step (1) in the step (3) is calculated as Al ₂ O ₃ , and the step (2) The weight and dosage ratio of the obtained product in terms of MnO ₂ and the boron source in terms of B ₂ O ₃ is (5-94.5) Al ₂ O ₃ : (5-94.5) MnO ₂ : (0.5-10) B ₂ O ₃ , for example, (20-80) Al ₂ O ₃ : (15-75) MnO ₂ : (1-8) B ₂ O ₃ . Preferably, in the obtained high specific heat capacity matrix material, the high specific heat capacity matrix material contains 5-94.5 wt % such as 15-80 wt % or 20-75 wt % or 20-62 wt % of alumina, 5-94.5 wt % such as 15- 80 wt % or 22-72 wt % or 30-72 wt % manganese oxide as MnO ₂ and 0.5-10 wt % or 0.8-8 wt % or 2-8 wt % boron oxide as B ₂ O ₃ .

According to the third embodiment of the catalytic cracking catalyst provided by the present invention, in the preparation method of the high specific heat capacity matrix material, in step (4), the solid precipitate obtained in step (3) is directly dried and roasted, or dried after washing. and roasting. The washing can be washed with water, for example, it can be mixed with water and washed with water, or washed with water. Usually, the solid precipitate after washing is neutral, that is, the pH value of the water after contacting with water is 6.5-7.5. The drying and roasting methods can be carried out with reference to the prior art, and the optional range is wide, and the present invention has no special requirements for this. For example, the drying can be carried out at 100-150°C for 12-24 hours; and the calcination can be carried out at 550-800°C, such as 550-750°C, for 4-8 hours.

According to the catalytic cracking catalyst provided by the present invention, the cracking active component contains Y-type molecular sieve. Wherein, the types of the Y-type molecular sieves may include various types of Y-type molecular sieves in which NaY is ion-modified or ultra-stable, and the ion-modification includes rare earth ions, alkaline earth metal ions, transition metal ions, phosphorus modification, etc., Ultra-stable modification includes hydrothermal ultra-stable, gas-phase ultra-stable, chemical ultra-stable, etc. For example, it can be Y-type molecular sieves containing rare earths such as REHY molecular sieves, Y-type molecular sieves containing phosphorus and rare earths such as DOSY molecular sieves, ultrastable Y-type molecular sieves Molecular sieves such as one or more of DASY molecular sieves, ultrastable Y molecular sieves containing phosphorus and/or rare earth, and the like. In addition, in addition to Y-type molecular sieve, optionally, the cracking active component also contains a second molecular sieve, such as other faujasite zeolite, Beta zeolite, MFI molecular sieve (such as ZRP-1 molecular sieve) and one or more of mordenite. Wherein, based on the total weight of the cracking active components, the content of the Y-type molecular sieve may be more than 75% by weight, preferably more than 90% by weight, more preferably more than 95% by weight; the content of the second molecular sieve The content (total content of other faujasite, Beta zeolite, MFI structured molecular sieve and mordenite) may be 25 wt % or less, preferably 10 wt % or less, more preferably 5 wt % or less.

According to the catalytic cracking catalyst provided by the present invention, the clay can be various existing clays that can be used in catalytic cracking catalysts, for example, can be selected from kaolin, halloysite, montmorillonite, diatomite, halloysite, One or more of soapstone, rectorite, sepiolite, ertypoite, hydrotalcite and bentonite.

According to the catalytic cracking catalyst provided by the present invention, the binder can be various existing binders that can be used in the catalytic cracking catalyst, for example, can be selected from one or more of silica sol, alumina sol and pseudo-boehmite kind.

In addition, the catalytic cracking catalyst may also contain additional rare earths. The additional rare earth may be formed by additionally adding rare earth chloride during the preparation of the catalytic cracking catalyst. In the catalytic cracking catalyst, the additional rare earth is usually present in the form of rare earth oxide (RE ₂ O ₃ ). Based on the dry weight of the catalytic cracking catalyst, the content of the additional rare earth in terms of rare earth oxide may be 0-3 wt %, preferably 0.5-2 wt %. Wherein, the rare earth elements in the added rare earths refer to various traditional rare earth elements involved in the field of catalytic cracking catalysts, such as lanthanum, cerium, strontium, neodymium, strontium, samarium, europium, and the like.

The preparation method of the catalytic cracking catalyst provided by the present invention includes mixing and beating cracking active components, high specific heat capacity matrix material, clay and binder, and then performing spray drying, washing, filtration and drying in sequence. In addition, when the catalytic cracking catalyst further contains additional rare earths, the preparation method of the catalytic cracking catalyst provided by the present invention further comprises combining the rare earth chloride with the cracking active component, a high specific heat capacity matrix material, clay and a binder Mix and beat, then spray dry, wash, filter and dry in sequence.

According to the preparation method of the catalytic cracking catalyst provided by the present invention, the cracking active component, the high specific heat capacity matrix material, the clay and the binder and the rare earth chloride optionally contained are mixed and pulped, and the subsequent spray drying, washing, filtration and Drying, the implementation methods of these operations can be implemented by traditional methods, and their specific implementation methods are described in detail in CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, which are incorporated into the present invention for reference. . In addition, generally, after the spray-drying and before the washing, the preparation method of the catalytic cracking catalyst usually further includes the step of calcining the spray-dried product. The calcination conditions generally include that the calcination temperature can be 500-700° C., and the calcination time can be 1-4 hours.

In addition, the present invention also provides the application of the above catalytic cracking catalyst in the catalytic cracking of heavy oil.

The application method of the catalytic cracking catalyst in the catalytic cracking of heavy oil provided by the present invention includes the step of contacting and reacting the catalytic cracking catalyst with heavy oil, such as vacuum residue, vacuum gas oil, and atmospheric residue. One or more of oil, atmospheric gas oil, and deasphalted oil. The reaction conditions of the contact reaction include: the reaction temperature is 480-530° C., the ratio of agent to oil (weight ratio) is 3-10, and the reaction time is 0.1-5 seconds.

In one embodiment of the present invention, the heavy oil satisfies one or more or all of the following conditions: (a) specific gravity (20°C) 0.82-0.95, preferably greater than 0.91 and not greater than 0.95; (b) carbon content 85wt%- 89wt%; (c) hydrogen content of 10wt%-13wt%; (d) sulfur content of 0.1%-4wt%; (e) solidification temperature of -10 to 40°C.

Specifically, the present invention provides the following technical solutions:

1. A high specific heat capacity host material comprising at least 5% by weight of manganese oxide, the high specific heat capacity host material having a specific heat capacity of 1.3-2.0 J/(g·K) at a temperature of 1000K.

2. According to the high specific heat capacity matrix material according to any one of the foregoing technical solutions, wherein, the high specific heat capacity matrix material contains Al ₂ O ₃ 5-95% by weight, such as 19.6-74.8% by weight of alumina, with 5-95% by weight, such as 15.3-71.8% by weight of manganese oxide based on _MnO , and 0-40% by weight, 0-25.2% by weight of a boron compound on a dry basis; for example, the high specific heat capacity matrix material contains _Al2 19.6-74.8 wt % alumina based on O ₃ , 15.3-71.8 wt % manganese oxide based on MnO ₂ , and 0-25.2 wt % boron compound on a dry basis.

3. The high specific heat capacity host material according to any one of the foregoing technical solutions, wherein, in the high specific heat capacity host material, the boron compound is boron nitride and/or boron oxide.

4. According to the high specific heat capacity matrix material described in any one of the foregoing technical solutions, wherein, the specific surface area of the high specific heat capacity matrix material is 150-500 m ² ·g ^-1 , such as 200-400 m ² ·g ^-1 , such as 221-365 m ² ·g ^-1 .

