A solid base catalyst, its preparation method and application

Abstract

The application provides a solid base catalyst and a preparation method and application thereof, and belongs to the field of heavy oil non-hydrogen reduction viscosity cracking catalysts. The solid base catalyst is composed of modified mesoporous materials, active metals, auxiliary metals and clay, and is applied in heavy oil catalytic conversion reaction. In the preparation method, a metal doping-dissolution process is innovatively adopted on the mesoporous material gel to construct a large number of defect sites, and under the action of an activation auxiliary and mechanical external force, the active gel is secondary sol-gelized, and has the dual functions of stabilizing the mesoporous material and the binder. Therefore, the traditional binder is not needed, the proportion of the mesoporous material can be greatly adjusted, and the pore structure of the mesoporous material is maximally reserved. The specific surface area of the solid base catalyst prepared by the method of the application is still not less than 270 m 2 / g after hydrothermal treatment at 800 DEG C for 17 hours. When the vacuum residue is treated, the heavy oil conversion rate is increased by more than 5 percentage points, the dry gas yield is reduced by more than 1 percentage point, and the coke yield is reduced by more than 5 percentage points.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of heavy oil non-hydro-visbreaking catalysts, and particularly relates to a solid base catalyst and a preparation method and application thereof. 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 the future development of oil refining; 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 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 carbanion, and the catalyst mostly uses acid molecular sieve as the active component, and the commonly used molecular sieves include ReY, USY, ZSM-5 molecular sieve, etc. The heavy and poor quality 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. The conventional acid catalytic cracking catalyst is difficult to effectively process heavy and poor quality heavy oil due to the diffusion limitation of the pore channel; the diffusion rate of heavy and poor quality heavy 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 macromolecules such as resin and asphaltene in 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 the focus of the world's oil industry and a world-wide technical problem, but also a major problem that needs to be solved in the domestic oil industry.

[0004] In recent years, solid base catalytic materials have developed rapidly, and have been applied in the preparation of biodiesel and ester exchange reaction processes, 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 catalyst has the characteristics of low hydrogen transfer activity and moderate conversion depth, and has unique advantages in heavy oil conversion reaction, and is becoming a research hotspot in this field; the stable and reliable alkali catalyst and the preparation method are the technical key to support its application 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, etc. as raw materials, and is prepared into catalyst particles with particle size of 100-200 mesh through impregnation, mixing, filtration, calcination and grinding; but the mechanical strength of the catalyst prepared by this method is poor, which 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 they have the characteristics of low yield of additional value products such as dry gas and coke. However, the existing solid base catalysts generally have problems such as poor hydrothermal stability and insufficient catalytic activity. Therefore, it is of good application prospect to develop a solid base catalyst with high hydrothermal stability, high activity and high selectivity for processing heavy and poor oil such as heavy oil and residual oil. SUMMARY

[0011] In view of the above, the present application aims to provide a solid base catalyst with high hydrothermal stability, high activity and selectivity, and a preparation method thereof, to solve the problem that the catalyst prepared by the prior art is difficult to process heavy and poor oil products 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 full-range residual oil, maximally inhibit hydrogen transfer reaction, and greatly reduce the generation of dry gas and coke.

[0012] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows: a solid base catalyst, wherein, based on the total weight of the solid base catalyst, the solid base catalyst contains 1 wt%-99 wt% of modified mesoporous material, 0.1 wt%-20 wt% of active metal oxide, and 0.1 wt%-10 wt% of auxiliary metal oxide, 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 modified mesoporous material is prepared by the following preparation method:

[0016] 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 metal, and the gel is then treated with inorganic acid solution and deionized water in sequence to remove the soluble metal salt of the doping metal and 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, the modified mesoporous material active gel is activated and dispersed: 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 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; the inorganic acid is added in an amount such that the pH of the slurry is 0.5-5.

[0018] Further, 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.

