Solid acid-base integrated catalyst, preparation method and application thereof

Abstract

The application provides a solid acid-base integrated catalyst and a preparation method and application thereof, and belongs to the technical field of heavy oil non-hydrogenation cracking catalysts. The catalyst is composed of an acidic mesoporous carrier, an alkaline metal and an auxiliary metal, and can be applied in heavy oil catalytic conversion reactions. In the catalyst preparation method, the mesoporous material is subjected to activation treatment and has good cohesiveness, and the forming process does not need to use a traditional binder, thereby avoiding the generation of unstable pore structures and improving the hydrothermal stability of the catalyst matrix; the coated molecular sieve can realize the directional loading of the alkaline metal, construct acid / alkali active centers in the micron scale and realize the microscopic relay catalysis of heavy oil macromolecules. Compared with a solid alkali catalyst or a solid acid catalyst, the solid acid-base integrated catalyst of the application has a significantly improved product distribution when treating atmospheric residue, and the yield of high-value-added liquefied gas and triene is increased by more than 5 percent points and 6.6 percent points, respectively, and the performance is better than that of an acid / alkali mechanically compounded catalyst.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of heavy oil non-hydrocracking catalysts, in particular to a solid acid-base integrated catalyst and its preparation method and application. BACKGROUND

[0002] With the increasing heavy and poor quality of oil resources worldwide, efficient conversion of heavy and poor quality feedstocks has become one of the main trends in future oil refining development; catalytic cracking process is one of the most effective means to convert heavy oil such as heavy oil and residual oil into high-value products such as gasoline, diesel, liquefied gas, etc., with the characteristics of flexible operation, low investment and operating cost.

[0003] Currently, the catalytic cracking process is an acid catalytic cracking process based on carbanion mechanism, and the catalyst mostly uses acid molecular sieve as active component, and the commonly used molecular sieves include ReY, USY, ZSM-5 molecular sieve, etc. Heavy oil and residual oil and other poor heavy oil have the characteristics of large relative molecular weight, high content of heteroatoms and heavy metals, and low hydrogen-carbon ratio. Due to the diffusion limitation of the pore channel of the conventional acid catalytic cracking catalyst, it is difficult to effectively process heavy oil and residual oil and other heavy poor quality oil; the diffusion rate of heavy poor quality oil and the heavy oil processing capacity of the catalytic cracking catalyst are improved by optimizing the pore structure of the catalyst and improving the substrate activity, but it is still difficult to avoid the dehydrogenation-condensation-coke on the acid center of the resin and asphaltene macromolecules in the heavy oil, resulting in high yield of low-value products such as dry gas and coke, affecting the overall economic benefit of the device. How to clean and efficiently process heavy oil to produce high-value chemicals is not only a focus of the world's oil industry and a world-wide technical problem, but also a major problem that needs to be solved by the domestic oil refining industry.

[0004] Patents such as CN103657712B and CN105214712B disclose various heavy oil catalytic cracking catalysts and their preparation methods, and the patent innovations include the application of different types of mesoporous materials, the introduction of different metal species, and the adjustment of meso-microporous structure, etc., but the problem of hydrothermal stability of mesoporous materials has not been solved, and the heavy oil conversion capacity of the catalyst is weak.

[0005] CN113509925A discloses a solid base catalyst and its preparation method, which is composed of active component, additive, molding additive, and solid base catalyst carrier. Among them, the solid base catalytic material is treated by pore thickening and transition metal doping, which improves the hydrothermal stability of the carrier and reduces the adsorption capacity of the catalyst to the coking components in the heavy oil, greatly improving the service life of the catalyst. According to the disclosure, a binder needs to be introduced in this method to improve the mechanical strength of the catalyst, but the binder will cause problems such as carrier pore blockage and decrease of active component proportion, affecting the overall activity of the catalyst.

[0006] Patents such as CN106807436B, CN109833904A disclose various acid-base bifunctional catalysts and their preparation methods. By physical mixing, deposition and precipitation method, the acid active component and the basic active component are combined to obtain an acid-base bifunctional catalyst. With the joint action of acid active center and base active center, the reaction is efficiently carried out. The reaction raw materials include coal, biomass, ethanol, etc.; but it does not solve the damage of basic metal to the active center of acid molecular sieve.

[0007] Patents CN113492013A and CN113492014A disclose a heavy metal resistant catalytic cracking catalyst with core-shell structure, which has good resistance to heavy metal pollution; the inner core of the core-shell structure catalyst is a catalytic cracking catalyst finished particle, and the outer shell is a rare earth oxide or an alkali metal oxide; but it does not solve the damage of alkali metal oxide or rare earth oxide to the active center of acid molecular sieve.