5. The high specific heat capacity matrix material according to any one of the foregoing technical solutions, wherein the pore volume of the high specific heat capacity matrix material is 0.3-1.5 cm ³ ·g ^-1 , such as 0.35-1.2 cm ³ ·g ^-1 , for example, 0.38-1.17 cm ³ ·g ^-1 .

6. The high specific heat capacity matrix material according to any one of the foregoing technical solutions, wherein the average pore diameter of the high specific heat capacity matrix material is 3-20 nm, such as 5-15 nm, such as 6.4-13.6 nm.

7. According to the high specific heat capacity host material described in any one of the foregoing technical solutions, wherein, the XRD pattern of the high specific heat capacity host material, at 2θ angle is 18 ± 0.5° and 2θ angle is the intensity of the peak at 37 ± 0.5° The ratio is 1:(3-10).

8. According to the preparation method of the high specific heat capacity matrix material described in any one of aforementioned technical solutions 1-7, comprise the following steps:

(1) mixing aluminum source and alkali to form a gel to obtain aluminum-containing colloid, and the pH value of the obtained aluminum-containing colloid is 7-11;

(2) make the manganese salt solution of pH value 3-7 mix with urea, obtain manganese source solution;

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

(4) Washing and/or drying and/or roasting.

9. According to the preparation method described in the technical scheme 8, wherein, the mixing of the aluminum source and the alkali into a gel comprises: mixing the aluminum source solution and the solution of the alkali, and the forming temperature is from room temperature to 85 ° C and the pH value is 7. -11 colloid.

10. According to the preparation method described in any one of technical solutions 8 to the previous technical solution, wherein, the concentration of alumina in the aluminum source solution is 150-350gAl ₂ O ₃ /L, and the concentration of the alkali in the alkali solution is 150-350gAl 2 O 3 /L. The concentration is 0.1-1 mol/L.

11. according to the preparation method described in any one of technical scheme 8 to the previous technical scheme, wherein, described aluminium source is selected from aluminium nitrate, aluminium sulfate, aluminium phosphate, aluminium chloride and its mixture; The base is selected from the group consisting of water-soluble carbonates, water-soluble bicarbonates, water-soluble hydroxides, and mixtures thereof.

12. according to the preparation method described in any one of technical scheme 8 to previous technical scheme, wherein, the solution of described alkali is selected from the alkali containing one or more in CO ₃ ^2- , HCO ₃ ^- and OH ^- In the alkaline solution, the concentration of CO ₃ ^2- is 0-0.6 mol/L, the concentration of ^OH- is 0-0.5 mol/L, ^and the concentration of HCO _3- is 0-1 mol/L, provided that The ^sum of the concentration of CO ₃ ^2- , the concentration of ^OH- , and the concentration of HCO _3- is not zero, where the concentration of CO ₃ ^2- , the concentration of ^OH- , ^and the concentration of HCO _3- are obtained by applying the concentration of It is obtained by dividing the molar amount (mol) of anionic groups in the base of the alkaline aqueous solution by the volume (L) of the alkaline aqueous solution.

13. According to the preparation method described in any one of technical scheme 8 to previous technical scheme, wherein, in step (2), urea and manganese ion molar ratio are 1-5, such as 2-4, the The concentration of the manganese salt in the manganese salt solution can be 50-500 g·L ^-1 in terms of MnO ₂ .

14. According to the preparation method described in any one of technical scheme 8 to the previous technical scheme, wherein, in step (2), in the manganese salt solution, add urea, then stir at room temperature for 30-60 minutes, A manganese source solution is obtained.

15. The preparation method according to any one of technical solutions 8 to the previous technical solution, wherein the boron compound is boron nitride and/or boron oxide and/or boron oxide precursor.

16. The catalytic cracking catalyst according to technical scheme 16, wherein the boron nitride is one or more of hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride and wurtzite boron nitride; The boron oxide precursor is one or more of ammonium borate, ammonium hydrogen borate and boric acid.

17. According to the preparation method described in any one of technical solutions 8 to the previous technical solution, wherein, in step (3), the process of ageing is also included after mixing the aluminum-containing colloid and the manganese source solution, and the The aging temperature is from room temperature to 120 ° C, the aging time is 4-72 hours, and the aging is performed under stirring or standing for aging; preferably, the aging is performed under stirring, and the aging temperature is 60-100 ° C. , the aging time is 12-36 hours.

18. The preparation method according to any one of technical solutions 8 to the previous technical solution, wherein the boron compound is boron nitride; step (3) makes the aluminum-containing colloid, the manganese source solution, and the boron compound to form The method of the mixture is as follows: the aluminum-containing colloid, the manganese source solution and the boron compound are mixed and aged.

19. According to the preparation method described in any one of technical solutions 8 to the previous technical solution, wherein, the boron compound is a precursor of boron oxide and/or boron oxide, and the step (3) is made to contain aluminum. The colloid, the manganese source solution, and the boron compound form the mixture as follows: the aluminum-containing colloid, the manganese source solution are mixed, aged, optionally washed, and then mixed with the boron compound.

20. The preparation method according to any one of technical solutions 8 to the previous technical solution, wherein the roasting temperature in step (4) is 500°C-900°C, and the roasting time is 4-8 hours.

21. A catalytic cracking catalyst, wherein the catalytic cracking catalyst contains the cracking active component comprising Y-type molecular sieve, the high specific heat capacity host material described in any one of the foregoing technical solutions 1-7 or by the foregoing technical solutions 8-20. The high specific heat capacity matrix material, clay and binder obtained by any one of the preparation methods.

22. The catalytic cracking catalyst according to the aforementioned technical solution 21, wherein, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60% by weight of cracking active components, 1-50% by weight. high specific heat capacity matrix material, 1-70 wt % clay and 1-70 wt % binder, or, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 10-50 wt % cracking Active component, 5-40% by weight of high specific heat capacity matrix material, 10-60% by weight of clay and 10-60% by weight of binder, wherein the mass of the catalytic cracking catalyst is 100% by weight.

23. The catalytic cracking catalyst according to any one of technical solutions 21 to the previous technical solution, wherein the cracking active component contains Y-type molecular sieve.

24. The catalytic cracking catalyst according to any one of technical solutions 21 to the previous technical solution, wherein the cracking active component also contains a second molecular sieve, and the second molecular sieve is faujasite, Beta zeolite, One or more of MFI structured molecular sieves and mordenite.

25. According to the catalytic cracking catalyst described in any one of technical solutions 21 to the previous technical solution, wherein, based on the total weight of the cracking active component, the content of the Y-type molecular sieve is more than 75% by weight. , the content of the second molecular sieve is less than 25% by weight.

26. According to the preparation method of the catalytic cracking catalyst described in any one of technical schemes 21-25, the method comprises mixing and beating the pyrolysis active component, high specific heat capacity matrix material, clay and binder, and then spraying successively. Dry, roast, wash, filter and dry.

27. According to the application of the catalytic cracking catalyst described in any one of technical solutions 21-25 in the catalytic cracking of heavy oil.

The present invention will be described in detail below by means of examples.