[0019] Further, the solid base catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0020] A preparation method of the above-mentioned solid base catalyst, comprising the following steps:

[0021] Step 1, preparation of modified mesoporous material active gel: mesoporous material is prepared by sol-gel method, and a soluble metal salt of doped metal is introduced in the sol stage to obtain a mesoporous material gel doped with metal, which is then treated with inorganic acid solution and deionized water in sequence to remove the soluble metal salt of doped metal and 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;

[0022] Step 2, activation and dispersion of the modified mesoporous material active gel: the active gel obtained in step 1 is mixed with an activation aid, 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; the inorganic acid is added in an amount such that the PH of the slurry is 0.5-5;

[0023] Step 3, preparation of a slurry of a stabilizing aid: the soluble metal salt of active metal and the soluble metal salt of aid metal are mixed with a stabilizing aid and deionized water, and then the sol slurry obtained in step 2 and clay are added in sequence, followed by stirring and mixing, and then spray drying and calcination to obtain a solid base catalyst.

[0024] 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 (calculated as the mass of metal oxide) to the dry mass of the modified mesoporous material active gel is 0.001-10:1.

[0025] Further, the activation aid 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 aid to the dry mass of the modified mesoporous material active gel is 0.001-10:1.

[0026] Further, the stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate.

[0027] Further, the calcination conditions of the solid base catalyst are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

[0028] The application also provides application of the above-mentioned base catalyst in catalytic conversion of heavy oil.

[0029] In the preparation method of the solid catalyst, a metal doping-dissolution process is innovatively adopted to construct a large number of defect sites on the mesoporous material gel, and under the action of an activation aid and mechanical external force, the active gel is sol-gelized again, which has the dual functions of stabilizing the mesoporous material and the binder, so that the traditional binder is not needed, the proportion of the mesoporous material can be greatly adjusted, and the pore structure of the mesoporous material is maximally reserved. Compared with the conventional binder, the pore structure of the modified mesoporous material is controllable, and the hydrothermal stability is significantly improved, so that the specific surface area of the solid base catalyst prepared by the method of the application is still not less than 270 m 2 / g after hydrothermal treatment at 800 DEG C for 17 hours.

[0030] Compared with the prior art, the solid base catalyst, the preparation method and the application thereof have the following advantages:

[0031] (1) High hydrothermal stability and unobstructed pore channel of the catalyst: the modified mesoporous material has excellent adhesion, so that the introduction of the traditional binder with poor hydrothermal stability and small specific surface area can be avoided in the catalyst forming process, 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 316 m 2 / g after hydrothermal treatment at 800 DEG C for 17 hours, and the mesopore volume is as high as 0.43 cm 3 / g.

[0032] (2) High catalytic performance: a large number of defect centers are generated in the mesoporous material by the metal doping-dissolution, which can effectively anchor the active metal to the position, and improve the stability of the active metal under high-temperature hydrothermal harsh conditions. Specifically, when the solid base catalyst provided by the application is used to treat the vacuum residue, the heavy oil conversion rate is increased by more than 5 percentage points, the dry gas yield is reduced by more than 1 percentage point, the coke yield is reduced by more than 5 percentage points, the liquefied gas yield is increased by more than 5 percentage points, and the content of low-carbon olefins in the liquefied gas is greater than 85 wt%. DETAILED DESCRIPTION

[0033] It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other without conflict.

[0034] The application relates to a solid base catalyst, in particular to a heavy oil non-hydrogen-assisted viscosity-reducing cracking solid base catalyst.

[0035] The active metal oxide is one or more of alkali metal or alkaline earth metal oxides, preferably one or more of potassium oxide, rubidium oxide, magnesium oxide, calcium oxide, and barium oxide.

[0036] The auxiliary metal oxide is one or more of Y, Ti, Zr, B, Al, Ga, La, and Ce oxides.

[0037] The modified mesoporous material is prepared by the following method:

[0038] First, the modified mesoporous material active gel is prepared: the mesoporous material is prepared by the sol-gel method, and 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 the modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid.

