Highly active solid base catalyst, its preparation method and application

Abstract

The application provides a high-activity solid alkali catalyst and a preparation method and application thereof, and belongs to the field of heavy oil non-hydrocracking catalysts. The high-activity solid alkali catalyst is composed of a high-activity mesoporous carrier, an active metal and an auxiliary metal, and is applied in heavy oil catalytic conversion reactions. The preparation method comprises the following steps: S1, preparing the high-activity mesoporous carrier; and S2, preparing the high-activity solid alkali catalyst. In S1, the mesoporous material is sequentially subjected to metal doping-dissolution and dispersion activation treatment, so that the modified mesoporous material subjected to secondary sol-gel has good cohesiveness, the forming process does not need to use a traditional binder, the pore structure of the mesoporous material can be maximally reserved, and unstable pore structures generated by the traditional binder are avoided, thereby greatly improving the hydrothermal stability of the high-activity mesoporous carrier. In addition, the active metal component can eliminate part of strong polar centers in the high-activity mesoporous carrier, further reduce the proportion of strong polar centers in the high-activity solid alkali catalyst, and improve the selectivity of low-carbon olefins.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of heavy oil non-hydrocracking catalysts, and particularly relates to a high-activity solid base catalyst and a preparation method and application thereof. BACKGROUND

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

[0003] At present, the catalytic cracking process is an acid catalytic cracking process based on the mechanism of carbenium ion, and the catalysts mostly use acid molecular sieves as active components, and the commonly used molecular sieves include ReY, USY, ZSM-5 molecular sieves and the like. The inferior heavy oil such as heavy oil and residual oil has the characteristics of large relative molecular weight, high content of heteroatoms and heavy metals, and low hydrogen-carbon ratio, and the conventional acid catalytic cracking catalysts are difficult to effectively process the heavy inferior oil due to the diffusion limitation of the pore channel; the diffusion rate of the heavy inferior oil and the heavy oil processing capacity of the catalytic cracking catalysts are improved by means of optimizing the pore channel structure of the catalyst and improving the substrate activity, but it is still difficult to avoid the dehydrogenation-condensation-coke on the acid center on the macromolecules such as resin and asphaltene in the heavy oil, resulting in high yield of low-value products such as dry gas and coke, and 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 oil industry and a world-wide technical problem, but also a major problem urgently needed to be solved by the domestic oil industry.

[0004] In recent years, solid base catalytic materials have developed rapidly, and have been applied in the industrial application of biodiesel preparation and ester exchange reaction, but there is no report on their application in the field of catalytic cracking. Due to the existence of basic active centers, the solid base catalysts have the characteristics of low hydrogen transfer activity and moderate conversion depth, and have unique advantages in heavy oil conversion reaction, and are becoming a research hotspot in this field; the stable and reliable alkali catalyst and the preparation method are the technical key to support the application of the catalyst in the heavy oil catalytic cracking process.

[0005] In the field of biodiesel preparation, patent CN109663585A discloses a preparation method of a solid base catalyst, which uses waste catalytic cracking catalyst, sepiolite, calcium chloride, calcium nitrate and the like as raw materials, and is prepared into catalyst particles with a particle size of 100-200 mesh through impregnation, mixing, filtration, calcination and grinding; but the mechanical strength of the catalyst prepared by the method is poor, and cannot meet the requirements of the catalytic cracking process.

[0006] In the field of ester exchange reaction, CN110833845A discloses a preparation method of a solid base catalyst, which loads metal nitrate on a carrier such as g-C3N4 or NMC, and prepares the solid base catalyst through drying and calcination. However, the carrier used in this method cannot meet the requirements of catalytic cracking process.

[0007] In the field of catalytic cracking process, CN101755036 uses silicon dioxide, aluminum oxide, titanium oxide and mixtures as carriers to load transition metals, alkali metals, alkaline earth metals and the like to prepare a solid base catalyst. In the catalyst preparation scheme, a certain amount of small-pore zeolite and other acidic components are also added. Although this patent introduces the base catalyst into the catalytic cracking reaction, the overall activity of the catalyst is still provided by the acidic components, and the catalyst has poor hydrothermal stability and low resistance to heavy metal pollution, which cannot meet the requirements of catalytic cracking process.

