WO2023036155A1

WO2023036155A1 - Solid base catalyst and preparation method therefor

Info

Publication number: WO2023036155A1
Application number: PCT/CN2022/117399
Authority: WO
Inventors: 吴青; 李滨; 郭春垒; 臧甲忠; 孙振海; 何鸣元; 范景新; 郭健; 靳凤英; 宫毓鹏
Original assignee: 中海油天津化工研究设计院有限公司; 中国海洋石油集团有限公司
Priority date: 2021-09-07
Filing date: 2022-09-06
Publication date: 2023-03-16
Also published as: CN113509925B; CN113509925A

Abstract

Disclosed are a solid base catalyst and a preparation method therefor. The solid base catalyst is composed of an active component, an auxiliary agent, a forming aid and a solid base catalyst carrier. The solid base catalyst carrier is a highly mesoporous catalytic carrier. The solid base catalyst carrier has undergone a pore thickening treatment, transition metal doping, and a surface modification treatment, which improves the hydrothermal stability of the catalyst, eliminates some polar centers, reduces the ability of the catalyst to adsorb polycyclic aromatic hydrocarbons and non-hydrocarbon impurities in heavy oil, and increases the service life of the catalyst. The present invention further provides a preparation method for the solid base catalyst, which prepares microspherical, strip-shaped and spherical catalysts, and may be used in the reaction processes of fluidized bed catalytic cracking, fixed beds, moving beds and the like. The solid base catalyst of the present invention has a coke yield of less than 10 wt% and a selectivity of low-carbon olefins in liquefied gas greater than 80% during the catalytic cracking process of heavy oil and residual oil having a residual carbon content greater than 10 wt%.

Description

A kind of solid base catalyst and preparation method thereof

technical field

The invention relates to a solid base catalyst and a preparation method.

Background technique

The research on solid base catalyst materials and solid base catalytic reactions has achieved rapid development. The use of solid base catalysts in the fields of biodiesel production, olefin isomerization, and heavy oil conversion and utilization has become a research hotspot. Base catalysts with stable and reliable performance and their preparation methods are key technologies.

With the depletion of light oil resources worldwide, the trend of heavy crude oil in the world has made refineries increasingly desire to convert heavy residue oil into light and high-priced products, especially the heavy and inferior crude oil in my country. The trend is more obvious. The common technology for converting heavy oil into light oil is catalytic cracking, and catalytic cracking units occupy an important position in my country's oil refining industry. Due to the characteristics of flexible operation, high light oil yield, low investment and operating costs, catalytic cracking technology has become one of the most important secondary processing methods for petroleum. At present, acidic molecular sieve catalysts are mostly used as active components in catalytic cracking. Common molecular sieves are Y-type molecular sieves or ZSM-5 molecular sieves. Acidic catalysts are prone to hydrogen transfer reactions, carbon deposition reactions, and low value-added product yields such as dry gas and coke. High, and the acidic catalytic cracking catalyst cannot directly process residual oil or even poorer unconventional petroleum resources. Basic catalysts have advantages in catalytic cracking reactions due to the presence of basic active centers.

Solid base catalysts have been applied industrially in biodiesel preparation, transesterification and other reaction processes. CN109663585A discloses a preparation method of a solid alkali catalyst, using waste catalyst, sepiolite, calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate and other materials as raw materials, after impregnation, mixing, filtration, and finally roasting at 500-900 ° C , cooled, and ground to 100-200 mesh particles, and the spent catalyst used in the method is catalytic cracking spent catalyst.

CN101755036 discloses the use of basic materials and a solid base catalyst with few large-pore zeolites or even no large-pore zeolites for the production of LCO distillates with lower aromatics content in catalytic cracking to increase the LCO yield or propylene yield . The patent discloses that the alkaline material is hydrotalcite, aluminum phosphate, transition metal, alkali metal, alkaline earth metal oxide or hydroxide, and the carrier used is high temperature resistant oxide silicon dioxide, aluminum oxide, titanium oxide and mixtures. According to the publication, the catalyst composition also includes a part of acid sites and small-pore zeolites, wherein the acid sites are composed of silica sol, metal-doped silica sol, and a mixture of silica sol and other high-temperature-resistant composite materials, with small pores Zeolite is ZSM-5 molecular sieve. This patent mainly introduces basic centers to suppress hydrogen transfer and dehydrogenation reactions, and reduce the content of aromatics in LCO oil.