[0008] In the heavy oil catalytic cracking reaction process, compared with the acid catalyst, the basic catalyst is more prone to induce the activation of hydrocarbon molecules, that is, at a relatively low reaction temperature, the hydrocarbon molecules can be dissociatively adsorbed on the basic catalytic active center to form active intermediates; but the basic catalyst has low cracking depth and no significant shape selective cracking effect. The acid-base integrated catalyst has both advantages, can realize micron-scale acid-base relay catalysis, maximize the inhibition of hydrogen transfer and aromatization reaction, and ultimately achieve the purpose of improving the selectivity and yield of low-carbon olefins and reducing the yield of coke. SUMMARY

[0009] Therefore, the present application aims to provide a solid acid-base integrated catalyst and a preparation method thereof, which is applied to the heavy oil catalytic cracking reaction process. The solid acid-base integrated catalyst provided by the present application has the characteristics of low coke yield, high heavy oil conversion rate and high triene yield.

[0010] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows: a solid acid-base integrated catalyst, based on the total weight of the solid acid-base integrated catalyst, the solid acid-base integrated catalyst contains 0.1 wt%-20 wt% of basic metal oxide and 0.1 wt%-10 wt% of auxiliary metal oxide, and the balance is an acid mesoporous carrier; based on the total weight of the acid mesoporous carrier, the acid mesoporous carrier contains 1 wt%-80 wt% of modified mesoporous material, 1 wt%-60 wt% of aluminum oxide material, 1 wt%-40 wt% of molecular sieve, and the balance is clay;

[0011] The basic metal oxide is one or more of alkali metal or alkaline earth metal oxides;

[0012] The auxiliary metal oxide is one or more of Y, Ti, Zr, B, Al, Ga, La, Ce oxide.

[0013] Further, the acid mesoporous carrier is prepared by the following preparation method:

[0014] Firstly, the modified mesoporous material active gel is prepared: the mesoporous material is prepared by sol-gel method, the soluble metal salt of the doping metal is introduced in the sol stage to obtain the mesoporous material gel doped with metal, and the gel is treated with inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining the active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid;

[0015] Then, the active dispersion of the active gel is carried out: the active gel of the modified mesoporous material obtained in the last step is mixed with the activation auxiliary agent, inorganic acid and deionized water in a strong shearing machine, and then the active dispersion is carried out on a sand mill to obtain the homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5;

[0016] Finally, the stable auxiliary agent is prepared into a slurry and sprayed: the stable auxiliary agent is added into the alumina material precursor slurry and stirred and mixed uniformly, then the sol slurry obtained in the last step, the coated molecular sieve and the clay are added in sequence, and after stirring and mixing uniformly, spray drying is carried out to obtain the acid mesoporous carrier; the coated molecular sieve is one or more of Y, beta, ZSM-5 and MCM-22 molecular sieve; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite;

[0017] The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide and silicon-potassium composite oxide.

[0018] Further, the solid acid-base integrated catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0019] The application further provides a preparation method of the solid acid-base integrated catalyst, which comprises the following steps:

[0020] Step S1, preparing the acidic mesoporous carrier; first, preparing the modified mesoporous material active gel; then, activating and dispersing the active gel so that the pH of the modified mesoporous material homogeneous sol slurry is 0.5-5; finally, stabilizing the auxiliary agent to prepare the slurry spray;

[0021] Step S2, preparing the solid acid-base integrated catalyst; the soluble metal salt of the basic metal and the soluble metal salt of the auxiliary metal are introduced into the acidic mesoporous carrier by one of the ion exchange method, the impregnation method, and the coprecipitation method, and then the solid acid-base integrated catalyst is obtained after drying and calcination.

[0022] Further, the step S1 is specifically:

[0023] Step S11, preparing the modified mesoporous material active gel: the mesoporous material is prepared by the sol-gel method, the doped metal soluble metal salt is introduced in the sol stage to obtain the metal-doped mesoporous material gel, and the gel is then treated with inorganic acid solution and deionized water in sequence to remove the doped metal soluble metal salt and inorganic acid in the gel, thereby obtaining the active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid;

[0024] Step S12, activating and dispersing the active gel: the active gel of the modified mesoporous material obtained in step S11 is mixed with the activation auxiliary agent, inorganic acid, and deionized water in a strong shear machine, and then activated and dispersed on a sand mill to obtain the homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; the inorganic acid is added in an amount so that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5;

[0025] Step S13, stabilizing the auxiliary agent to prepare the slurry spray: the stabilizing auxiliary agent is added to the alumina material precursor slurry, stirred and mixed uniformly, then the sol slurry obtained in step S12, the coated molecular sieve, and the clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain the acidic mesoporous carrier; the coated molecular sieve is one or more of Y, β, ZSM-5, and MCM-22 molecular sieves; the clay is one or more of kaolin, montmorillonite, bentonite, and hydrotalcite.