The raw materials used in the following preparation examples, comparative preparation examples, examples and comparative examples are as follows:

Hydrochloric acid is produced by Beijing Chemical Plant, chemically pure, and the concentration is 36% by weight;

Soda water glass is commercially available, the _SiO2 concentration is 26.0% by weight, and the modulus is 3.2;

Kaolin is the product of Suzhou Kaolin Company, and the solid content is 74.0% by weight;

The pseudo-boehmite is an industrial product of Shandong Aluminum Factory, and the solid content is 62.0% by weight;

The aluminum sol is a product of Sinopec Catalyst Qilu Branch, and the Al ₂ O ₃ content is 21.5% by weight;

DASY molecular sieve (solid content 92.0 wt%, RE ₂ O ₃ 1.8 wt %, Na ₂ O 1.0 wt %, crystallinity 60%), ZRP-1 molecular sieve (solid content 97.8 wt %, Na ₂ O 1.1 Weight %, crystallinity 70%), REHY molecular sieve (solid content is 88.0 weight %, RE ₂ O ₃ is 5.0 weight %, Na ₂ O is 0.9 weight %, crystallinity 65%), Beta molecular sieve (solid content is 95.2 weight %) %, Na ₂ O 1.2 wt %, crystallinity 60%), DOSY molecular sieve (solid content 93.5 wt %, RE ₂ O 8.0 wt _{%, Na 2 O} 0.8 wt %, crystallinity 80%), HSY Molecular sieves (solid content 91.5% by weight, RE ₂ O 10.5% by weight, Na ₂ O 0.9 _% by weight, crystallinity 85%) were all produced by Sinopec Catalyst Qilu Branch;

Rare earth chloride was purchased from Baotou Steel Rare Earth High-Tech Co., Ltd., and the rare earth elements were La and Ce.

The present invention will be further illustrated by the following examples, but the present invention is not limited thereby.

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

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

The BN used is hexagonal boron nitride.

In each example and control example, the contents of Al ₂ O ₃ , MnO ₂ , B, N, and Fe in the samples were determined by X-ray fluorescence method (see "Analysis Method of Petrochemical Industry (RIPP Experimental Method)", edited by Yang Cuiding et al. , Science Press, 1990). The phase of the sample was determined by X-ray diffraction. The specific surface area, pore volume, and average pore diameter of the samples were measured by the low-temperature nitrogen adsorption-desorption method, and the pore size distribution was calculated by the BJH method.

Preparation Example 1

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

The Al ₂ (SO ₄ ) ₃ solution with a concentration of 300 gAl ₂ O ₃ /L and the ammonium carbonate solution with a CO ₃ ^2- concentration of 0.10 mol/L were mixed at 20 ° C to form a gel, the pH value of the obtained colloid=7.5, and slurry A was obtained . Add hydrochloric acid to the MnCl ₂ solution of concentration 450gMnO ₂ /L, control pH=3.5, then add urea to the solution, the molar ratio of urea and manganese ions is 2, and stir at room temperature for 30 minutes to obtain solution B. Add solution B to slurry A, stir and age at 80°C for 4 hours, wait for the system temperature to drop to room temperature, rinse with deionized water until the washed water is neutral, and dry at 120°C for 12 hours to obtain the precursor of the matrix material and then calcined at 550° C. for 6 hours, and cooled to room temperature with the furnace to obtain the matrix material with high specific heat capacity provided by the present invention, which is denoted as AM-1. The ratio of AM-1, preparation condition parameters, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in Table 1.

The X-ray diffraction pattern of AM-1 is shown in Figure 1, in which there are characteristic peaks at 2θ angles of 18±0.5° and 2θ angles of 37±0.5°, and the intensity ratio (I ₁ /I ₂ ) of the two is 1 : 5.2; its elemental analytical chemical composition formula (by weight) is 60.5 mnO ₂ ·39.5Al ₂ O ₃ ; its specific heat capacity is 1.36 J/(g·K), its specific surface area is 238 m ² /g, and its pore volume is 0.38 cm ³ /g , with an average pore size of 6.4 nm.

Preparation Example 2-4

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

The high specific heat capacity matrix materials AM-2 to AM-4 were prepared according to the method of Preparation Example 1, except that the ratio of raw materials, preparation condition parameters, elemental composition of products, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in Table 1 , wherein solution B is added to slurry A, and then boron nitride is added, followed by said aging.

Preparation Example 5

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

Al(NO ₃ ) ₃ solution with a concentration of 350gAl ₂ O ₃ /L and a solution with a CO ₃ ^2- concentration of 0.1 mol/L (ammonium carbonate) and an OH ^- concentration of 0.1 mol/L (ammonia) at a temperature of 25 ℃ The mixture was mixed to form a gel, and the pH value was controlled to be 10.5 to obtain slurry A. Mn ₃ O ₄ is mixed with hydrochloric acid and water to obtain a manganese chloride solution with a concentration of 116.5gMnO ₂ /L, and the pH value is controlled to be 6. Then, urea is added to the solution, and the molar ratio of urea and manganese ions is 3. At room temperature, Stirred for 40 minutes, solution B was obtained. Add solution B and 145.6g BN (solid content 80% by weight) to slurry A, stir and age at 60°C for 24 hours, wait until the temperature of the system drops to room temperature, rinse with deionized water until the washed water is neutral, then The matrix material precursor is obtained by drying at 120° C. for 12 hours, then calcined at 650° C. for 4 hours, and cooled to room temperature with the furnace to obtain the high specific heat capacity matrix material provided by the present invention, which is designated 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.

The X-ray diffraction pattern of AM-5 is the same as Figure 1, in which there are characteristic peaks at 2θ angles of 18±0.5° and 2θ angles of 37±0.5°, and the intensity ratio of the two is 1:6.6; the chemical composition calculation of AM-5 The formula is 20.6MnO ₂ ·59.4Al ₂ O ₃ ·19.4BN by weight; the specific heat capacity is 1.48 J/(g·K), the specific surface area is 243 m ² /g, the pore volume is 0.46 cm ³ /g, and the average pore diameter is 7.6 nm.

Preparation Example 6

Preparation Example 6 is used to illustrate the preparation process 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 Preparation Example 5. The composition, specific heat capacity, specific surface area, pore volume and average pore diameter of different raw material ratios and preparation condition parameters are listed in Table 1. The CO ₃ ^2- concentration was 0.2 mol/L, and the ^OH- concentration was 0.15 mol/L.

The X-ray diffraction patterns of AM-2 to AM-6 are shown in Fig. 1, with peaks at 2θ angles of 18±0.5° and 2θ angles of 37±0.5°.

Comparative Preparation Example 1

Al(NO ₃ ) ₃ solution with a concentration of 350gAl ₂ O ₃ /L and a manganese nitrate solution with a concentration of 525gMnO ₂ /L were prepared with deionized water, and mixed uniformly to obtain solution A. Prepare ammonium bicarbonate solution, control PH=10.0, record as solution B. Under continuous stirring, the solution A and the solution B are mixed to obtain the mother liquor C, and the pH of the mother liquor C is controlled to be 8-9 by controlling the addition of the solution B during the mixing process. After mixing, aged at 180°C for 20 hours, after the system temperature dropped to room temperature, rinsed with deionized water until neutral, dried at 120°C for 12 hours to obtain a manganese-aluminum matrix precursor, and then calcined at 1000°C for 4 hours , and cooled to room temperature with the furnace to obtain the control matrix material, denoted as DAM-1.

X-ray diffraction pattern of DAM-1, with characteristic peaks at 2θ angle of 18±0.5° and 2θ angle of 37±0.5°, and the intensity ratio of the two is 1:1.9; elemental analysis chemical composition calculation of DAM-1 The formula is 60.6MnO ₂ ·39.4Al ₂ O ₃ ; the specific heat capacity is 0.62 J/(g·K), the specific surface area is 224 m ² /g, the pore volume is 0.31 cm ³ /g, and the average pore diameter is 5.5 nm.

Comparative Preparation Example 2

A solution of Al ₂ (SO ₄ ) ₃ with a concentration of 350 g Al ₂ O ₃ /L was mixed with ammonium carbonate to form a gel, and the pH was controlled to be 10.0 to obtain slurry A. A MnSO ₄ solution with a concentration of 209.7 g MnO ₂ /L was added to the slurry A, and stirred at room temperature for 30 minutes to obtain a slurry B. 95.4g of boron nitride (solid content of 80% by weight) was added to slurry B, aged at 80°C for 24 hours, after the system temperature dropped to room temperature, rinsed with deionized water until neutral, and dried at 120°C for 12 hours The manganese-aluminum matrix precursor was obtained, which was then calcined at 900° C. for 6 hours, and cooled to room temperature with the furnace to obtain a sample of the control matrix material, which was denoted as DAM-2.