The solid base catalyst disclosed in patent CN109663585A is used in the field of biodiesel preparation, and the catalyst particles are prepared by a grinding method. The mechanical strength of the catalyst cannot meet the requirements of industrial cracking units for the catalyst. Although CN107115853A and CN101755036 introduce basic centers into catalytic cracking reactions, the catalysts have poor high-temperature stability, low resistance to metal and non-hydrocarbon impurities, and cannot stably process full-fraction residues and oils with high residual carbon content for a long period of time. Super heavy oil such as sand bitumen.

CN100389177C discloses a heavy oil catalytic cracking catalyst containing alumina and molecular sieves, which uses type zeolite as the main active component, and contains a certain amount of phosphorus and rare earth metals. For liquefied gas, the catalyst can be used to treat the mixed oil of vacuum wax oil and vacuum residue, and the saturated hydrocarbon content is not less than 50%, the colloid content is not more than 14%, and the residual carbon content is not more than 4%.

CN107115853A discloses a Mg-Al hydrotalcite catalyst for treating residual oil and super heavy oil raw materials and a preparation method thereof. The preparation method of the disclosed catalyst includes preparing a mixed aqueous solution of magnesium nitrate and aluminum nitrate, preparing an alkaline aqueous solution of sodium carbonate and sodium hydroxide, then adding the mixed aqueous solution and the alkaline aqueous solution to water, and stirring to prepare Mg-Al hydrotalcite The material is obtained by mixing Mg-Al hydrotalcite material with clay and binder slurry, followed by spray drying and roasting. The Mg-Al hydrotalcite catalyst can be directly used in conventional catalytic cracking to produce high-quality gasoline and diesel oil, and the Mg-Al hydrotalcite catalyst also belongs to the solid base catalyst.

In the above method CN100389177C and other similar patents, the existing acidic catalytic cracking catalysts cannot directly process super-heavy oils such as whole distillate residues with high residual carbon content and oil sand bitumen, and when processing lighter heavy oils, due to the presence of acid centers, occurrence Hydrogen transfer and dehydrogenation reactions, resulting in high dry gas yield, high coke yield, and low selectivity to light olefins. The solid base catalyst has a basic center, which can avoid hydrogen transfer and dehydrogenation reactions and improve the selectivity of low-carbon olefins. However, the existing solid base catalysts generally have poor stability problems. For example, hydrotalcite solid base catalysts gradually transform into low-activity spinel structures under high temperature conditions, and it is difficult to process low-quality heavy oil with high carbon residues. Therefore, it is necessary to develop a Inferior heavy oil alkali catalysts with excellent structural properties have good application prospects.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a solid base catalyst suitable for heavy oil processing, with moderate alkalinity, excellent mass transfer effect, high hydrothermal stability, and high stability against metal poisoning, and a preparation method thereof. The solid base catalyst provided by the invention can stably process full distillate residual oil with high residual carbon content and ultra-heavy oil such as oil sand bitumen for a long period of time, and can also be used for processing conventional heavy oil.

The present invention realizes above-mentioned object by following technical means:

A solid base catalyst, which is composed of an active component, an auxiliary agent, a forming aid, and a solid base catalyst carrier. In terms of the total mass percentage of the catalyst, the active component is 0.02-70 wt%, the auxiliary agent is 0.02-5 wt%, and the forming aid is Agent 2～20wt%, solid alkali catalyst carrier is 20～95wt%, solid alkali catalyst carrier is made up of solid alkali catalyst structure carrier and solid alkali catalyst carrying heat carrier, solid alkali catalyst structure carrier and carrying heat carrier mass ratio are (3: 1)-(1:3);

The active component is one or more of alkali metal or alkaline earth metal oxides, alkali metal or alkaline earth metal salts;

The auxiliary agent is one or several kinds of rare earth metals;

The forming aid is one or more of silica sol, aluminum sol, and water glass;

The mesoporous (2-50nm) pore volume of the solid base catalyst structure carrier accounts for greater than 95% of the total pore volume, preferably greater than 98%, and is prepared by the following preparation method:

1) Channel thickening treatment: the carrier precursor gel is first treated with an alcohol solvent, then treated with an alcohol solvent containing modified components, and finally treated with water, and dried to obtain a carrier precursor with thickened channels. The active component is one or more of tetraethyl orthosilicate, silicon tetrachloride, titanium tetrachloride, and n-butyl titanate, and the mass proportion of the modified component in the carrier is 0.05-10 wt %; The carrier precursor gel is one or more of silicon-containing composite oxide gel, high silicon molecular sieve gel, silica gel, alumina gel, and the alcohol solvent is methanol, ethanol One or more of , propanol, isopropanol and ethylene glycol;

2) Transition metal doping: Doping the transition metal skeleton on the carrier precursor with thickened channels, dissolving the transition metal salt in the inorganic acid solution, treating the carrier precursor with thickened channels, and washing the residual metal salt after treatment Obtain a transition metal doped carrier precursor; the transition metal salt is a soluble metal salt such as manganese, tungsten, molybdenum, titanium, germanium, tin, zirconium; the inorganic acid solution is one of sulfuric acid solution, nitric acid solution, hydrochloric acid solution or Several;

3) Surface modification treatment: modify the surface of the transition metal-doped carrier precursor with a modified solution, and make it after drying, wherein the solvent of the modified solution is water, ethanol, acetone, cyclohexane One or more, the solute is one or more of methylchlorosilane, dimethylchlorosilane and trimethylchlorosilane.

In the above technical solution of the present invention, the solid base catalyst is a microspherical solid base catalyst with a particle size of 10-200 μm, which is used for fluidized bed base catalytic cracking reaction.

In the above technical solution of the present invention, the solid base catalyst is a strip-shaped catalyst with a diameter of 0.8-2 mm, and the cross-sectional shape of the strip is cylindrical, clover, four-leaf clover or Raschig ring.

In the above technical solution of the present invention, the solid base catalyst is spherical with a diameter of 0.5-3.0 mm.

In the above technical solution of the present invention, the silicon-containing composite oxide is preferably one or more of silicon-aluminum composite oxide, silicon-titanium composite oxide, and silicon-magnesium composite oxide.

In the above technical solution of the present invention, preferably, the forming aid is one or more of large particle size silica sol, high viscosity silica sol, low sodium silica sol, and water glass.

The heat-carrying carrier of the solid base catalyst is kaolin.

In the above-mentioned technical solution of the present invention, it is preferred that the rare earth metal is one of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu species or several.

In the above technical solution of the present invention, preferably the active component is one of the first main group metal oxide, the second main group metal oxide, the first main group metal salt, and the second main group metal salt or several, more preferably one or more of potassium oxide, magnesium oxide, calcium oxide, barium oxide, potassium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, potassium carbonate, magnesium carbonate, and calcium carbonate.

The solid base catalyst structure carrier of the above composition has a higher mesopore ratio, and the mesopore (2-50nm) pore volume ratio of the carrier is greater than 95%, preferably the mesopore (2-50nm) pore volume ratio of the carrier is greater than 98%. It has a good mass transfer effect in the treatment of heavy oil such as residual oil and oil sand bitumen.

The present invention also provides a method for preparing a solid base catalyst, comprising the steps of:

1) Preparation of solid base catalyst structure support

a) Pore thickening treatment: replace the water in the carrier precursor gel with an alcohol solvent, then replace it with an alcohol solvent containing a modified component, and finally replace the ethanol solution with water and catalyze the hydrolysis of the modified component After drying, the carrier precursor with thickened pores is obtained, and the modified component used is one or more of ethyl orthosilicate, silicon tetrachloride, titanium tetrachloride, and n-butyl titanate. The carrier precursor gel is one or more of silicon-containing composite oxide gel, high-silicon molecular sieve gel, silica gel, and alumina gel, and the alcohol solvent is methanol, ethanol, acrylic acid, etc. One or more of alcohol, isopropanol, and ethylene glycol;

b) Transition metal doping: dope the transition metal skeleton to the carrier precursor with thickened channels, dissolve the transition metal salt in the inorganic acid solution, and treat the carrier precursor with thickened channels at 10-90°C, after treatment After washing the residual metal salt, a transition metal-doped carrier precursor is obtained; the transition metal salt is a soluble metal salt of manganese, tungsten, molybdenum, titanium, germanium, tin, zirconium, etc.; the inorganic acid solution is sulfuric acid solution, nitric acid solution, One or more of the hydrochloric acid solution;

c) Surface modification treatment: modify the surface of the transition metal-doped carrier precursor, and then dry it. The solvent of the modified solution is one or more of water, ethanol, acetone, and cyclohexane, and the solute One or more of methylchlorosilane, dimethylchlorosilane, and trimethylchlorosilane;