[0026] Further, the doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium, and molybdenum; the weight ratio of the doped metal (in terms of the mass of the metal oxide) to the dry basis mass of the mesoporous active material is 0.001-10:1;

[0027] The activation auxiliary agent is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol, and polyvinyl alcohol; the weight ratio of the activation auxiliary agent to the dry basis mass of the active gel is 0.001-10:1;

[0028] The stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid, and methacrylic acid-methoxy polyethylene glycol methacrylate; and the weight ratio of the stabilizing aid to the alumina material is 0.001-10:1.

[0029] Further, the coated molecular sieve is prepared by adding polyvinyl alcohol to a molecular sieve slurry at 85-95℃, mixing uniformly, and then spray drying to obtain the coated molecular sieve.

[0030] The alumina material precursor is one or more of an aluminum sol, an aluminum oxide stone sol, and a soluble aluminum salt solution.

[0031] Further, the aluminum oxide stone sol is prepared by mixing aluminum stone with deionized water, adding inorganic acid at a ratio of inorganic acid:alumina of 0.05-0.2, and mixing and slushing, and controlling the aluminum stone content in the slurry to be 1 wt%-25 wt%; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; and the aluminum stone is one or more of pseudo-boehmite, monohydrate, trihydrate, bayerite, and aluminum hydroxide.

[0032] The soluble aluminum salt is one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.

[0033] Further, the calcination conditions of the solid acid-base integrated catalyst are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

[0034] In addition, the application also provides the use of the above solid acid-base integrated catalyst in a heavy oil catalytic conversion reaction.

[0035] Compared with the prior art, the solid acid-base integrated catalyst and the preparation method and application thereof have the following advantages: in the preparation method of the solid acid-base integrated catalyst, the modified mesoporous material has good adhesion after activation treatment, and no traditional binder is needed in the forming process, thereby avoiding the generation of unstable pore structures; the coated molecular sieve can realize the directional loading of alkaline metals, the acid-base active center is constructed in the micron scale, and the relay catalysis of heavy oil macromolecules is realized.

[0036] (1) The catalyst has abundant and stable mesopores: the modified mesoporous material has excellent adhesion, replaces the traditional binder, significantly increases the mesopore proportion in the catalyst, and improves the accessibility of heavy oil macromolecules. After hydrothermal treatment of the catalyst at 800℃ for 17h, the specific surface area of the mesopores in the catalyst is as high as 215 m 2 / g, and the mesopore volume is as high as 0.17 cm 3 / g.

[0037] (2) High-efficiency synergistic catalytic performance: the molecular sieve is treated by coating to effectively avoid the influence of alkali metal on the acid center of the molecular sieve, the surface of the modified mesoporous material has rich defect centers, which can effectively anchor the alkali metal, and the acid-base active center is constructed in the micron scale, so that the primary cracking of the heavy oil macromolecule is completed in the alkali catalytic active center, and then the deep cracking is completed in the acid center, so that the step-by-step gradient cracking of the heavy oil macromolecule is realized; the alkali catalytic active center in the mesoporous material can effectively avoid the condensation and coking of the heavy oil macromolecule in the primary cracking stage. Specifically, the solid acid-base integrated catalyst provided by the present application can significantly improve the product distribution when treating atmospheric residue, and the yield of high-value-added liquefied gas and triene is increased by more than 5 percentage points and 6.6 percentage points, respectively, and the performance is better than that of the acid / alkali mechanically compounded catalyst. DETAILED DESCRIPTION

[0038] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0039] The present application relates to a solid acid-base integrated catalyst, in particular to a solid acid-base integrated catalyst for catalytic conversion of atmospheric residue, wherein the solid acid-base integrated catalyst contains 0.1 wt%-20 wt% of alkali metal oxide and 0.1 wt%-10 wt% of auxiliary metal oxide, and the balance is an acid mesoporous carrier, based on the total weight of the solid acid-base integrated catalyst; wherein the acid mesoporous carrier contains 1 wt%-80 wt% of modified mesoporous material, 1 wt%-60 wt% of alumina material and 1 wt%-40 wt% of molecular sieve, and the balance is clay, based on the total weight of the acid mesoporous carrier.