The chemical composition formula of elemental analysis of DAM-2 is 33.3MnO ₂ ·54.7Al ₂ O ₃ ·11.7BN by weight; specific heat capacity is 0.85 J/(g·K), specific surface area is 219 m ² /g, and pore volume is 0.25 cm ³ /g, the average pore size is 4.6 nm.

Table 1 Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Serum A Aluminum source type Aluminum sulfate Aluminum sulfate Aluminum nitrate Aluminum nitrate Aluminum nitrate Aluminum sulfate Concentration of aluminum source solution (calculated as Al ₂ O ₃ )/g·L ^-1 300 350 350 150 350 350 Base type Ammonium carbonate Ammonium carbonate Ammonium bicarbonate Ammonium bicarbonate Ammonium carbonate + ammonia water Ammonium carbonate + ammonia water Alkali solution concentration (calculated as anion)/mol·L ^-1 0.10 0.50 0.40 0.95 0.20 0.35 gelling pH 7.5 11 8.5 10.5 10.5 11 Glue temperature/℃ 20 25 65 40 75 30 Solution B Manganese source type Manganese chloride Manganese sulfate Manganese nitrate Manganese chloride Mn ₃ O ₄ MnO ₂ Concentration of manganese salt solution (calculated as MnO ₂ )/g·L ^-1 450 400 455 487.5 116.5 70 Acid type hydrochloric acid hydrochloric acid sulfuric acid Manganese salt solution pH 3.5 7 7 7 6 5 Urea: Mn (mol ratio) 2 3 2.5 4 3 3.5 BN(dry basis)/g 0 250 70 112.5 116.5 46.7 aging conditions 80℃/4 hours 80℃/24 hours 60℃/30 hours 60℃/60 hours 60℃/24 hours 80℃/24 hours Roasting conditions 550℃/6 hours 600℃/6 hours 750℃/4 hours 700℃/4 hours 650℃/4 hours 600℃/6 hours High specific heat capacity matrix material MnO ₂ /wt% 60.5 39.5 52.9 65.4 20.6 15.3 Al ₂ O ₃ /wt% 39.5 35.3 39.1 19.6 59.4 73.9 BN/wt% 0 25.2 8.0 14.6 19.4 10.8 I ₁ /I ₂ 1:5.2 1:10 1:8.5 1:3.5 1:6.6 1:7.2 Specific heat capacity/J·g ^-1 ·K ^-1 1.36 1.95 1.62 1.39 1.48 1.44 Specific surface/m ² ·g ^-1 238 250 235 221 243 239 Pore volume/cm ³ ·g ^-1 0.38 0.42 0.63 0.54 0.46 0.52 Average pore diameter/nm 6.4 6.7 10.7 9.8 7.6 8.7

Note: In Tables 1 and 4, I ₁ /I ₂ is the ratio of the peak intensity at the 2θ angle of 18±0.5° to the peak intensity at the 2θ angle of 37±0.5° in the XRD pattern

Example 1

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

20 parts by weight of pseudo-boehmite on a dry basis and deionized water are mixed and beaten (the solid content of the slurry is 15% by weight), and hydrochloric acid is added to the obtained slurry for peptization, and the ratio of aluminum acid (36% by weight hydrochloric acid) The weight ratio of boehmite to alumina was 0.20:1, then the temperature was raised to 65°C for acidification for 1 hour, and then 28 parts by weight of kaolin slurry (solid content of 25% by weight) on a dry basis were added respectively. , the aluminum sol of 13 parts by weight on a dry basis and the slurry (solid content of 18% by weight) of the high specific heat capacity matrix material AM-1 prepared by Preparation Example 1 of 10 parts by weight on a dry basis, stirred for 20 minutes, Then, 29 parts by weight of the DASY molecular sieve slurry (solid content of 35% by weight) on a dry basis was added to it, and the catalyst was spray-dried to prepare a microsphere catalyst after continuous stirring. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25 wt %, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C1, wherein the total amount of the catalytic cracking catalyst C1 is used. Based on weight, the catalytic cracking catalyst C1 contains 10% by weight of high specific heat capacity matrix material, 29% by weight of DASY molecular sieve, 28% by weight of kaolin, and 33% by weight of Al ₂ O ₃ binder.

Comparative Example 1

This comparative example is used to illustrate the comparative catalytic cracking catalyst and its preparation method.

The catalytic cracking catalyst was prepared according to the method of Example 1, except that the high specific heat capacity matrix material AM-1 prepared in Preparation Example 1 was replaced with the matrix material DAM-1 prepared in Comparative Preparation Example 1 in the same weight portion to obtain a control catalyst. Cracking catalyst CB1, wherein, based on the total weight of the contrast catalytic cracking catalyst CB1, the contrast catalytic cracking catalyst CB1 contains 10% by weight of the contrast host material, 29% by weight of DASY molecular sieves, 28% by weight of kaolin, 33 wt% Al ₂ O ₃ binder.

Comparative Example 2

This comparative example is used to illustrate the comparative catalytic cracking catalyst and its preparation method.

The catalytic cracking catalyst was prepared according to the method of Example 1, except that the high specific heat capacity matrix material AM-1 prepared in Preparation Example 1 was replaced with the same weight portion of matrix material DAM-2 prepared in Comparative Preparation Example 1 to obtain a control catalyst Cracking catalyst CB2, wherein, based on the total weight of the contrast catalytic cracking catalyst CB2, the contrast catalytic cracking catalyst CB2 contains 10% by weight of the contrast host material, 29% by weight of DASY molecular sieves, 28% by weight of kaolin, 33 wt% Al ₂ O ₃ binder.

Comparative Example 3

This comparative example is used to illustrate the comparative catalytic cracking catalyst and its preparation method.

The catalytic cracking catalyst was prepared according to the method of Example 1. The difference was that the high specific heat capacity matrix material AM-1 was not added, and the high specific heat capacity matrix material AM-1 was replaced with kaolin of the same dry basis weight to obtain a control catalytic cracking catalyst CB3, Wherein, based on the total weight of the control catalytic cracking catalyst CB3, the control catalytic cracking catalyst CB3 contains 29% by weight of DASY molecular sieves, 38% by weight of kaolin, and 33% by weight of Al ₂ O ₃ binder.

Example 2

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

20 parts by weight of kaolin on a dry basis is mixed with deionized water to make a slurry (solid content of the slurry is 40% by weight), then 20 parts by weight of pseudo-boehmite on a dry basis is added, and the resulting slurry is added The hydrochloric acid was peptized, the acid-aluminum ratio (weight) was 0.20:1, then the temperature was raised to 65°C for acidification for 1 hour, and then 5 parts by weight of aluminum sol on a dry basis, 30 parts by weight on a dry basis of aluminum sol were added respectively. The slurry of the high specific heat capacity matrix material AM-2 (solid content of 20% by weight) prepared in Preparation Example 2 was stirred for 20 minutes, and then 20 parts by weight of DASY molecular sieves based on dry basis, DASY molecular sieves based on dry basis were added to it for 20 minutes. The mixed slurry of 5 parts by weight of ZRP-1 molecular sieve (solid content is 35% by weight) is continuously stirred and spray-dried to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110° C. to obtain a catalytic cracking catalyst C2, wherein the total amount of the catalytic cracking catalyst C2 Based on weight, the catalytic cracking catalyst C2 contains 30% by weight of high specific heat capacity matrix material, 20% by weight of DASY molecular sieve, 5% by weight of ZRP-1 molecular sieve, 20% by weight of kaolin, 25% by weight of Al ₂ O ₃ binders.