2) Preparation of solid base catalyst

The forming aid, solid base catalyst structure carrier and heat-carrying carrier are pulverized into powder, then mixed with active components and aids, and then shaped, dried and calcined to obtain a solid base catalyst.

In the above preparation method of the present invention, step c) surface modification treatment is preferably carried out under the conditions of a temperature of 10-100° C. and a pressure of 0-1.0 MPa.

In the above preparation method of the present invention, the molding described in the step of preparing the solid base catalyst is preferably spray drying, rolling ball molding, extrusion molding or intensive granulation molding.

The present invention further provides the application of the above-mentioned solid base catalyst in heavy oil catalytic cracking reaction. In the above applications, the solid base catalyst is a microspherical solid base catalyst with a particle size of 10-200 μm, preferably used in heavy oil fluidized catalytic cracking reactions, more preferably used to treat residual oil with high residual carbon content, Vacuum residual oil, crude oil and other heavy oil fluidized catalytic cracking reaction.

The present invention further provides the application of the strip-shaped solid base catalyst in fixed-bed base-catalyzed reaction.

The present invention further provides the application of the above-mentioned spherical solid base catalyst in fixed bed or moving bed base catalytic reaction.

The solid base catalyst used in the fluidized bed base catalytic cracking reaction is a microspherical catalyst, the particle size distribution is 20-200 μm, the forming method is spray drying method, the inlet temperature of the spray drying tower is 300-500 °C, and the outlet temperature is 90-90 °C 120°C.

The solid base catalyst used in fixed bed or moving bed adopts spherical solid base catalyst, and the forming aid, solid base catalyst structural support and heat carrier are crushed into powder with a D50 particle size of 20-100um, and then mixed with active components, auxiliary Mix the catalyst, put it into the rolling molding equipment, spray into the deionized water, prepare the spherical catalyst with a particle size of 0.2-4.0mm, and obtain it after low-temperature drying and high-temperature roasting.

The preparation method of the bar-shaped solid base catalyst for fixed bed is: crush the forming aid, the solid base catalyst structure carrier and the heat-carrying carrier into a powder with a D50 particle size of 20-100um, and then mix it with the active component and the aid , put it into a kneader, add deionized water, knead and extrude to prepare a strip catalyst, and obtain it after low-temperature drying and high-temperature roasting.

Compared with existing catalyzer at present, the prepared solid base catalytic cracking catalyst of the present invention has the following advantages:

(1) The solid base catalyst has a high proportion of mesopores (above 95%, preferably above 98%) and unobstructed pores, which is suitable for processing heavy oils such as residual oil and oil sand bitumen containing macromolecular compounds;

(2) The structural carrier of the solid base catalyst is modified by silicon/titanium, which increases the wall thickness of the carrier channel and improves the hydrothermal stability of the catalyst, and then undergoes transition metal skeleton doping and rare earth metal loading to gradually improve the hydrothermal stability of the catalyst The specific surface area of the catalyst is maintained at 100-350m ² /g when the catalyst is treated under hydrothermal conditions at 800°C for a long time. It has excellent high-temperature hydrothermal stability and is suitable for heavy oil catalytic cracking reactions under high-temperature hydrothermal conditions;

(3) The catalyst is treated with chlorosilane to eliminate most of the acid centers on the surface and reduce the adsorption of the catalyst to polycyclic aromatic hydrocarbons in heavy oil and non-hydrocarbon impurities (non-hydrocarbon macromolecules containing metals, sulfides, nitrides, oxides) and poisoning after adsorbing impurities, prolonging the life of the catalyst;

(4) The prepared solid base catalytic cracking catalyst handles heavy oil and residual oil with a residual carbon content greater than 10wt%, the heavy oil conversion rate is greater than 75%, the coke yield is less than 10wt%, and the selectivity of propylene butene in the liquefied gas is greater than 80%, with the characteristics of high conversion rate of heavy oil, low yield of dry gas and coke, and high selectivity of low-carbon olefins. It is also suitable for the processing of conventional heavy oil;

(5) The solid base catalyst provided by the present invention and its preparation method can also be processed into strip-shaped and spherical solid base catalysts for use in fixed-bed and moving-bed catalytic reaction processes.