[0008] CN107115853A discloses a catalyst for treating super heavy oil such as residual oil and a preparation method thereof. The method uses Mg-Al hydrotalcite as an active component, mixes it with clay and a binder, and then sprays, dries and calcines to obtain the catalyst. Although the catalyst has good hydrothermal stability, its catalytic activity is low and cannot meet the requirements of the catalytic cracking riser process.

[0009] CN113509925A discloses a solid base catalyst and a preparation method thereof. The solid base catalyst provided by the method is composed of an active component, an additive, a molding aid and a solid base catalyst carrier. The solid base catalyst material is treated by pore thickening and transition metal doping to improve the hydrothermal stability of the carrier and reduce the adsorption capacity of the catalyst for coking components in heavy oil, thereby greatly improving the service life of the catalyst. According to the disclosure, a binder needs to be introduced in the method to improve the mechanical strength of the catalyst, but the binder will cause problems such as carrier pore blocking and reduction of the proportion of active components, affecting the overall activity of the catalyst.

[0010] In summary, the existing acid catalytic cracking catalysts with molecular sieves as active components cannot effectively process heavy and poor oil such as heavy oil and residual oil. Solid base catalysts have unique advantages in heavy oil conversion reactions, but the yield of additional value products such as dry gas and coke is low. However, the existing solid base catalysts generally have problems such as poor hydrothermal stability and insufficient catalytic activity. Therefore, it is necessary to develop a solid base catalyst with strong resistance to heavy metal pollution and high catalytic activity, and a preparation method thereof, for processing heavy and poor oil such as heavy oil and residual oil, which has good application prospects. SUMMARY

[0011] In view of this, the present application aims to provide a solid base catalyst with strong heavy metal pollution resistance and high catalytic activity, which is applied in heavy oil catalytic conversion reaction, and can solve the problem that the heavy oil catalytic cracking catalyst prepared by the prior art is difficult to process heavy and poor oil such as heavy oil and residual oil for a long period of time with high efficiency. The solid base catalyst provided by the present application can stably process atmospheric residual oil, has excellent product distribution, and greatly improves the olefin yield.

[0012] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows: a high-activity solid base catalyst, based on the total weight of the high-activity solid base catalyst, contains 0.1 wt%-20 wt% of active metal oxide and 0.1 wt%-10 wt% of auxiliary metal oxide, and the balance is a high-activity mesoporous carrier; based on the total weight of the high-activity mesoporous carrier, the high-activity mesoporous carrier contains 1 wt%-80 w% of modified mesoporous material and 1 wt%-50 w% of alumina material, and the balance is clay;

[0013] The active metal oxide is one or more of alkali metal or alkaline earth metal oxides;

[0014] The auxiliary metal oxide is one or more of Y, Ti, Zr, B, Al, Ga, La, and Ce oxides.

[0015] Further, the high-activity mesoporous carrier is prepared by the following preparation method:

[0016] First, prepare a modified mesoporous material active gel: prepare a mesoporous material by sol-gel method, introduce a soluble metal salt of a doping metal in the sol stage to obtain a metal-doped mesoporous material gel, and then treat the gel 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 a modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid;

[0017] Then, activate and disperse the active gel: mix the modified mesoporous material active gel obtained in the previous step with an activation aid, inorganic acid, and deionized water in a strong shear machine, and then activate and disperse it 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 amount of inorganic acid added is such that the pH of the homogeneous sol slurry of the modified mesoporous material is 0.5-5;

[0018] Finally, the stabilizing aid is added to the slurry of the alumina material precursor, stirred and mixed uniformly, and then the homogeneous sol slurry of the modified mesoporous material and clay obtained in the previous step are added in sequence, stirred and mixed uniformly, and then spray dried to obtain the high-activity mesoporous carrier; the clay is one or more of kaolin, montmorillonite, bentonite, and hydrotalcite.