[0040] The alkali metal oxide is one or more of alkali metal or alkaline earth metal oxides, and is preferably one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide and barium oxide.

[0041] The auxiliary metal oxide is one or more of Y, Ti, Zr, B, Al, Ga, La and Ce oxides.

[0042] The acid mesoporous carrier is prepared by the following preparation method:

[0043] First, the modified mesoporous material active gel is prepared: the mesoporous material is prepared by the sol-gel method, the doped metal soluble metal salt is introduced in the sol stage to obtain the mesoporous material gel doped with metal, and then the gel is treated with inorganic acid solution and deionized water in sequence to remove the doped metal soluble metal salt and inorganic acid in the gel to obtain the active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.

[0044] Then, the activated dispersion of the modified mesoporous material active gel is prepared: the modified mesoporous material active gel obtained in the last step is mixed with an activating additive, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5;

[0045] Finally, the stabilizing additive is slurried and sprayed: the stabilizing additive is added to the alumina material precursor slurry, and stirred and mixed uniformly, then the sol slurry obtained in the last step, a coated molecular sieve and clay are sequentially added, stirred and mixed uniformly, and then spray dried to obtain an acidic mesoporous carrier; the coated molecular sieve is one or more of Y, beta, ZSM-5 and MCM-22 molecular sieves; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite;

[0046] The mesoporous material is one or more of a silicon-containing composite oxide, silicon dioxide and white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of a silicon-aluminum composite oxide, a silicon-calcium composite oxide, a silicon-magnesium composite oxide and a silicon-potassium composite oxide.

[0047] The solid acid-base integrated catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0048] The application further provides a preparation method of the solid acid-base integrated catalyst, comprising the following steps:

[0049] Step S1, preparation of an acidic mesoporous carrier;

[0050] Step S11, preparation of a modified mesoporous material active gel: a mesoporous material is prepared by a sol-gel method, a doped metal soluble metal salt is introduced in the sol stage to obtain a mesoporous material gel doped with metal, and the gel is then treated with an inorganic acid solution and deionized water in sequence to remove the doped metal soluble metal salt and the inorganic acid in the gel to obtain a modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid;

[0051] The doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; and the weight ratio of the doped metal (calculated as the mass of metal oxide) to the dry mass of the mesoporous active material is 0.001-10:1;

[0052] Step S12, activating and dispersing the active gel: the active gel of the modified mesoporous material obtained in step S11 is mixed with an activating additive, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5;

[0053] The activating additive is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; the weight ratio of the activating additive to the dry basis of the active gel is 0.001-10:1;

[0054] Step S13, preparing a slurry by spraying a stabilizing additive: a stabilizing additive is added to the alumina material precursor slurry, and stirred and mixed uniformly, then the sol slurry obtained in step S12, a coated molecular sieve and clay are added in sequence, and stirred and mixed uniformly before spray drying to obtain an acidic mesoporous carrier; the coated molecular sieve is one or more of Y, β, ZSM-5 and MCM-22 molecular sieves; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite;

[0055] The stabilizing additive is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate (PCE); the weight ratio of the stabilizing additive to the alumina material is 0.001-10:1;

[0056] The coated molecular sieve is prepared by adding polyvinyl alcohol to a molecular sieve slurry at 85-95℃, mixing uniformly and then spray drying to obtain the coated molecular sieve;

[0057] The alumina material precursor is selected from one or more of an aluminum sol, an acidified aluminum stone sol and a soluble aluminum salt solution; the acidified aluminum stone sol is prepared by mixing aluminum stone with deionized water, adding inorganic acid at a ratio of inorganic acid:alumina of 0.05-0.2, and controlling the aluminum stone content in the slurry to be 1 wt%-25 wt%; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the aluminum stone is selected from one or more of pseudoboehmite, monohydrate, trihydrate, bayerite and aluminum hydroxide; the soluble aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

[0058] Step S2, preparing the solid acid-base integrated catalyst; the soluble metal salt of the basic metal and the soluble metal salt of the auxiliary metal are introduced into the acidic mesoporous carrier by one of ion exchange method, impregnation method and coprecipitation method, and then the solid acid-base integrated catalyst is obtained by drying and calcination.

[0059] The calcination condition of the solid acid-base integrated catalyst is calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

[0060] In addition, the application further provides the application of the above solid acid-base integrated catalyst in heavy oil catalytic conversion reaction.

[0061] The application process is illustrated by examples below, and it should be understood that the specific embodiments described herein are only used to illustrate and explain the application, but not to limit the application.