Example 3

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

Mix 28 parts by weight of kaolin on a dry basis with deionized water to make a slurry (solid content of the slurry is 40% by weight), then add 25 parts by weight of pseudoboehmite on a dry basis, and add hydrochloric acid to the resulting slurry Peptizing was carried out, the acid-aluminum ratio (weight ratio) was 0.20:1, then the temperature was raised to 65 ° C for acidification for 1 hour, and then 20 parts by weight of the high specific heat capacity matrix material AM prepared in Preparation Example 3 on a dry basis were added respectively. -3 slurry (solid content of 25% by weight) and 5 parts by weight of aluminum sol on a dry basis, stirred for 20 minutes, and then 15 parts by weight of the REHY molecular sieve on a dry basis and 15 parts by weight of the REHY molecular sieve on a dry basis were added thereto. 5 parts by weight of the mixed slurry of the Beta molecular sieve (solid content of 35% by weight) and 2 parts by weight of rare earth chloride solution calculated as rare earth oxides, continue stirring and spray drying to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C3, wherein the total amount of the catalytic cracking catalyst C3 Based on weight, the catalytic cracking catalyst C3 contains 20% by weight of high specific heat capacity matrix material, 15% by weight of REHY molecular sieve, 5% by weight of Beta molecular sieve, 28% by weight of kaolin, 30% by weight of Al ₂ O ₃ binding agent, 2% by weight of rare earth oxide.

Example 4

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

40 parts by weight of kaolin on a dry basis, 15 parts by weight of aluminum sol on a dry basis and 15 parts by weight on a dry basis of the high specific heat capacity matrix material AM-4 prepared in Preparation Example 4 The slurry (solid The content is 20% by weight) mixing and beating, stirring for 120 minutes, then adding the DOSY molecular sieve slurry (solid content of 35% by weight) of 30 parts by weight on a dry basis to it, continuing to stir and then spray drying to make microspheres catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110° C. to obtain a catalytic cracking catalyst C4, wherein the total amount of the catalytic cracking catalyst C4 Based on weight, the catalytic cracking catalyst C4 contains 15% by weight of high specific heat capacity matrix material, 30% by weight of DOSY molecular sieve, 40% by weight of kaolin, and 15% by weight of Al ₂ O ₃ binder.

Example 5

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

(1) Preparation of silica sol:

1.7 L of hydrochloric acid was diluted with 8.0 kg of decationized water, 7.7 kg of sodium water glass was diluted with 8.0 kg of decationized water, and the diluted sodium water glass was slowly added to the above dilute hydrochloric _acid solution under stirring to obtain a SiO concentration of 7.8 wt% silica sol, pH 2.8.

(2) prepare catalytic cracking catalyst:

10 parts by weight of kaolin on a dry basis was added to 20 parts by weight of the above silica sol on a dry basis, and 40 parts by weight of the high specific heat capacity matrix material prepared in Preparation Example 5 was added after stirring for 1 hour. The slurry of AM-5 (solid content of 18 wt %) was mixed and beaten, and then 30 parts by weight of the DASY molecular sieve slurry (solid content of 30 wt %) on a dry basis was added to it, and the mixture was spray-dried after continuous stirring. microsphere catalyst. The microsphere catalyst was then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05:1:10) to Na ₂ O content less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain catalytic cracking catalyst C5, wherein, based on the total weight of the catalytic cracking catalyst C5, the catalytic cracking catalyst C5 C5 contains 40% by weight of high specific heat capacity matrix material, 30% by weight of DASY molecular sieve, 10% by weight of kaolin, and 20% by weight of SiO ₂ binder.

Example 6

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

40 parts by weight of kaolin on a dry basis, 15 parts by weight of aluminum sol on a dry basis and 15 parts by weight on a dry basis of the high specific heat capacity matrix material AM-6 prepared by Preparation Example 6 The slurry (solid The content is 20% by weight) mixing and beating, stirring for 120 minutes, then adding 30 parts by weight of the HSY molecular sieve slurry (solid content is 35% by weight) on a dry basis to it, continuing to stir and then spray drying to make microspheres catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C6, wherein the total amount of the catalytic cracking catalyst C6 is used. Based on weight, the catalytic cracking catalyst C6 contains 15% by weight of high specific heat capacity matrix material, 30% by weight of HSY molecular sieve, 40% by weight of kaolin, and 15% by weight of Al ₂ O ₃ binder.

Examples 7-12

Examples 7-12 are used to illustrate the performance test of the catalytic cracking catalyst provided by the present invention.

The catalytic cracking catalysts C1-C6 prepared above are respectively used to impregnate pollution iron 5000 ppm, nickel 5000 ppm, vanadium 5000 ppm by Mitchell method, namely take vanadium naphthenate as vanadium source, nickel naphthenate as nickel source, iron naphthenate As an iron source, toluene is used as a solvent to prepare a metal-containing solution, the catalyst is immersed in the metal-containing solution, then dried, and then calcined at about 600° C. to remove organic matter. After aging treatment at 780 °C and 100% water vapor for 6 hours, the cracking performance was evaluated on a small fixed fluidized bed. The evaluation process of each sample was carried out five times of reaction-regeneration cycles, that is, the same catalyst was not discharged. In this case, the feedstock oil reaction and regeneration process were carried out continuously for five times, and the result of the last reaction was taken as the evaluation result of the catalyst cracking performance. The evaluation conditions of heavy oil micro-reaction are: agent-oil ratio 5 (weight ratio), sample loading 9g, reaction temperature 520 ℃, WHSV 8 hours ^-1 , oil feeding time 70 seconds, regeneration temperature 720 ℃, raw material oil is decompressed gas oil. The properties of the feedstock oil are shown in Table 2. The evaluation results are listed in Table 3.

Comparative Example 4-6

The catalytic cracking control agents CB1-CB3 prepared above were tested for performance according to the same method as in Examples 7-12, and the evaluation results are listed in Table 3.

Table 2 Raw oil properties Density (20℃), g/cm ³ 0.9154 Refraction (70℃) 1.4717 Freezing point, °C 37 Carbon residue, m% 4.3 Four-component composition, m% Saturated hydrocarbons 63.1 Aromatic hydrocarbons 21.2 colloid 14.9 Asphaltene 0.8 Elemental composition, m% C 85.95 H 12.78 S 0.62 N 0.65 Metal elements, (ppm) Ca 21.4 Fe 30.6 Mg 0.6 Na 1.5 Ni 7.4 V 11.8 Pb 2.1

table 3 Example number 7 Comparative Example 4 Comparative Example 5 Comparative Example 6 8 9 10 11 12 catalyst C1 CB1 CB2 CB3 C2 C3 C4 C5 C6 Conversion rate/w% 65.19 61.87 62.03 62.47 65.83 64.71 66.78 66.23 64.66 Product yield Dry gas/w% 1.29 2.28 1.71 1.48 1.31 1.22 1.43 1.30 1.20 LPG/w% 12.12 9.86 10.03 10.23 12.55 12.45 12.61 12.58 12.17 Gasoline/w% 46.52 44.35 44.86 45.21 46.79 46.03 47.28 46.94 46.24 Diesel/w% 19.49 20.16 19.92 19.73 18.64 19.71 18.99 19.07 19.85 Oil slurry/w% 15.32 17.97 18.05 17.80 15.53 15.58 14.23 14.70 15.49 Coke/w% 5.26 5.38 5.43 5.55 5.18 5.01 5.46 5.41 5.05 Total liquid yield/w% 78.13 74.37 74.81 75.17 77.98 78.19 78.88 78.59 78.26 Dry gas selectivity 1.98 3.69 2.76 2.36 1.99 1.89 2.14 1.96 1.86 Coke selectivity 8.07 8.70 8.75 8.88 7.87 7.74 8.18 8.17 7.81 H ₂ /CH ₄ 0.11 0.2 0.17 0.16 0.13 0.11 0.14 0.12 0.1

In Table 3 and Table 5, w% is weight %, and H ₂ /CH ₄ is weight ratio.