[0019] Further, 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; and the active metal is one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide, and barium oxide.

[0020] Further, the high-activity solid alkali catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0021] The application further provides a preparation method of the high-activity solid alkali catalyst, comprising the following steps:

[0022] S1, preparing a high-activity mesoporous carrier;

[0023] First, a modified mesoporous material active gel is prepared: 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 mesoporous material gel doped with the metal, 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 a modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid;

[0024] Then, the modified mesoporous material active gel 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 active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid; and the inorganic acid is added in an amount such that the pH of the homogeneous sol slurry of the modified mesoporous material active gel is 0.5-5;

[0025] Finally, the stabilizing agent is added to the alumina material precursor slurry, stirred and mixed uniformly, then the modified mesoporous material active gel homogeneous sol slurry obtained in the previous step and clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain a high-activity mesoporous carrier; the clay is one or more of kaolin, montmorillonite, bentonite, and hydrotalcite;

[0026] S2, preparing a high-activity solid base catalyst;

[0027] The soluble metal salt of the active metal and the soluble metal salt of the auxiliary metal are introduced into the high-activity mesoporous carrier by one of ion exchange, impregnation, and coprecipitation, and then the high-activity solid base catalyst is obtained after drying and calcination.

[0028] Further, the doping metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium, and molybdenum; the weight ratio of the doping metal, in terms of the mass of the metal oxide, to the dry mass of the mesoporous material active gel is 0.001-10:1;

[0029] The activating 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 activating agent to the dry mass of the modified mesoporous material active gel is 0.001-10:1;

[0030] The stabilizing agent is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid, and methacrylic acid-methoxy polyethylene glycol methacrylate; the weight ratio of the stabilizing agent to the alumina material is 0.001-10:1.

[0031] Further, 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 soluble aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.

[0032] Further, the acidified aluminum stone sol is prepared by the following method: aluminum stone is mixed with deionized water, an inorganic acid is added in a ratio of inorganic acid:alumina of 0.05-0.2, and the slurry is mixed and slurried, with the aluminum stone content being controlled 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 selected from one or more of pseudoboehmite, monohydrate, trihydrate, Bayer stone, and aluminum hydroxide.

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

[0034] In addition, the application further provides application of the high-activity solid alkali catalyst in a heavy oil catalytic conversion reaction.

[0035] Compared with the prior art, the high-activity solid alkali catalyst and the preparation method and application thereof have the following advantages:

[0036] (1) High hydrothermal stability and unobstructed pore channel: the modified mesoporous material has excellent adhesion, so that the introduction of a traditional binder with poor hydrothermal stability and small specific surface area can be avoided during catalyst shaping, and the pore blocking problem of the traditional binder to the mesoporous material is completely solved; the specific surface area of the catalyst is as high as 226 m 2 / g after hydrothermal treatment at 800℃ for 17 hours, and the mesoporous pore volume is as high as 0.42 cm 3 / g.

[0037] (2) High catalytic performance: a large number of defect centers are generated in the mesoporous material through metal doping-dissolution, which can effectively anchor the active metal and improve the stability of the active metal under high-temperature hydrothermal harsh conditions. In addition, the active metal can eliminate the strong polar center generated by the aluminum oxide material, thereby improving the selectivity of low-carbon olefins. Specifically, when the high-activity solid alkali catalyst provided by the application is used to treat atmospheric residue, the heavy oil conversion rate is increased by more than 8 percentage points, the liquefied gas yield and triene yield are each increased by more than 7 percentage points, and the content of low-carbon olefins in the liquefied gas is greater than 83 wt%. DETAILED DESCRIPTION

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

[0039] The application aims to provide a solid alkali catalyst with strong heavy metal pollution resistance and high catalytic activity and a preparation method thereof, and particularly relates to a heavy oil non-hydrocracking catalyst, which solves the problem that the heavy oil non-hydrocracking catalyst prepared by the prior art is difficult to efficiently process heavy and poor oil products such as heavy oil and residue for a long period.