Detailed ways

The preparation method of the solid base catalyst of the present invention and the obtained catalyst technical scheme will be further described below in conjunction with specific examples.

The invention is a solid base catalyst, which is used for catalytic cracking fluidized bed reaction, and is especially suitable for processing heavy oil such as residual oil and oil sand bitumen. The chemical composition of the specific components of the solid base catalyst includes active components, additives, and forming aids , solid base catalyst carrier, the concrete mass composition of catalyzer and preparation method are as follows:

Based on the total mass percentage of the catalyst, the active component is 0.02-70wt%, the auxiliary agent is 0.02-5wt%, the forming aid is 2-20wt%, the solid alkali catalyst carrier is 20-95wt%, and the solid alkali catalyst carrier is composed of a solid alkali catalyst The structure carrier is composed of a solid base catalyst and a heat-carrying carrier, and the mass ratio of the solid base catalyst structure carrier to the heat-carrying carrier is (3:1)-(1:3).

The solid base catalyst structure carrier, the ratio of the mesopore volume to the total pore volume is greater than 95%, and is prepared by the following preparation method:

(1) Channel thickening treatment: replace the water in the carrier precursor gel with an alcohol solvent, then replace it with an alcohol solvent containing the modified component, and finally replace the ethanol solution and the catalytic modified component with water Hydrolyze and dry to obtain a carrier precursor with thickened pores;

(2) Transition metal doping: The doping metal is one or more of manganese, tungsten, molybdenum, titanium, germanium, tin, and zirconium. The addition is to dissolve the doped metal salt in the acidic solution before the oxide and composite oxide gel, gradually add it dropwise to the alkaline or neutral oxide and composite oxide gel, and complete the gel stage after filtration and drying Metal doping; ion exchange addition is to dissolve the doped metal salt in acidic or neutral solution, fully contact the solution with high silicon molecular sieve, ion exchange reaction occurs, wash and filter the exchanged high silicon molecular sieve, and dry it. Complete the ion exchange addition step;

(3) Surface modification treatment: Treat the metal-doped and modified precursor with chlorosilane, make a solution of chlorosilane and solvent, and treat the carrier at a temperature of 10-100°C and a pressure of 0-1.0MPa , preferably silicon/titanium modification first, and then chlorosilane treatment, the molar concentration of chlorosilane in the solution is 0.01-0.1mol/L, after subsequent high-temperature roasting, chlorosilane decomposes into small gas molecules, and obtains a solid base catalyst structure Carrier; the chlorosilane is one or more of methylchlorosilane, dimethylchlorosilane and trimethylchlorosilane;

(4) Grinding the forming aid, solid base catalyst structure carrier and heat-carrying carrier into powder, then mixing with active components and aids, forming, drying and roasting to obtain a solid base catalyst.

The inventors found that the mass transfer effect of the solid base catalytic cracking catalyst can be effectively improved by screening the structural carrier with high mesopore ratio, silicon/titanium modification, chlorosilane treatment, transition metal skeleton doping, and rare earth metal loading on the structural carrier. , hydrothermal stability, anti-poisoning stability, more suitable for processing heavy oil such as residue oil, oil sand bitumen, etc., the alkaline active center and the catalyst structure support form an efficient catalyst system, in the reaction of processing heavy oil, the product distribution is better, and the conversion rate of heavy oil High, low coke yield, low dry gas yield, high selectivity of low carbon olefins.

Solid base catalytic cracking catalyst performance evaluation method of the present invention is as follows:

A fluidized bed pilot plant was used to evaluate the catalyst, and the catalyst used for the evaluation of heavy oil catalytic cracking performance was subjected to aging treatment at 800°C and 100% water vapor for 17 hours in advance. The performance evaluation of the solid base catalytic cracking catalyst was carried out on the fluidized bed pilot plant. The process conditions were: reaction pressure 0.2MPa, temperature 520°C, steam/feedstock oil weight ratio 0.3:1, agent-oil ratio 12:1, contact time 2s . The properties of the raw materials used are shown in Table 1. The collected gas phase products are measured by refinery gas chromatography, the liquid products are measured by true boiling point distillation, and the composition of the liquid product family is determined by chromatography-mass spectrometry. The analysis data are shown in Table 2.