In the present invention, conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield, total liquid yield (also known as total liquid product yield) = gasoline yield + diesel yield + liquefied gas yield rate, coke selectivity = coke yield/conversion, dry gas selectivity = dry gas yield/conversion.

Preparation Example B1

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

The Al ₂ (SO ₄ ) ₃ solution with a concentration of 350g Al ₂ O ₃ /L and the ammonium carbonate solution with a CO ₃ ^2- concentration of 0.10 mol/L were mixed to form a gel at 30°C, and the pH value was controlled to be 7.5 to obtain a slurry BA . Urea was added to the MnCl ₂ solution with a concentration of 145 g MnO ₂ /L, the molar ratio of urea and manganese ions was 2, and the mixture was stirred at room temperature for 30 minutes to obtain solution BB. Add solution BB to slurry BA, age at 80°C under stirring for 24 hours, wait until the temperature of the system drops to room temperature, and then filter the obtained solid precipitate according to the ratio of solid precipitate (dry basis): H ₂ O=1:10 The weight ratio is mixed with water to make a slurry, and ammonium borate is added according to the weight ratio of B ₂ O ₃ : dry basis of high specific heat capacity base material=0.01:1, and then stirred at 50 ° C for 2 hours, filtered, and the solid precipitate was pressed according to the precipitate ( Dry basis): H ₂ O=1:8 weight ratio, exchanged 3 times at room temperature for 0.5 hours each time, the obtained solid precipitate after washing was neutral, and then dried at 120 ° C for 12 hours to obtain the matrix material The precursor is then calcined at 550° C. for 6 hours, and cooled to room temperature with the furnace to obtain the matrix material with high specific heat capacity provided by the present invention, which is denoted as BAM-1. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore size of BAM-1 are listed in Table 4.

The elemental analysis chemical composition formula of BAM-1 is 29.7MnO ₂ ·69.2Al ₂ O ₃ ·1.1B ₂ O ₃ by weight; specific heat capacity 1.3 J/(g·K), specific surface area 310 m ² /g, pore volume 0.65 cm ³ /g, the average pore size is 8.4 nm.

Preparation Examples B2-B4

Preparation examples B2-B4 are used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.

The high specific heat capacity mesoporous matrix materials BAM-2 to BAM-4 were prepared according to the method of Preparation Example B1. The difference was the formulation and preparation parameters. The elemental composition, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in Table 4.

Preparation Example B5

Preparation Example B5 is used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.

The Al(NO ₃ ) ₃ solution with a concentration of 350g Al ₂ O ₃ /L, the ammonium carbonate with a CO ₃ ^2- concentration of 0.30 mol/L, and the ammonia solution with an ^OH- concentration of 0.1 mol/L were mixed to form a gel, and the pH was controlled = 10.5, obtain slurry BA. Mn ₃ O ₄ is mixed with hydrochloric acid and water to obtain the manganese chloride solution of concentration 201.7g MnO ₂ /L, control pH value=6, then add urea to the solution, the molar ratio of urea and manganese ion is 3, room temperature Under stirring for 40 minutes, solution BB was obtained. Add solution BB to slurry BA, stir and age at 60°C for 24 hours, wait for the temperature of the system to drop to room temperature, then filter the obtained solid precipitate according to the weight ratio of precipitate (dry basis):H ₂ O=1:10 Mixing with water and beating, and adding ammonium borate according to the weight ratio of B ₂ O ₃ : the obtained high specific heat capacity base material dry basis=0.01:1, stirring at 50 ° C for 2 hours, filtering, washing (that is, washing with water), Then, it is dried at 120° C. for 12 hours to obtain the matrix material precursor, then calcined at 650° C. for 4 hours, and cooled to room temperature with the furnace to obtain the matrix material provided by the present invention, which is designated 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.

The elemental analysis chemical composition formula of BAM-5 is 34.8MnO ₂ ·60.4Al ₂ O ₃ ·4.8B ₂ O ₃ by weight; specific heat capacity 1.43 J/(g·K), specific surface area 338 m ² /g, pore volume 0.94 cm ³ /g, the average pore size is 11.1 nm.

Preparation Example B6

Preparation Example B6 is used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.

The matrix material BAM-6 was prepared according to the method of Preparation Example B5, except that the formula and preparation parameters were different, and its elemental composition, specific surface area, pore volume and average pore diameter are listed in Table 4.

Table 4 Preparation example B1 B2 B3 B4 B5 B6 Serum BA Aluminum source type Aluminum sulfate Aluminum sulfate Aluminum nitrate Aluminum nitrate Aluminum nitrate Aluminum sulfate Concentration of aluminum source solution (calculated as Al ₂ O ₃ )/g·L ^-1 350 350 350 150 350 350 Base type Ammonium carbonate Ammonium carbonate Ammonium bicarbonate Ammonium bicarbonate Ammonium carbonate + ammonia water Ammonium carbonate + ammonia water Alkali solution concentration (calculated as anion)/mol·L ^-1 0.10 0.50 0.40 0.95 0.30 0.35 (CO ₃ ^2- concentration 0.2, OH ^- concentration 0.15) gelling pH 7.5 11 10 10.5 10.5 11 Solution BB Manganese source type Manganese chloride Manganese sulfate Manganese nitrate Manganese chloride Mn ₃ O ₄ MnO ₂ Concentration of manganese salt solution (calculated as MnO ₂ )/g·L ^-1 145 267.3 481.25 540 201.7 104.3 Acid type hydrochloric acid sulfuric acid Manganese salt solution pH 7 7 7 7 6 5 Urea: Mn (mol ratio) 2 3 2.5 4 3 3.5 Boron source type Ammonium borate Boric acid Ammonium hydrogen borate Boric acid Ammonium borate Boric acid Boron source solution concentration (calculated as B ₂ O ₃ )/g·L ^-1 5 19 43.75 60 27.8 13.6 aging conditions 80℃/24 hours 80℃/24 hours 60℃/30 hours 60℃/24 hours 60℃/24 hours 80℃/24 hours Roasting conditions 550℃/6 hours 600℃/6 hours 750℃/4 hours 700℃/4 hours 650℃/4 hours 600℃/6 hours High specific heat capacity matrix material MnO ₂ /wt% 29.7 42.1 54.6 71.8 34.8 22.3 Al ₂ O ₃ /wt% 69.2 55.6 40.3 20.2 60.4 74.8 B ₂ O ₃ /wt% 1.1 2.3 5.1 8 4.8 2.9 Specific heat capacity/J·g ^-1 ·K ^-1 1.3 1.45 1.51 1.92 1.43 1.32 Specific surface/m ² ·g ^-1 310 352 365 345 338 331 Pore volume/cm ³ ·g ^-1 0.65 0.78 1.06 1.17 0.94 0.85 Average pore diameter/nm 8.4 8.9 11.6 13.6 11.1 10.3 I ₁ /I ₂ 1:3.8 1:6.5 1:7.2 1:9.4 1:6.1 1:4.2

Example 13

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

13 parts by weight of pseudo-boehmite and deionized water on a dry basis are mixed and beaten (the solid content of the slurry is 15% by weight), and hydrochloric acid is added to the obtained slurry for peptization, and the acid-aluminum ratio (weight ratio) is 0.20:1, then the temperature was raised to 65°C for acidification for 1 hour, followed by adding 35 parts by weight of kaolin slurry (solid content of 25% by weight) on a dry basis, 5 parts by weight of aluminum sol on a dry basis, and 15 parts by weight of the high specific heat capacity matrix material BAM-1 (solid content of 18% by weight) prepared by Preparation Example B1 on a dry basis, stirred for 20 minutes, and then added 32 parts by weight on a dry basis. The described DASY molecular sieve slurry (solid content is 35% by weight) is spray-dried to make a microsphere catalyst after continuous stirring. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110° C. to obtain a catalytic cracking catalyst C19, wherein the total amount of the catalytic cracking catalyst C19 is used. Based on weight, the catalytic cracking catalyst C19 contains 15% by weight of high specific heat capacity matrix material, 32% by weight of DASY molecular sieve, 35% by weight of kaolin, and 18% by weight of Al ₂ O ₃ binder.