[0062] Example 1

[0063] The solid acid-base integrated catalyst is composed of an acidic mesoporous carrier, a basic metal and an auxiliary metal. Based on the total weight of the solid acid-base integrated catalyst, the basic metal oxide is 3 wt%, the auxiliary metal oxide is 2 wt%, and the acidic mesoporous carrier is 95 wt%; the mesoporous material in the acidic mesoporous carrier is silica, and based on the total weight of the acidic mesoporous carrier, the silica is 25 wt%, the alumina is 10 wt%, the Y molecular sieve is 20 wt%, the ZSM-5 molecular sieve is 10 wt%, and the kaolin is 35 wt%.

[0064] (1) Preparation of modified mesoporous material active gel: 2000g of water glass solution with a modulus of 3.2 and a silica content of 29.5 wt% is placed in a reactor and heated to 50℃, and 26.3g of gallium nitrate nonahydrate is slowly added under constant stirring at a dry basis weight ratio of gallium oxide to silica of 0.02:1, followed by slow addition of dilute nitric acid (15%), adjusting the PH value to about 6, stirring for 30 minutes to obtain gallium-modified silica hydrogel; 10 wt% of dilute nitric acid solution (1000g) is added and treated at 50℃ for 15 hours, and then washed with deionized water until the filtrate is neutral to obtain gallium-modified silica active gel (the silica solid content in the gel is 19%);

[0065] (2) Activation and dispersion of active gel: 17.7g of citric acid is added at a weight ratio of citric acid to gallium-modified silica gel (dry basis) of 0.03:1, followed by the addition of appropriate amounts of nitric acid and deionized water to control the slurry PH to 1.5 and the silica solid content to 17%, and then the above slurry is mixed with a high shear machine for 30 minutes and treated with a sand mill for 60 minutes at a speed of 3000rpm to obtain a homogeneous sol slurry of gallium-modified silica.

[0066] (3) Preparation of coated molecular sieve: 300 g of Y molecular sieve (solid content 90%), 150 g of ZSM-5 molecular sieve (solid content 90%) and 1500 g of deionized water were mixed uniformly, heated to 90°C, then 45 g of polyvinyl alcohol was added and stirred for 30 minutes, dried and formed using a spray drying device, and the sample with a particle size of 0-20 μm was collected to prepare the coated molecular sieve.

[0067] (4) Preparation of stable additive slurry for spraying: 391.3 g of aluminum sol (solid content 23%) and 2280 g of deionized water were mixed, 45 g of disodium ethylenediaminetetraacetate was added and stirred for 30 minutes at a weight ratio of stable additive to aluminum oxide of 0.5:1, then 1324 g of gallium modified silica homogeneous sol slurry (solid content 17%) was added and stirred for 30 minutes, 366 g of kaolin (solid content 86%) was added and stirred for 120 minutes, 300 g of coated molecular sieve (solid content 90%) was added and stirred for 30 minutes, dried and formed using a spray drying device, the outlet temperature was controlled at 135°C, and the catalyst sample with a particle size in the range of 0-200 μm was collected to obtain the acidic mesoporous carrier;

[0068] (5) Preparation of solid acid-base integrated catalyst: 114.8 g of calcium nitrate tetrahydrate and 24.2 g of lanthanum nitrate hexahydrate were dissolved in 855 g of deionized water to prepare an impregnation solution; 855 g of high-activity mesoporous carrier (water absorption rate of 1) was used to load the basic metal and the additive metal by the equal-volume impregnation method, the catalyst was dried at 120°C for 6 hours and calcined at 650°C for 4 hours in a 100% water vapor atmosphere to obtain the solid acid-base integrated catalyst.

[0069] Example 2

[0070] The solid acid-base integrated catalyst is composed of the acidic mesoporous carrier, the basic metal and the additive metal, and the basic metal oxide is 7 wt%, the additive metal oxide is 3 wt%, and the acidic mesoporous carrier is 90 wt% based on the total weight of the solid acid-base integrated catalyst; the mesoporous material in the acidic mesoporous carrier is a silicon-aluminum composite oxide, and the silicon-aluminum composite oxide is 25 wt%, the aluminum oxide is 10 wt%, the Y molecular sieve is 20 wt%, the ZSM-5 molecular sieve is 10 wt%, and the kaolin is 35 wt% based on the total weight of the acidic mesoporous carrier;