[0040] The high-activity solid alkali catalyst provided by the application contains 0.1 wt%-20 wt% of active metal oxides and 0.1 wt%-10 wt% of auxiliary metal oxides, and the balance is a high-activity mesoporous carrier, based on the total weight of the high-activity solid alkali catalyst; the high-activity mesoporous carrier contains 1 wt%-80 wt% of a modified mesoporous material and 1 wt%-50 wt% of an aluminum oxide material, and the balance is clay, based on the total weight of the high-activity mesoporous carrier.

[0041] The active metal oxides are one or more of alkali metal or alkaline earth metal oxides, and are preferably one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide and barium oxide.

[0042] The auxiliary metal oxide is one or more of Y, Ti, Zr, B, Al, Ga, La, Ce oxide.

[0043] The high-activity mesoporous carrier is prepared by the following preparation method:

[0044] First, the modified mesoporous material active gel is prepared: the mesoporous material is prepared by sol-gel method, the soluble metal salt of the doped metal 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 soluble metal salt of the doped metal and the inorganic acid in the gel, thereby obtaining the modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid;

[0045] Then, the active dispersion of the active gel is carried out: the modified mesoporous material active gel obtained in the last step is mixed with the activation auxiliary agent, inorganic acid and deionized water in a strong shearing machine, and then activated and dispersed on a sand mill to obtain a modified mesoporous material homogeneous sol slurry; 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 modified mesoporous material homogeneous sol slurry is 0.5-5;

[0046] Finally, the stable auxiliary agent is prepared into a slurry and sprayed: the stable auxiliary agent is added to the alumina material precursor slurry and stirred and mixed uniformly, then the modified mesoporous material homogeneous sol slurry obtained in the last step and clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain a high-activity mesoporous carrier; the clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite.

[0047] 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; and the active metal is one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide and barium oxide.

[0048] The high-activity solid alkali catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0049] The application further provides a preparation method of the high-activity solid alkali catalyst, which comprises the following steps:

[0050] S1, preparing a high-activity mesoporous carrier;

[0051] First, the preparation of modified mesoporous material active gel: using sol-gel method to prepare mesoporous material, in the sol stage to introduce the soluble metal salt of doped metal, to get the metal doped mesoporous material gel, the gel is treated with inorganic acid solution and deionized water in turn, to remove the soluble metal salt of doped metal and inorganic acid in the gel, to get the modified mesoporous material active gel; the inorganic acid is one or several of nitric acid, sulfuric acid, hydrochloric acid;

[0052] Then, the activation and dispersion of mesoporous material active gel: the modified mesoporous material active gel obtained in the last step is mixed with activation aids, inorganic acid and deionized water in a strong shear machine, and then activated and dispersed on a sand mill to obtain a homogeneous sol slurry of modified mesoporous material active gel; the inorganic acid is one or several of nitric acid, sulfuric acid, hydrochloric acid; the amount of inorganic acid added is such that the pH of the homogeneous sol slurry of modified mesoporous material active gel is 0.5-5;

[0053] Finally, the stable aid is prepared by spraying: the stable aid is added to the alumina material precursor slurry, stirred and mixed uniformly, then the homogeneous sol slurry of modified mesoporous material active gel obtained in the last step and clay are added in turn, stirred and mixed uniformly, and then spray dried to obtain a high-activity mesoporous carrier; the clay is one or several of kaolin, montmorillonite, bentonite and hydrotalcite;

[0054] Among them, the doped metal is one or more of boron, aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the mass of the doped metal, calculated as the mass of metal oxide, to the dry basis mass of the mesoporous material active gel is 0.001-10:1;

[0055] The activation aid is one or several of sodium gluconate, sodium citrate, citric acid, potassium sodium tartrate, tartaric acid, sorbitol, maltitol and polyvinyl alcohol; the weight ratio of the activation aid to the dry basis mass of the modified mesoporous material active gel is 0.001-10:1;

[0056] The stable aid is one or several of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; the weight ratio of the stable aid to the alumina material is 0.001-10:1.