The inventive process is illustrated by examples below, but not limited to these examples.

Comparative example 1

(1) Select silica: the measured BET specific surface area is 632m ² /g, the average pore diameter is 4.5nm, the pore volume is 0.64cm ³ /g, the mesopore volume is 0.62cm ³ /g, the mesopore volume (2nm～50nm pore volume) volume) ratio of 96.88%.

(2) Preparation of microsphere catalyst by spray drying integrated method: adopting magnesium nitrate as active component metal salt, magnesium oxide accounts for 8wt% of catalyst mass ratio, first magnesium nitrate is dissolved in water, stirs evenly, then kaolin is added into beating, kaolin accounts for The mass ratio of the catalyst is 35wt%, and then add silica to continue beating. The mass ratio of silica to the catalyst is 38wt%. After stirring evenly, add silica sol. The silica sol in silica sol accounts for the mass ratio of silica in the catalyst. 19wt% (other impurities in the silica sol are ignored), adjust the amount of water appropriately, control the water content of the final slurry to 73wt%, continue to stir for 1 hour, use a spray drying device to dry and shape the slurry, control the outlet temperature to 105 ° C, and collect particles The particles with a diameter of 40-120um were dried at 120°C for 12 hours and calcined at 550°C for 4 hours to obtain a microsphere catalyst.

(3) Catalyst evaluation and product analysis: The catalyst was subjected to aging treatment at 800° C. and 100% water vapor for 17 hours in advance. Catalyst performance evaluation was carried out on a fluidized bed pilot plant. Process conditions: reaction pressure 0.2MPa, temperature 520°C, steam/feedstock oil weight ratio 0.3:1, agent-oil ratio 12:1, contact time 2s.

In the catalyst evaluation and product analysis experiments, the properties of the raw materials used are shown in Table 1. The collected gas phase products were measured by refinery gas chromatography, the liquid products were measured by true boiling point distillation, and the composition of the liquid product family was determined by chromatography-mass spectrometry. Comparative example 1 and each embodiment product analysis data are shown in Table 2.

Example 1

(1) The selection of the silica carrier is the same as in Comparative Example 1.

(2) Pore thickening treatment: the silica carrier is first modified by silicon in the stage of synthesizing the gel, and the silica carrier gel is first replaced with ethanol to replace the water in the gel, and then the ethanol solution containing ethyl orthosilicate replacement, and finally the ethanol solution was replaced with water, and dried at 120° C. to obtain a silicon-modified silica carrier. The mass proportion of the modified component in the silica carrier was 1.5 wt%.

(3) Transition metal doping: Doping the transition metal with manganese, using 0.1mol/L manganese nitrate dilute solution to treat silicon-modified silica carrier, dissolving with dilute sulfuric acid to adjust pH=3, washing and drying to obtain manganese-modified A permanent silica carrier, manganese forms a bond with silicon in the carrier, and the mass ratio of manganese to the silica carrier is 0.25wt%.

(4) Surface modification treatment: make a solution of trimethylchlorosilane and cyclohexane solvent, the molar concentration of trimethylchlorosilane in the solution is 0.05mol/L, at a temperature of 80°C and a pressure of 0.5MPa The manganese-modified silicon dioxide carrier is treated under conditions, and the solid alkali catalyst structure carrier is obtained through drying.

(5) Preparation of microsphere catalyst by spray drying integrated method: adopting magnesium nitrate as active component metal salt, cerium nitrate as rare earth metal salt, wherein magnesium oxide accounts for 8wt% of catalyst mass ratio, cerium oxide accounts for catalyst mass ratio of 1.5wt%, first Dissolve magnesium nitrate and cerium nitrate in water, stir evenly, then add kaolin for beating, the proportion of kaolin in catalyst mass is 33.5wt%, then add the solid alkali catalyst structure carrier prepared in the above step (4) to continue beating, the solid alkali catalyst structure The mass ratio of the carrier to the catalyst is 38wt%, and the silica sol is added after stirring evenly. The silica in the silica sol accounts for 19wt% by mass of the catalyst (other impurities in the silica sol are ignored), and the amount of water is appropriately adjusted to control the water content of the final slurry. 83wt%, continue stirring for 1 hour, use a spray drying device to dry and shape the slurry, control the outlet temperature at 105°C, collect particles with a particle size of 40-120um, dry at 120°C for 12 hours, and bake at 650°C for 4 hours. A microsphere catalyst is obtained.