[0039] Then, the modified mesoporous material active gel is activated and dispersed: 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 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; the inorganic acid is added in an amount such that the pH of the slurry is 0.5-5.

[0040] 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.

[0041] The solid base catalyst is a microspherical catalyst with a particle size of 0-200 μm.

[0042] A preparation method of the above solid base catalyst, comprising the following steps:

[0043] Step 1, preparation of the modified mesoporous material active gel: the mesoporous material is prepared by the sol-gel method, and 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 the modified mesoporous material active gel; the inorganic acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid.

[0044] Step 2, activation dispersion modification mesoporous material active gel: the active gel obtained in step 1 is mixed with 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 modified mesoporous material active gel; 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 slurry is 0.5-5;

[0045] Step 3, stable aid slurry spraying: the soluble metal salt of the active metal and the soluble metal salt of the aid metal are mixed with the stable aid and deionized water, then the sol slurry obtained in step 2 and clay are added in turn, and after stirring and mixing uniformly, spray drying and calcination are carried out to obtain a solid base catalyst.

[0046] Among them, the doping metal is one or more of boron, 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 basis mass of the modified mesoporous material active gel is 0.001-10:1.

[0047] The activation aid 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 aid to the dry basis mass of the modified mesoporous material active gel is 0.001-10:1.

[0048] The stable aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate.

[0049] The solid base catalyst calcination condition is calcination treatment at 450-750 DEG C under 0-100% water vapor for 0.5-4h.

[0050] The application also provides the use of the above-mentioned solid base catalyst in heavy oil catalytic conversion reactions.

[0051] The solid base catalyst provided by the application is composed of modified mesoporous material, active metal, aid metal and clay. In the preparation method of the solid catalyst, the metal doping-dissolution process is innovatively adopted to construct a large number of defect sites on the mesoporous material gel, and under the action of activation aid and mechanical external force, the active gel is solubilized again, which has the dual functions of stabilizing the mesoporous material and the binder, so that the traditional binder is not needed, the proportion of the mesoporous material can be greatly adjusted, and the pore structure of the mesoporous material is maximally reserved. Compared with the conventional binder, the pore structure of the modified mesoporous material is controllable, and the hydrothermal stability is significantly improved, so that the specific surface area of the solid base catalyst prepared by the method of the application is still not less than 270 m 2 / g after hydrothermal treatment at 800 DEG C for 17 hours.

[0052] The following describes the process of the present application in detail through specific comparative examples and examples. 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.

[0053] Example 1

[0054] The solid base catalyst is composed of modified mesoporous material, active metal, auxiliary metal and kaolin, wherein the mesoporous material is selected from silica; based on the total weight of the solid base catalyst, the silica is 60 wt%, the active metal oxide is 3 wt%, the auxiliary metal oxide is 2 wt%, and the kaolin is 35 wt%;

[0055] (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 the slow addition of dilute nitric acid (15%) to adjust the pH to about 6, and stirring for 30 minutes to obtain a gallium-modified silica hydrogel; 10 wt% of dilute nitric acid solution (1000g) is added at 50℃ for 15 hours, followed by washing with deionized water until the filtrate is neutral, to obtain a gallium-modified silica active gel (the silica solid content in the gel is 19%);

[0056] (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 at 1.5 and the silica solid content at 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 3000 revolutions / minute to obtain a gallium-modified silica homogeneous sol slurry;

[0057] (3) Stabilizing auxiliary agent slurry spraying: 114.8g of calcium nitrate tetrahydrate and 24.2g of lanthanum nitrate hexahydrate are dissolved in 950g of deionized water, and 4.5g of disodium ethylenediaminetetraacetate is added at a weight ratio of stabilizing auxiliary agent to active metal and auxiliary metal oxide of 0.1:1, and stirred for 30 minutes, followed by the addition of 3176g of gallium-modified silica homogeneous sol slurry (solid content 17%) and stirring for 30 minutes, and finally 366g of kaolin (solid content 86%) is added and stirred for 120 minutes, and then dried and formed using a spray drying device, with the outlet temperature controlled at 135℃, and the catalyst sample with a particle size in the range of 0-200 μm is collected, and calcined in a 100% water vapor atmosphere at 650℃ for 4 hours to obtain a solid base microsphere catalyst.