[0057] The alumina material precursor is selected from one or more of an aluminum sol, an acid-alumina sol, and a soluble aluminum salt solution; wherein the soluble aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride; the acid-alumina sol is prepared by mixing alumina stone with deionized water, adding inorganic acid at a ratio of inorganic acid: alumina of 0.05-0.2, and mixing and beating, and controlling the alumina 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 alumina stone is selected from one or more of pseudo-boehmite, monohydrate, trihydrate, bayerite, and aluminum hydroxide.

[0058] S2, preparing a high-activity solid base catalyst;

[0059] The soluble metal salt of the active metal and the soluble metal salt of the auxiliary metal are introduced into the high-activity mesoporous carrier by one of ion exchange, impregnation, and coprecipitation, and then the high-activity solid base catalyst is obtained through drying and calcination.

[0060] The calcination conditions of the high-activity solid base catalyst are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

[0061] The high-activity solid base catalyst of the present application is composed of a high-activity mesoporous carrier, an active metal, and an auxiliary metal. In the preparation method of the high-activity solid catalyst, the mesoporous material is sequentially subjected to metal doping- elution and dispersion activation treatment, so that the modified mesoporous material after secondary solation has good cohesiveness, the forming process does not need to use a traditional binder, the pore structure of the mesoporous material can be maximally preserved, and the hydrothermal stability of the high-activity mesoporous carrier is greatly improved, so that the high-activity solid base catalyst prepared in the present application has a specific surface area of not less than 200 m 2 / g after being treated at 800℃ for 17h. In addition, the active metal component can eliminate part of the strong polar centers in the high-activity mesoporous carrier, further reduce the proportion of strong polar centers in the high-activity solid base catalyst, and improve the selectivity of low-carbon olefins.

[0062] In addition, the present application also provides the use of the above high-activity solid base catalyst in a heavy oil catalytic conversion reaction.

[0063] The technical solutions and technical effects of the present application are further described below through specific examples, and it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, but not to limit the present application.

[0064] Example 1

[0065] The high-activity solid base catalyst is composed of a high-activity mesoporous carrier, an active metal and an auxiliary metal, the active metal oxide is 3 wt%, the auxiliary metal oxide is 2 wt% and the high-activity mesoporous carrier is 95 wt% based on the total weight of the high-activity solid base catalyst; the modified mesoporous material in the high-activity mesoporous carrier is silica, the silica is 55 wt%, the alumina is 10 wt% and the kaolin is 35 wt% based on the total weight of the high-activity mesoporous carrier;

[0066] (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 in a dry weight ratio of gallium oxide to silica of 0.02:1 under constant stirring, followed by slow addition of dilute nitric acid (15%), adjusting the pH 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%);

[0067] (2) Activation and dispersion of active gel: 17.7g of citric acid is added in 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%, the above slurry is mixed with a high shear machine for 30 minutes, and then treated with a sand mill for 60 minutes at a speed of 3000 revolutions / minute to obtain a gallium-modified silica homogeneous sol slurry;

[0068] (3) Stabilizing agent slurry preparation and spraying: 434.8g of aluminum sol (solid content 23%) and 840g of deionized water are taken, 45g of ethylenediaminetetraacetic acid disodium salt is added in a weight ratio of stabilizing agent to aluminum oxide of 0.5:1 and stirred for 30 minutes, followed by the addition of 3235g of gallium-modified silica homogeneous sol slurry (solid content 17%) and stirring for 30 minutes, and finally 407g of kaolin (solid content 86%) is added and stirred for 120 minutes, and then dried and formed using a spray drying device, the outlet temperature is controlled at 135℃, and the catalyst sample with a particle size in the range of 0-200 μm is collected to obtain a high-activity mesoporous carrier;

[0069] (4) Preparation of high-activity solid base catalyst: 114.8g of calcium nitrate tetrahydrate and 24.2g of lanthanum nitrate hexahydrate are dissolved in 855g of deionized water to prepare an impregnation solution; 855g of high-activity mesoporous carrier (water absorption rate 1) is used to load active metal and auxiliary metal by equal volume impregnation method, the catalyst is dried at 120℃ for 6 hours and calcined at 650℃ for 4 hours in a 100% water vapor atmosphere to obtain a high-activity solid base microsphere catalyst.