Example 14

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

Mix 21 parts by weight of kaolin on a dry basis with deionized water (the solid content of the slurry is 40% by weight), add 20 parts by weight of pseudoboehmite on a dry basis, and add to the resulting slurry Hydrochloric acid is peptized, the acid-aluminum ratio (weight ratio) is 0.20:1, then the temperature is raised to 65 ° C for acidification for 1 hour, and then 4 parts by weight of aluminum sol on a dry basis and 20 parts by weight on a dry basis are added respectively. The slurry (solid content of 20% by weight) of the high specific heat capacity matrix material BAM-2 prepared by Preparation Example B2 was stirred for 20 minutes, and then 35 parts by weight of the REHY molecular sieves (solid content on a dry basis) were added thereto. be 35% by weight), continue to stir and then spray-dry to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C20, wherein the total amount of the catalytic cracking catalyst C20 Based on weight, the catalytic cracking catalyst C20 contains 20% by weight of high specific heat capacity matrix material, 35% by weight of REHY molecular sieve, 21% by weight of kaolin, and 24% by weight of Al ₂ O ₃ binder.

Example 15

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

Mix 28 parts by weight of kaolin on a dry basis with deionized water (the solid content of the slurry is 40% by weight), add 20 parts by weight of pseudoboehmite on a dry basis, and add to the resulting slurry Hydrochloric acid is peptized, the acid-aluminum ratio (weight ratio) is 0.20:1, then the temperature is raised to 65 ° C for acidification for 1 hour, and then 25 parts by weight of the high specific heat capacity matrix material prepared by Preparation Example B3 on a dry basis are respectively added. The slurry of BAM-3 (solid content of 25% by weight) was stirred for 20 minutes, then 27 parts by weight of the HSY molecular sieve slurry (solid content of 35% by weight) on a dry basis was added to it, and sprayed after continuous stirring Dry to make microsphere catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C21, wherein the total amount of the catalytic cracking catalyst C21 is used. Based on weight, the catalytic cracking catalyst C21 contains 25% by weight of high specific heat capacity matrix material, 27% by weight of HSY molecular sieve, 28% by weight of kaolin, and 20% by weight of Al ₂ O ₃ binder.

Example 16

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

42 parts by weight of kaolin on a dry basis, 20 parts by weight of aluminum sol on a dry basis and 10 parts by weight on a dry basis of the high specific heat capacity matrix material BAM-4 prepared by Preparation Example B4 The slurry (solid The content is 20% by weight) mixing and beating, stirring for 120 minutes, then adding 28 parts by weight of the DASY molecular sieve slurry (solid content is 35% by weight) on a dry basis, and spray drying after stirring for 30 minutes to make Microsphere catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C22, wherein the total amount of the catalytic cracking catalyst C22 Based on weight, the catalytic cracking catalyst C22 contains 10% by weight of high specific heat capacity matrix material, 28% by weight of DASY molecular sieve, 42% by weight of kaolin, and 20% by weight of Al ₂ O ₃ binder.

Example 17

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

(1) Preparation of silica sol:

1.7L hydrochloric acid is diluted with 8.0kg decationized water, 7.7kg sodium water glass is diluted with 8.0kg decationized water, and the diluted sodium water glass is slowly added to the above-mentioned dilute hydrochloric acid solution under stirring to obtain SiO Concentration is _: 7.8 wt% silica sol, pH 2.8.

(2) prepare catalytic cracking catalyst:

35 parts by weight of kaolin on a dry basis was added to 30 parts by weight of the above silica sol on a dry basis, and 10 parts by weight on a dry basis of the high specific heat capacity matrix material prepared in Preparation Example B5 was added after stirring for 1 hour. The slurry of BAM-5 (solid content is 18% by weight) is mixed and beaten, and then 25 parts by weight of the DOSY molecular sieve slurry (solid content is 30% by weight) on a dry basis is added to it, and the mixture is spray-dried after stirring. microsphere catalyst. The microsphere catalyst was then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05:1:10) to Na ₂ O content less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain catalytic cracking catalyst C23, wherein, based on the total weight of the catalytic cracking catalyst C23, the catalytic cracking catalyst C23 C23 contains 10% by weight of high specific heat capacity matrix material, 25% by weight of DASY molecular sieve, 35% by weight of kaolin, and 30% by weight of SiO ₂ binder.

Example 18

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

42 parts by weight of kaolin on a dry basis, 15 parts by weight of aluminum sol on a dry basis and 40 parts by weight on a dry basis of the high specific heat capacity matrix material BAM-6 prepared by Preparation Example B6 The slurry (solid The content is 20% by weight) mixing and beating, stirring for 120 minutes, then adding 33 parts by weight of the REHY molecular sieve slurry (solid content is 35% by weight) on a dry basis, and spray-drying to make microspheres after continuing to stir catalyst. Then the microsphere catalyst was calcined at 500°C for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) to a Na ₂ O content of less than 0.25% by weight, then rinsed with deionized water and filtered, and then dried at 110 ° C to obtain a catalytic cracking catalyst C24, wherein the total amount of the catalytic cracking catalyst C24 is used. Based on weight, the catalytic cracking catalyst C24 contains 40% by weight of high specific heat capacity matrix material, 33% by weight of REHY molecular sieve, 42% by weight of kaolin, and 15% by weight of Al ₂ O ₃ binder.

Examples 19-24

Examples 25-30 are used to illustrate the test of the performance of the catalytic cracking catalyst provided by the present invention.

The catalytic cracking catalysts C19-C24 prepared above were impregnated with 5,000 ppm of contaminated iron, 5,000 ppm of nickel, and 5,000 ppm of vanadium by the Mitchell method, aged at 780 °C and 100% water vapor for 6 hours, and placed on a small fixed fluidized bed. To evaluate the cracking performance, the evaluation process of each sample was carried out five times of reaction-regeneration cycle, that is, the same catalyst was not unloaded for five consecutive feedstock reactions and regeneration processes, and the result of the last reaction was taken as the catalyst cracking. Performance evaluation results. The evaluation conditions of heavy oil micro-reaction are: agent-oil ratio 5 (weight ratio), sample loading 9g, reaction temperature 520 ℃, WHSV 8 hours ^-1 , oil feeding time 70 seconds, regeneration temperature 720 ℃, raw material oil is decompressed gas oil. The properties of the feedstock oil are shown in Table 2. The evaluation results are listed in Table 5.