[0058] Example 2

[0059] The solid base catalyst is composed of modified mesoporous material, active metal, auxiliary metal and kaolin, wherein the mesoporous material is selected from silicon-aluminum composite oxide; based on the total weight of the solid base catalyst, the silicon-aluminum composite oxide is 50 wt%, the active metal oxide is 8 wt%, the auxiliary metal oxide is 2 wt%, and the kaolin is 40 wt%;

[0060] (1) The mesoporous material active gel was prepared as follows: 2000 g 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 20.18 g of chromium nitrate nonahydrate was slowly added under constant stirring at an oxygen weight ratio of gallium to silicon dioxide of 0.005:1, followed by the slow addition of 215.8 g 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 (1000 g) was added 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%);

[0061] (2) The active gel was activated and dispersed by the same method as in Example 1, except that 32.5 g 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;

[0062] (3) The auxiliary agent was stabilized by slurry spraying by the same method as in Example 1, except that 68.3 g of potassium nitrate and 157.5 g of titanium nitrate nonahydrate were used instead of calcium nitrate tetrahydrate and lanthanum nitrate hexahydrate, and the amount of deionized water was 1430 g.

[0063] Example 3

[0064] The solid base catalyst is composed of modified mesoporous material, active metal, auxiliary metal and kaolin, wherein the modified mesoporous material is selected from silicon-magnesium composite oxide; based on the total weight of the solid base catalyst, the silicon-magnesium composite oxide is 70 wt%, the active metal oxide is 5 wt%, the auxiliary metal oxide is 5 wt%, and the kaolin is 20 wt%;

[0065] (1) The modified mesoporous material active gel was prepared by the same method as in Example 2, except that 250.2 g of magnesium nitrate hexahydrate was used instead of aluminum nitrate nonahydrate;

[0066] (2) The active gel was activated and dispersed in the same way as in Example 2;

[0067] (3) The same method as in Example 1 was used to stabilize the pulp spray aid, except that 72.7 g of cerium nitrate hexahydrate was used instead of lanthanum nitrate hexahydrate, and the amount of calcium nitrate tetrahydrate was 153.1 g.

[0068] Comparative Example 1

[0069] The catalyst was composed of mesoporous material, active metal, auxiliary metal, silica sol and kaolin, wherein the mesoporous material was selected from silica; based on the total weight of the catalyst, the silica was 36 wt%, the active metal oxide was 3 wt%, the auxiliary metal oxide was 2 wt%, the silica sol (dry basis) was 24 wt%, and the kaolin was 35 wt%; wherein the main physical property indexes of the silica were: 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.

[0070] 360 g of dry silica powder (solid content 90%) and 2650 g of deionized water were mixed and pulped for 30 minutes, 366 g of kaolin (solid content 86%) was added, stirred for 120 minutes, 982 g of silica sol (solid content 22%) was added and stirred for 60 minutes, finally 114.8 g of calcium nitrate tetrahydrate and 24.2 g of lanthanum nitrate hexahydrate were added and stirred for 60 minutes, then a spray drying device was used for drying and shaping, the outlet temperature was controlled at 135°C, the particles with a particle size in the range of 0-200 μm were collected, and the solid base microspherical catalyst was obtained by calcining at 650°C for 4 hours in a 100% water vapor atmosphere.

[0071] Comparative Example 2

[0072] The catalyst was composed of mesoporous material, active metal, auxiliary metal, silica sol and kaolin, wherein the mesoporous material was selected from amorphous silica aluminum; based on the total weight of the catalyst, the amorphous silica aluminum was 36 wt%, the active metal oxide was 3 wt%, the auxiliary metal oxide was 2 wt%, the silica sol (dry basis) was 24 wt%, and the kaolin was 35 wt%; wherein the main physical property indexes of the amorphous silica aluminum were: 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) volume 0.54 cm 3 / g.