(6) Catalyst evaluation and product analysis are the same as in Comparative Example 1.

Example 2

(1) Select the silicon-aluminum composite oxide carrier, the measured BET specific surface area is 583m ² /g, the average pore diameter is 4.9nm, the pore volume is 0.68cm ³ /g, the mesopore volume is 0.65cm ³ /g, the mesopore volume (greater than 2nm pore volume) ratio 95.59%.

(2) Pore thickening treatment: the silicon-aluminum composite oxide carrier is first modified with titanium in the gel synthesis stage, and the silicon-aluminum composite oxide carrier gel is first replaced with ethanol to replace the water in the gel, and then with titanium tetrachloride The ethanol solution was replaced, and finally the ethanol solution was replaced with water, and finally dried at 120°C to obtain a titanium-modified silicon-aluminum composite oxide carrier. The mass ratio of the modified component titanium dioxide to the silicon-aluminum composite oxide carrier was 1.5wt %.

(3) Transition metal doping: Doping the transition metal with manganese, using 0.1mol/L manganese nitrate dilute solution to treat the titanium-modified silicon-aluminum composite oxide carrier, dissolving with dilute sulfuric acid to adjust pH=2, washing and drying to obtain manganese In the modified silicon-aluminum composite oxide carrier, manganese forms a bond with silicon in the silicon-aluminum composite oxide carrier, and the mass ratio of manganese to the silicon-aluminum composite oxide carrier is 0.35 wt%.

(4) Surface modification treatment: make a solution of dimethylchlorosilane and cyclohexane solvent, the molar concentration of dimethylchlorosilane in the solution is 0.05mol/L, at a temperature of 80°C and a pressure of 0.5MPa The manganese-modified silicon-aluminum composite oxide support is treated under conditions, and the solid alkali catalyst structure support is obtained through drying.

(5) Preparation of microsphere catalyst by spray drying integrated method: calcium nitrate is used as active component metal salt, cerium nitrate is rare earth metal salt, wherein calcium oxide accounts for 8wt% of catalyst mass ratio, cerium oxide accounts for catalyst mass ratio of 1.5wt%, first Dissolve calcium nitrate and cerium nitrate in water, stir evenly, then add kaolin for beating, the proportion of kaolin in catalyst mass is 33.5wt%, then add the solid alkali catalyst structure carrier through the above step (4) to continue beating, the solid alkali catalyst structure The mass ratio of the carrier to the catalyst is 38wt%, and the silica sol is added after stirring evenly. The silica in the silica sol accounts for 19wt% by mass of the catalyst (other impurities in the silica sol are ignored), and the amount of water is appropriately adjusted to control the water content of the final slurry. 73wt%, continue to stir for 1 hour, use a spray drying device to dry and shape the slurry, control the outlet temperature to 105°C, collect particles with a particle size of 40-120um, dry at 120°C for 12 hours, and bake at 550°C for 4 hours. A microsphere catalyst is obtained.

(6) Catalyst evaluation and product analysis are the same as those of Comparative Example 1.

Example 3

(1) Select the silicon-aluminum composite oxide carrier, and the measured BET specific surface area is 556m ² /g, the average pore diameter is 5.6nm, the pore volume is 0.72cm ³ /g, the mesopore volume is 0.71cm ³ /g, the mesopore volume (greater than 2nm pore volume) ratio 98.61%.

(2) The channel thickening treatment is the same as that in Example 2.

(3) Transition metal doping is the same as in Example 2.

(4) The surface modification treatment is the same as in Example 2.

(5) The preparation of the microsphere catalyst by spray-drying integrated method is the same as in Example 2.