[0070] Example 2

[0071] The high-activity solid base catalyst is composed of a high-activity mesoporous carrier, an active metal and an auxiliary metal, the active metal oxide is 7 wt%, the auxiliary metal oxide is 3 wt%, and the high-activity mesoporous carrier is 90 wt% based on the total weight of the high-activity solid base catalyst; the modified mesoporous material in the high-activity mesoporous carrier is a silicon-aluminum composite oxide, the silicon-aluminum composite oxide is 50 wt%, the aluminum oxide is 8 wt%, and the kaolin is 42 wt% based on the total weight of the high-activity mesoporous carrier;

[0072] (1) Preparation of mesoporous material active gel: 2000g of water glass solution with a modulus of 3.2 and a silica content of 29.5 wt% was placed in a reactor and heated to 50°C, and 20.18g of chromium nitrate nonahydrate was slowly added under constant stirring at a dry basis weight ratio of gallium oxide to silicon dioxide of 0.005:1, followed by the slow addition of 215.8g of aluminum nitrate nonahydrate, and finally the addition of an appropriate amount of dilute nitric acid (15%) to adjust the pH to about 6, and stirring for 30 minutes to obtain a chromium-modified silicon-aluminum composite oxide gel; 10 wt% of dilute nitric acid solution (1000g) was added and treated at 50°C for 15 hours, and then washed with deionized water until the filtrate was neutral to obtain a chromium-modified silicon-aluminum composite oxide active gel (the solid content of the silicon-aluminum composite oxide in the gel was 19%);

[0073] (2) The active gel was activated and dispersed by the same method as in Example 1, except that 32.47g of tartaric acid was added at a weight ratio of tartaric acid to chromium-modified silicon-aluminum composite oxide active gel (dry basis) of 0.05:1;

[0074] (3) The auxiliary agent was stabilized by slurry spraying by the same method as in Example 1, except that the amounts of aluminum sol (solid content 23%), deionized water and kaolin were 347.8g, 1200g and 488g, respectively;

[0075] (4) The high-activity solid base catalyst was prepared by the same method as in Example 1, except that 68.3g of potassium nitrate and 157.5g of titanium nitrate nonahydrate were used instead of calcium nitrate tetrahydrate and lanthanum nitrate hexahydrate, and the amount of deionized water was 810g.

[0076] Example 3

[0077] The high-activity solid base catalyst is composed of a high-activity mesoporous carrier, an active metal and an auxiliary metal, the active metal oxide is 4 wt%, the auxiliary metal oxide is 3 wt% and the high-activity mesoporous carrier is 93 wt% based on the total weight of the high-activity solid base catalyst; the mesoporous material in the high-activity mesoporous carrier is silica, the silica is 45 wt%, the alumina is 20 wt% and the kaolin is 35 wt% based on the total weight of the high-activity mesoporous carrier;

[0078] (1) The mesoporous material active gel is prepared in the same manner as in Example 1;

[0079] (2) The dispersed active gel is activated in the same manner as in Example 1, except that 5.9 g of polyvinyl alcohol is added in a polyvinyl alcohol to gallium-modified silica active gel (dry basis) weight ratio of 0.01:1;

[0080] (3) Stable auxiliary agent slurry spraying: 285.7 g of pseudoboehmite (solid content of 70%) is added to 1600 g of deionized water and mixed for 30 minutes, 29.2 g of concentrated hydrochloric acid (concentration of 36%) is added, and stirring is continued for 60 minutes, 90 g of citric acid is added in a stable auxiliary agent to alumina weight ratio of 1:1, and stirring is continued for 30 minutes, then 2647 g of gallium-modified silica homogeneous sol slurry (solid content of 17%) is added and stirring is continued for 30 minutes, and finally 407 g of kaolin (solid content of 86%) is added and stirring is continued for 120 minutes, and a spray drying device is used for drying and molding, the outlet temperature is controlled at 135°C, and the catalyst sample with a particle size in the range of 0-200 μm is collected to obtain the high-activity mesoporous carrier;

[0081] (4) The high-activity solid base catalyst is prepared in the same manner as in Example 1, except that 60.6 g of barium acetate is used instead of calcium nitrate hexahydrate, and the amounts of lanthanum nitrate hexahydrate and deionized water are 36.2 g and 930 g, respectively.