[0071] (1) Preparation of modified mesoporous material active gel: take 2000g of water glass solution with modulus of 3.2 and silica content of 29.5 wt%, place it in a reactor and heat to 50℃, slowly add 20.18g of chromium nitrate nonahydrate and then 215.8g of aluminum nitrate nonahydrate at a dry basis weight ratio of gallium oxide to silicon dioxide of 0.005:1, and finally add an appropriate amount of dilute nitric acid (15%) to adjust the pH to about 6, stir for 30 minutes to obtain a chromium-modified silicon-aluminum composite oxide gel; add 10 wt% of dilute nitric acid solution (1000g) at 50℃ for 15 hours, and then wash with deionized water until the filtrate is neutral to obtain a chromium-modified silicon-aluminum composite oxide active gel (the solid content of the silicon-aluminum composite oxide in the gel is 19%);

[0072] (2) Activate and disperse the active gel in the same way as in Example 1, except that 32.47g of tartaric acid is added at a weight ratio of tartaric acid to chromium-modified silicon-aluminum composite oxide active gel (dry basis) of 0.05:1;

[0073] (3) Preparation of coated molecular sieve is the same as in Example 1;

[0074] (4) The same as in Example 1 for preparing a slurry spray of stabilizing additives;

[0075] (5) The same method as in Example 1 is used to prepare a high-activity solid base catalyst, except that 68.3g of potassium nitrate and 157.5g of titanium nitrate nonahydrate are used instead of calcium nitrate hexahydrate and lanthanum nitrate hexahydrate, respectively, and the amount of deionized water is 810g.

[0076] Example 3

[0077] The solid acid-base integrated catalyst is composed of an acidic mesoporous carrier, a basic metal and an additive metal. Based on the total weight of the solid acid-base integrated catalyst, the basic metal oxide is 4 wt%, the additive metal oxide is 3 wt%, and the acidic mesoporous carrier is 93 wt%. The mesoporous material in the acidic mesoporous carrier is silica, based on the total weight of the acidic mesoporous carrier, the silica is 15 wt%, the alumina is 10 wt%, the Y molecular sieve is 25 wt%, the ZSM-5 molecular sieve is 15 wt%, and the kaolin is 35 wt%.

[0078] (1) Preparation of mesoporous material active gel is the same as in Example 1;

[0079] (2) Activate and disperse the active gel in the same way as in Example 1, except that 32.47g of tartaric acid is added at a weight ratio of tartaric acid to chromium-modified silicon-aluminum composite oxide active gel (dry basis) of 0.05:1;

[0080] (3) The same method as in Example 1 was used to prepare the coated molecular sieve, except that the amounts of Y molecular sieve, ZSM-5 molecular sieve, deionized water and polyvinyl alcohol were 360 g, 216 g, 1920 g and 58 g, respectively;

[0081] (4) Stabilizing additive pulping and spraying: 128.6 g of pseudoboehmite (solid content 70%) was added to 950 g of deionized water and mixed for 30 minutes, 13.1 g of concentrated hydrochloric acid (concentration 36%) was added, and stirring was continued for 60 minutes, 90 g of citric acid was added according to the weight ratio of stabilizing additive to alumina of 1:1, and stirring was continued for 30 minutes, then 794 g of gallium-modified silica homogeneous sol slurry (solid content 17%) was added and stirred for 30 minutes, 366 g of kaolin (solid content 86%) was added and stirred for 120 minutes, 300 g of coated molecular sieve (solid content 90%) was added and stirred for 30 minutes, and a spray drying device was used for drying and molding, with the outlet temperature controlled at 135°C, and the catalyst sample with a particle size in the range of 0-200 μm was collected, to obtain an acidic mesoporous carrier;

[0082] (5) The same method as in Example 1 was used to prepare a high-activity solid base catalyst, except that 60.6 g of barium acetate was used instead of calcium nitrate hexahydrate, and the amounts of lanthanum nitrate hexahydrate and deionized water were 36.2 g and 930 g, respectively.

[0083] Comparative Example 1

[0084] To compare the performance of the solid acid-base integrated catalyst, an alkaline catalyst containing a mesoporous material with good hydrothermal stability but not containing an acidic molecular sieve material was prepared. The specific preparation method is as follows:

[0085] The catalyst of Comparative Example 1 was composed of a mesoporous carrier, an alkaline metal and an additive metal, and based on the total weight of the catalyst of Comparative Example 1, the alkaline metal oxide was 3 wt%, the additive metal oxide was 2 wt%, and the mesoporous carrier was 95 wt%; the mesoporous material in the mesoporous carrier was silica, and based on the total weight of the mesoporous carrier, the silica was 55 wt%, the alumina was 10 wt%, and the kaolin was 35 wt%;

[0086] (1) The preparation of the mesoporous material active gel was the same as in Example 1;

[0087] (2) The activation and dispersion of the active gel were the same as in Example 1;