table 5 Example number 19 20 twenty one twenty two twenty three twenty four catalyst number C19 C20 C21 C22 C23 C24 Conversion rate/w% 69.32 69.57 68.81 68.45 68.37 69.18 Dry gas/w% 1.56 1.52 1.52 1.50 1.59 1.54 LPG/w% 12.86 13.07 12.82 12.71 12.54 12.76 Gasoline/w% 49.26 49.36 48.94 48.88 48.62 49.17 Diesel/w% 16.81 16.87 16.71 16.52 16.36 16.58 Oil slurry/w% 13.87 13.56 14.48 15.03 15.27 14.24 Coke/w% 5.64 5.62 5.53 5.36 5.62 5.71 Total liquid yield/w% 78.93 79.30 78.47 78.11 77.52 78.51 Dry gas selectivity 2.25 2.18 2.21 2.19 2.33 2.23 Coke selectivity 8.14 8.08 8.04 7.83 8.22 8.25 H ₂ /CH ₄ 0.11 0.1 0.12 0.13 0.12 0.11

As can be seen from the results of Table 3 and Table 5, compared with the catalyst with the same zeolite content but not containing the high specific heat capacity matrix material, the catalyst provided by the invention has excellent anti-metal pollution ability, the heavy oil conversion ability is greatly improved, and the product distribution is obviously improved, In particular, the selectivity of dry gas and coke can be significantly improved, the yield of total liquid and the yield of light oil can be increased. Compared with the catalyst with the same component content but using different matrix materials, the catalyst provided by the invention has lower dry gas and coke yields and significantly improved dry gas and coke selectivities. It can be seen that the catalytic cracking catalyst provided by the present invention can exhibit better metal pollution resistance, catalytic cracking activity and dry gas and coke selectivity in the process of heavy oil catalytic cracking. The catalyst provided by the invention is used for the conversion of heavy oil and can have higher total liquid yield and higher gasoline and liquefied gas yield. When the boron compound is boron oxide, it can have higher gasoline yield and conversion.

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The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the specification, and together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. in: FIG. 1 is an X-ray diffraction pattern of the high specific heat capacity host material of Example 1. FIG. There are diffraction peaks at 2ɵ angles in the spectrum at 18±0.5°, 37±0.5°, 48±0.5°, 59±0.5°, and 66±0.5°.

Claims (15)

A catalytic cracking catalyst, the catalytic cracking catalyst contains a cracking active component comprising a Y-type molecular sieve, a high specific heat capacity matrix material, clay and a binder; the high specific heat capacity matrix material contains at least 5% by weight of manganese oxide, the high specific heat capacity matrix material The specific heat capacity of the matrix material at a temperature of 1000K is 1.3-2.0 J/(g·K), wherein, preferably, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60% by weight of cracking activity Component, 1-50 wt % high specific heat capacity matrix material, 1-70 wt % clay and 1-70 wt % binder, or, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst It contains 10-50% by weight of cracking active components, 5-40% by weight of high specific heat capacity matrix material, 10-60% by weight of clay and 10-60% by weight of binder. The catalytic cracking catalyst of any one of the preceding claims, wherein the high specific heat capacity matrix material contains 5-95 wt % alumina as Al ₂ O ₃ and 5-95 wt % manganese oxide as MnO ₂ and 0-40% by weight of a boron compound on a dry basis, wherein preferably, the boron compound is boron nitride and/or boron oxide. The catalytic cracking catalyst according to any one of the preceding claims, wherein the specific surface area of the high specific heat capacity matrix material is 150-500 m ² ·g ^-1 ; and/or the pore volume of the high specific heat capacity matrix material and/or, the average pore diameter of the high specific heat capacity matrix material is ^{3-20 nm} . The catalytic cracking catalyst according to any one of the preceding claims, wherein, in the XRD pattern of the high specific heat capacity matrix material, the intensity ratio of peaks at 2θ angles of 18±0.5° and 2θ angles of 37±0.5° is 1 :(3-10). The catalytic cracking catalyst according to any one of the preceding claims, wherein, the preparation method of the high specific heat capacity host material comprises the steps: (1) mixing aluminum source and alkali to form a gel to obtain aluminum-containing colloid, and the pH value of the obtained aluminum-containing colloid is 7-11; (2) make the manganese salt solution of pH value 3-7 mix with urea, obtain manganese source solution; (3) forming a mixture of the aluminum-containing colloid, the manganese source solution, and the optional boron compound; and optionally (4) Washing and/or drying and/or roasting. The catalytic cracking catalyst according to claim 5, wherein, in step (1), the mixing of the aluminum source and the alkali to form a gel comprises: mixing the aluminum source solution and the alkali solution, and the forming temperature ranges from room temperature to 85° C. , a colloid with a pH value of 7-11; and/or, the concentration of alumina in the aluminum source solution is 150-350 gAl ₂ O ₃ /L, and the concentration of the alkali in the alkali solution is 0.1-1 mol/L; and /or, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, etc.; the alkali is (soluble) carbonate, (soluble) in water One or more of bicarbonate, (soluble in water) hydroxide, wherein, preferably, the solution of the base is selected from one or more of CO ₃ ^2- , HCO ₃ ^- or OH ^- In the alkaline aqueous solution, the concentration of CO ₃ ^2- in the alkali solution is 0-0.6 mol/L, the concentration of ^OH- is 0-0.5 mol/L, ^and the concentration of HCO _3- is 0-1 mol/L. The catalytic cracking catalyst according to any one of the preceding claims 5-6, wherein, in step (2), the molar ratio of urea to manganese ions is 1-5, for example, 2-4, and manganese in the manganese salt solution The concentration of the salt may be 50-500 g·L ⁻¹ in terms of MnO ₂ . The catalytic cracking catalyst according to any one of the preceding claims 5-7, wherein, in step (2), urea is added to the manganese salt solution, and then stirred at room temperature for 30-60 minutes to obtain a manganese source solution. The catalytic cracking catalyst according to any one of the preceding claims 5-8, wherein the boron compound is boron nitride and/or boron oxide and/or boron oxide precursor, Wherein, preferably, the boron nitride is one or more of hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride and wurtzite boron nitride; the boron oxide precursor is ammonium borate, One or more of ammonium biborate or boric acid. The catalytic cracking catalyst according to any one of the preceding claims 5-9, wherein in step (3), an aging process is included after mixing the aluminum-containing colloid and the manganese source solution, and the aging temperature is room temperature Warm to 120 ° C, the aging time is 4-72 hours, and the aging is carried out under stirring or standing for aging; preferably, the aging is carried out under stirring, the aging temperature is 60-100 ° C, and the aging time is 12-36 hours. The catalytic cracking catalyst according to any one of the preceding claims 5 to 9, wherein the boron compound is boron nitride; and the method for forming a mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in step (3) is as follows : Aluminium-containing colloid, manganese source solution and boron compound are mixed and aged; or The boron compound is a precursor of boron oxide and/or boron oxide. The method for forming a mixture of the aluminum-containing colloid, the manganese source solution and the boron compound in step (3) is as follows: mixing the aluminum-containing colloid and the manganese source solution, Aged, optionally washed, then mixed with boron compound. The catalytic cracking catalyst according to any one of the preceding claims 5-9, wherein the calcination temperature in step (4) is 500°C-900°C, and the calcination time is 4-8 hours. The catalytic cracking catalyst according to any one of the preceding claims 1-4, wherein the cracking active component contains Y-type molecular sieve, optionally, the cracking active component further contains a second molecular sieve, and the first Two molecular sieves are one or more of faujasite, Beta zeolite, MFI molecular sieve and mordenite; Wherein, preferably, based on the total weight of the cracking active components, the content of the Y-type molecular sieve is more than 75% by weight, and the content of the second molecular sieve is less than 25% by weight. A method for preparing a catalytic cracking catalyst as described in any one of the preceding claims 1-13, the method comprising mixing and beating the pyrolysis active component, a high specific heat capacity matrix material, clay and a binder, and then spraying sequentially Dry, roast, wash, filter and dry. A use of the catalytic cracking catalyst according to any one of the preceding claims 1-13 in the catalytic cracking of heavy oil.

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