[0073] The catalyst preparation method was the same as in Comparative Example 1.

[0074] The catalyst performance evaluation method of the examples and comparative examples of the present application is as follows:

[0075] The catalysts prepared in the examples and comparative examples were treated at 800°C for 17 hours in a 100% water vapor atmosphere. The pore structure characterization data of each catalyst before and after hydrothermal treatment are detailed in Table 1. Subsequently, the catalysts were loaded into a fixed fluidized bed evaluation device for performance evaluation, with a catalyst loading of 600 g. The reaction was conducted at a temperature of 520°C, a catalyst-to-oil weight ratio of 6, and a weight hourly space velocity of 15 h⁻¹. -1 Under 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:

[0076] Heavy oil conversion index =

[0077] Table 1. Changes in pore structure of catalysts in the examples and comparative examples before and after hydrothermal treatment.

[0078]

[0079] Table 2. Basic properties of raw materials used in the examples and comparative examples.

[0080]

[0081] Table 3 Evaluation results of hydrothermal samples of catalysts in the examples and comparative examples.

[0082]

[0083] The comparison of the above tables shows that when the solid alkali catalyst (Examples 1-3) provided by the present invention is used to treat vacuum residue, the product distribution is significantly improved. Compared with Comparative Example 2, the heavy oil conversion rate is increased by more than 5 percentage points, the dry gas yield is reduced by more than 1 percentage point, the coke yield is reduced by more than 5 percentage points, the liquefied gas yield is increased by more than 5 percentage points, and the low-carbon olefin content in the liquefied gas is greater than 85 wt%.

[0084] 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 base catalyst, characterized by: The solid base catalyst contains 1 wt%-99 wt% of the modified mesoporous material, 0.1 wt%-20 wt% of the active metal oxide and 0.1 wt%-10 wt% of the auxiliary metal oxide, with the balance being clay, based on the total weight of the solid base catalyst; the sum of the mass fractions of the components in the solid base catalyst 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 preparation method of the solid base catalyst comprises the following steps: 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 in terms 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 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 active gel; 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 slurry 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; The soluble metal salt of the active metal and the soluble metal salt of the auxiliary metal are stirred and mixed uniformly with a stabilizing auxiliary agent and deionized water, and then the sol slurry obtained in the previous step and clay are added in sequence, stirred and mixed uniformly, and then spray dried, calcined, to obtain the solid base catalyst; 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 calcination conditions are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

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

3. A process for the preparation of the solid base catalyst according to claim 1 or 2, characterized in that, The preparation method comprises the following steps: Step 1, preparation of the modified mesoporous material active gel: 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 doping metal to the dry mass of the modified mesoporous material active gel is (0.001-10):

1. Step 2, activation and dispersion of the modified mesoporous material active gel: The modified mesoporous material active gel obtained in step 1 is mixed with an activation aid, 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 active gel; 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 slurry 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; Step 3, stabilizing aid slurry spraying: The soluble metal salt of the active metal and the soluble metal salt of the aid metal are mixed with the stabilizing aid and deionized water, and then the sol slurry obtained in step 2 and clay are added in sequence, stirred and mixed uniformly, and then spray dried, calcined to obtain a solid alkali catalyst; The stabilizing aid is one or more of polyacrylamide, melamine, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, citric acid and methacrylic acid-methoxy polyethylene glycol methacrylate; The calcination conditions are calcination treatment at 450-750℃ under 0-100% water vapor for 0.5-4h.

4. The method for preparing a solid base catalyst according to claim 3, characterized by: The weight ratio of the activation aid to the dry mass of the modified mesoporous material active gel is (0.001-10):

1.

5. Use of the solid alkali catalyst of claim 1 or 2 in a heavy oil non-hydrogen-assisted viscosity reduction and cracking reaction.

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