[0082] Comparative Example 1

[0083] The catalyst is composed of a carrier, an active metal and an auxiliary metal, the active metal oxide is 3 wt%, the auxiliary metal oxide is 2 wt% and the carrier is 95 wt% based on the total weight of the catalyst; the mesoporous material in the carrier is silica, the silica is 40 wt%, the silica sol (dry basis) is 15 wt%, the aluminum sol (dry basis) is 10 wt% and the kaolin is 35 wt% based on the total weight of the carrier; wherein the main physical property indexes of the silica are: specific surface area 692 m 2 / g, average pore size 5.4 nm, micropore volume 0.01 cm 3 / g, mesopore (2-50 nm pore volume) volume 0.65 cm 3 / g;

[0084] (1) Preparation of catalyst carrier: 400 g of dry silica powder (solid content 90%) and 2730 g of deionized water were mixed and beaten for 30 minutes, 366 g of kaolin (solid content 86%) was added, stirred for 120 minutes, 614 g of silica sol (solid content 22%) was added and stirred for 60 minutes, finally 391.3 g of aluminum sol (solid content 23%) was added, stirred for 30 minutes, and dried and formed using a spray drying device, the outlet temperature was controlled at 135℃, and particles with a particle size in the range of 0~200 um were collected, to obtain a solid base microsphere catalyst.

[0085] (2) Preparation of the catalyst of the comparative example is the same as example 1.

[0086] Comparative example 2

[0087] The catalyst is composed of a carrier, an active metal and an auxiliary metal. Based on the total weight of the catalyst, the active metal oxide is 3 wt%, the auxiliary metal oxide is 2 wt%, and the carrier is 95 wt%; the mesoporous material in the carrier is amorphous silica-alumina, based on the total weight of the carrier, the amorphous silica-alumina is 40 wt%, the silica sol (dry basis) is 15 wt%, the aluminum sol (dry basis) is 10 wt%, and the kaolin is 35 wt%; wherein the main physical property indexes of the amorphous silica-alumina are: specific surface area 597 m 2 / g, average pore size 6.7 nm, micropore volume 0.03 cm 3 / g, mesopore (2-50 nm pore volume) pore volume 0.54 cm 3 / g;

[0088] (1) Preparation of catalyst carrier is the same as comparative example 1;

[0089] (2) Preparation of the catalyst of the comparative example is the same as example 1.

[0090] The catalyst performance evaluation method of the examples and comparative examples of the present application is as follows:

[0091] The catalysts prepared in the examples and comparative examples were 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 they were packed in a fixed fluidized bed evaluation device for catalyst performance evaluation, and the catalyst loading was 600 g. Under the conditions of a reaction temperature of 520℃, a catalyst to oil weight ratio of 6, and a weight hourly space velocity of 15 h -1 , the raw oil with a composition as shown in Table 2 was injected into the fixed fluidized bed device, and the reaction results are shown in Table 3. The heavy oil conversion index calculation formula is as follows:

[0092] Heavy oil conversion index=

[0093] Table 1. Change in pore structure of catalysts before and after hydrothermal treatment

[0094]

[0095] Table 2. Basic properties of raw materials used in examples and comparative examples

[0096]

[0097] Table 3. Evaluation results of samples after hydrothermal treatment of catalysts in examples and comparative examples

[0098]

[0099] As can be seen from the comparison of the above tables, when the high-activity solid alkali catalyst (Examples 1-3) provided by the present application is used to treat atmospheric residue, the product distribution is significantly improved, the heavy oil conversion rate is increased by more than 8 percentage points compared with Comparative Example 2, the liquefied gas yield and triene yield are each increased by more than 7 percentage points, and the low-carbon olefin content in the liquefied gas is greater than 83 wt%.