[0088] (3) Stabilizing additive pulping spray: take 391.3 g of aluminum sol (solid content 23%) and 840 g of deionized water, according to the weight ratio of stabilizing additive to aluminum oxide of 0.5:1, add 45 g of ethylenediaminetetraacetic acid disodium salt and stir for 30 minutes, then add 2912 g of gallium modified silica homogeneous sol slurry (solid content 17%) and stir for 30 minutes, finally add 366 g of kaolin (solid content 86%) and stir for 120 minutes, dry and shape using a spray drying device, control the outlet temperature at 135℃, collect the catalyst samples with particle size in the range of 0-200 μm, and obtain a high-activity mesoporous carrier;

[0089] (4) The catalyst of Comparative Example 1 is prepared in the same way as Example 1.

[0090] Comparative Example 2

[0091] In order to compare the performance of the solid acid-base integrated catalyst, a conventional heavy oil catalytic cracking catalyst is prepared, which does not contain alkaline metals and mesoporous materials. The specific preparation method is as follows:

[0092] Add 257.1 g of pseudoboehmite (solid content 70%) to 3430 g of deionized water and mix for 30 minutes, add 26.2 g of concentrated hydrochloric acid (concentration 36%), continue to stir for 60 minutes, and then add 200 g of Y molecular sieve (solid content 90%), 100 g of ZSM-5 molecular sieve, 471 g of kaolin (solid content 86%) and 195.7 g of aluminum sol (alumina content 23.1%) respectively, and stir for 1 hour each. Dry and shape using a spray drying device, control the outlet temperature at 135℃, collect the particles with particle size in the range of 0-200 μm, and calcine in air atmosphere at 650℃ for 4 hours to obtain the catalyst of Comparative Example 2.

[0093] Comparative Example 3

[0094] In order to compare the performance of the solid acid-base integrated catalyst, a solid acid-base catalyst prepared by mechanically mixing an alkaline catalyst and an acidic catalyst is prepared, and the specific preparation method is as follows:

[0095] Mix Comparative Example 1 and Comparative Example 2 according to the mass ratio of 1:1 to obtain Comparative Example 3.

[0096] The catalyst performance evaluation method of the examples and comparative examples of the present application is as follows:

[0097] The catalysts prepared in the examples and comparative examples are respectively treated in 100% steam atmosphere at 800℃ for 17 hours, and the pore structure characterization data of each catalyst before and after hydrothermal treatment are shown in Table 1; then the catalysts are filled in a fixed fluidized bed evaluation device for catalyst performance evaluation, and the catalyst loading amount is 600 g. The reaction temperature is 520℃, the weight ratio of catalyst to oil is 6, the weight hourly space velocity is 15 h -1Under the specified conditions, the feedstock oils with the compositions shown in Table 2 were injected into a fixed fluidized bed reactor, and the reaction results are shown in Table 3. The heavy oil conversion index was calculated using the following formula:

[0098] Heavy oil conversion index =

[0099] Table 1. Changes in pore structure of catalysts in the examples and comparative examples before and after hydrothermal treatment.

[0100]

[0101] Table 2. Basic properties of raw materials used in the examples and comparative examples.

[0102]

[0103] Table 3 Evaluation results of hydrothermal samples of catalysts in the examples and comparative examples.

[0104]

[0105] The comparison of the above tables shows that the solid acid-base integrated catalyst (Examples 1-3) provided by the present invention significantly improves the product distribution when treating atmospheric residue oil. Compared with Comparative Example 2, the yield of high-value-added liquefied gas and trienes is increased by more than 5 percentage points and 6.6 percentage points, respectively, and its performance is better than that of the acid / base mechanical compound catalyst (Comparative Example 3).

[0106] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A solid acid-base integrated catalyst, characterized by: The solid acid-base integrated catalyst contains 0.1 wt%-20 wt% of the basic metal oxide and 0.1 wt%-10 wt% of the auxiliary metal oxide, with the balance being the acidic mesoporous carrier; the acidic mesoporous carrier contains 1wt%-80wt% of the modified mesoporous material, 1wt%-60wt% of the alumina material and 1wt%-40wt% of the molecular sieve, with the balance being clay; the sum of the mass fractions of the components in the acidic mesoporous carrier is 100%, based on the total weight of the acidic mesoporous carrier; The basic metal oxide is one or more of alkali metal or alkaline earth metal oxides; The auxiliary metal oxide is one or more of Y, Ti, Zr, Al, Ga, La, Ce oxides; The acidic mesoporous carrier is prepared by the following preparation method: First, a mesoporous material is prepared by a sol-gel method, a soluble metal salt of a doping metal is introduced in the sol stage to obtain a metal-doped mesoporous material gel, and the gel is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining an active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide, white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide, silicon-potassium composite oxide. The doping metal is one or more of aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doping metal in terms of the mass of the metal oxide to the dry mass of the mesoporous material is (0.001-10):1; Then, the active gel of the modified mesoporous material obtained in the previous step is mixed with an activation auxiliary agent, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5; The activation auxiliary agent is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; Finally, a stabilizing auxiliary agent is added to an alumina material precursor slurry, stirred and mixed uniformly, and then the sol slurry obtained in the previous step, a coated molecular sieve and clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain an acidic mesoporous carrier; The stabilizing auxiliary agent is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; The coated molecular sieve is prepared by the following method: polyvinyl alcohol is added to a molecular sieve slurry at 85-95℃, mixed uniformly and then spray dried to obtain the coated molecular sieve; The molecular sieve is one or more of Y, β, ZSM-5 and MCM-22 molecular sieves; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite.