[0100] The above description is merely preferred embodiments of the present application but not to confine the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A solid base catalyst, characterized by: The solid base catalyst contains 0.1 wt%-20 wt% of active metal oxide and 0.1 wt%-10 wt% of auxiliary metal oxide, with the balance being a mesoporous carrier, based on the total weight of the solid base catalyst; the mesoporous carrier contains 1 wt%-80 wt% of modified mesoporous material and 1 wt%-50 wt% of alumina material, with the balance being clay, based on the total weight of the mesoporous carrier; the sum of the mass fractions of the components in the mesoporous carrier is 100%; The active 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, and Ce oxides. The mesoporous carrier is prepared by the following method: First, a mesoporous material is prepared by a sol-gel method, and a soluble metal salt of a doping metal is introduced in the sol stage to obtain a metal-doped mesoporous material gel, 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 a modified mesoporous material active gel; 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 as metal oxide to the dry mass of the modified mesoporous material active gel is (0.001-10):

1. Then, the modified mesoporous material active gel obtained in the previous step is mixed with an activation auxiliary agent, an inorganic acid, and deionized water in a strong shear 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, then the homogeneous sol slurry of the modified mesoporous material obtained in the previous step and clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain a 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 clay is one or more of kaolin, montmorillonite, bentonite, and hydrotalcite.

2. The solid base catalyst according to claim 1, characterized by: The active metal oxide is one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide, and barium oxide.

3. The solid base catalyst according to claim 1, characterized by: The solid base catalyst is a microspherical catalyst with a particle size of 0-200 μm, and 0 is not included.

4. A process for the preparation of a solid base catalyst according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: S1, preparing a mesoporous carrier: First, the mesoporous material is prepared by sol-gel method, and a soluble metal salt of a doped metal is introduced in the sol stage to obtain a mesoporous material gel doped with the metal, and then the gel is treated with inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doped metal and the inorganic acid in the gel, thereby obtaining a modified mesoporous material active gel; 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 doped metal is one or more of aluminum, gallium, copper, chromium, vanadium, zirconium and molybdenum; the weight ratio of the doped metal (calculated as the mass of metal oxide) to the dry mass of the modified mesoporous material active gel is (0.001-10):1; Then, the modified mesoporous material active gel obtained in the previous step is mixed with an activation aid, inorganic acid and deionized water in a strong shear 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, stirred and mixed uniformly, and then the homogeneous sol slurry of the modified mesoporous material obtained in the previous step and clay are added in sequence, stirred and mixed uniformly, and then spray dried to obtain a 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 clay is one or more of kaolin, montmorillonite, bentonite and hydrotalcite; S2, preparation of a solid base catalyst: The soluble metal salt of the active metal and the soluble metal salt of the aid metal are introduced into the mesoporous carrier by any one of ion exchange method, impregnation method and coprecipitation method, and then dried and calcined to obtain the solid base catalyst; The calcination conditions are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

5. The preparation method of the solid base catalyst according to claim 4, characterized in that: The weight ratio of the activation aid to the dry mass of the modified mesoporous material active gel is (0.001-10):1; The weight ratio of the stabilizing aid to the alumina material is (0.001-10):

1.

6. The method of preparing a solid base catalyst according to claim 4, characterized by: 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 = 0.05-0.2, and controlling the aluminum stone content in the slurry to be 1 wt%-25 wt%; the aluminum stone is selected from one or more of pseudoboehmite, monohydrate, trihydrate, bayerite and aluminum hydroxide; the inorganic acid is one or more of nitric acid, sulfuric acid and hydrochloric acid; The soluble aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

7. Use of the solid base catalyst according to any one of claims 1 to 3 in a heavy oil non-hydrocracking reaction.

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