2. The solid acid-base integrated catalyst according to claim 1, characterized in that: The solid acid-base integrated catalyst is a microspherical catalyst with a particle size of 0-200μm.

3. A method for producing the solid acid-base integrated catalyst according to claim 1 or 2, characterized by, The method comprises the following steps: Step S1, preparing an acidic mesoporous carrier: First, the mesoporous material is prepared by sol-gel method, and a soluble metal salt of a doping metal is introduced in the sol stage to obtain a gel of the metal-doped mesoporous material, which is then treated with an inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and the inorganic acid in the gel, thereby obtaining an active gel of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; The mesoporous material is one or more of silicon-containing composite oxide, silicon dioxide, white carbon black; and the specific surface area of the mesoporous material is 300-800 m 2 / g, the pore volume is 0.3-1.8 cm 3 / g, and the average pore size is 5-50 nm; the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-calcium composite oxide, silicon-magnesium composite oxide, silicon-potassium composite oxide. The doping metal is one or more of aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doping metal in terms of the mass of metal oxide to the dry mass of the mesoporous material is (0.001-10):1; Then, the active gel of the modified mesoporous material obtained in the previous step is mixed with an activation aid, an inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of the modified mesoporous material; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5; The activation aid is one or more of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; Finally, a stabilizing aid is added to the alumina material precursor slurry, and then the sol slurry obtained in the previous step, a coated molecular sieve and clay are added in sequence, and the mixture is stirred and mixed uniformly, followed by spray drying to obtain an acidic mesoporous carrier; The stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; The coated molecular sieve is prepared by adding polyvinyl alcohol to a molecular sieve slurry at 85-95℃, mixing uniformly and then spray drying to obtain the coated molecular sieve; The molecular sieve is one or more of Y, β, ZSM-5 and MCM-22 molecular sieves; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite; Step S2, preparation of a solid acid-base integrated catalyst: The soluble metal salt of the basic metal and the soluble metal salt of the auxiliary metal are introduced into the acidic mesoporous carrier by any one of ion exchange method, impregnation method and coprecipitation method, and then dried and calcined to obtain the solid acid-base integrated catalyst; The calcination conditions are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

4. The method of claim 3, wherein the solid acid-base integrated catalyst is prepared by the steps of: (a) preparing a mixture of a solid acid catalyst and a solid base catalyst; (b) mixing the mixture with a solvent; (c) drying the mixture; and (d) calcining the mixture. The weight ratio of the activation aid to the dry mass of the active gel is (0.001-10):1; The weight ratio of the stabilizing aid to the alumina material is (0.001-10):

1.

5. The method for preparing the solid acid-base integrated catalyst according to claim 3, characterized in that: The alumina material precursor is selected from one or more of an aluminum sol, an acidified aluminum stone sol and a soluble aluminum salt solution. The acidified aluminum stone sol is prepared by the following method: aluminum stone is mixed with deionized water to make a slurry, inorganic acid is added to the slurry at a ratio of inorganic acid:aluminum oxide=0.05-0.2, and the content of aluminum stone in the slurry is controlled to be 1 wt%-25 wt%; the aluminum stone is selected from one or more of pseudoboehmite, monohydrate, trihydrate, bayerite and aluminum hydroxide; and the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid.

6. The method of claim 5, wherein the solid acid-base integrated catalyst is prepared by the steps of: (a) preparing a mixture of a solid acid catalyst and a solid base catalyst; (b) mixing the mixture with a solvent; (c) drying the mixture; and (d) calcining the mixture. The soluble aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

7. Application of the solid acid-base integrated catalyst of claim 1 or 2 in a heavy oil catalytic cracking reaction.

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