Example 4

(1) The silicon-titanium composite oxide carrier is selected, and the measured BET specific surface area is 493m ² /g, the average pore diameter is 6.8nm, the pore volume is 0.842cm ³ /g, the mesopore volume is 0.836cm ³ /g, and the mesopore volume (greater than 2nm pore volume) ratio 99.29%.

(2) The channel thickening treatment is the same as that in Example 2.

(3) Transition metal doping is the same as in Example 2.

(4) The surface modification treatment is the same as in Example 2.

Example 5

(1) Select SBA-15 molecular sieve carrier, the measured BET specific surface area is 525m ² /g, the average pore diameter is 6.3nm, the pore volume is 0.764cm ³ /g, the mesopore volume is 0.761cm ³ /g, the mesopore volume (greater than 2nm Pore volume) ratio of 99.61%.

(2) The channel thickening treatment is the same as that in Example 2.

(3) Transition metal doping is the same as in Example 2.

(4) The surface modification treatment is the same as in Example 2.

The basic properties of raw materials used in the embodiment of table 1

Table 2 Catalyst evaluation data table

Comparative example 2

(2) Carry out catalyst molding by extruding method, wherein active component metal salt is magnesium nitrate, magnesium oxide accounts for catalyst mass ratio 8wt%, kaolin accounts for catalyst mass ratio is 35wt%, silicon dioxide accounts for catalyst mass ratio and is 38wt%, The silicon dioxide in the silica sol accounted for 19 wt% of the catalyst mass (other impurities in the silica sol were ignored), dried at 120° C. for 12 hours, and calcined at 550° C. for 4 hours to obtain a cylindrical catalyst with a diameter of 1 mm.

(3) Catalyst evaluation and product analysis: The catalyst was subjected to aging treatment at 800° C. and 100% water vapor for 17 hours in advance. Catalyst performance evaluation was carried out on a fixed-bed pilot plant, and the process conditions were: reaction pressure 0.2MPa, temperature 520°C, steam/feedstock oil weight ratio 0.3:1, agent-oil ratio 12:1.

In the catalyst evaluation and product analysis experiments, the properties of the raw materials used are shown in Table 1. The collected gas phase products were measured by refinery gas chromatography, the liquid products were measured by true boiling point distillation, and the composition of the liquid product family was determined by chromatography-mass spectrometry. Comparative example 2 Catalyst evaluation and product analysis data are shown in Table 3.

Example 6

(2) The channel thickening treatment is the same as that in Example 1.

(3) Transition metal doping is the same as in Example 1.

(4) The surface modification treatment is the same as in Example 1.

(5) adopt extrusion method to carry out catalyst molding, wherein active component metal salt is magnesium nitrate, magnesium oxide accounts for catalyst mass ratio 8wt%, kaolin accounts for catalyst mass ratio and is 35wt%, silicon dioxide accounts for catalyst mass ratio and is 38wt%, The silicon dioxide in the silica sol accounted for 19 wt% of the catalyst mass (other impurities in the silica sol were ignored), dried at 120° C. for 12 hours, and calcined at 550° C. for 4 hours to obtain a cylindrical catalyst with a diameter of 1 mm.

(6) Catalyst evaluation and product analysis: The catalyst was subjected to aging treatment at 800° C. and 100% water vapor for 17 hours in advance. Catalyst performance evaluation was carried out on a fixed-bed pilot plant, and the process conditions were: reaction pressure 0.2MPa, temperature 520°C, steam/feedstock oil weight ratio 0.3:1, agent-oil ratio 12:1. Catalyst evaluation and product analysis data are shown in Table 3.

Comparative example 3

(2) adopt rolling ball method to carry out catalyst shaping, wherein active component metal salt is magnesium nitrate, magnesium oxide accounts for catalyst mass ratio 8wt%, kaolin accounts for catalyst mass ratio and is 35wt%, silicon dioxide accounts for catalyst mass ratio and is 38wt%, The silicon dioxide in the silica sol accounted for 19 wt% of the catalyst mass (other impurities in the silica sol were ignored), dried at 120° C. for 12 hours, and calcined at 550° C. for 4 hours to obtain a spherical catalyst with a diameter of 1 mm.

In the catalyst evaluation and product analysis experiments, the properties of the raw materials used are shown in Table 1. The collected gas phase products were measured by refinery gas chromatography, the liquid products were measured by true boiling point distillation, and the composition of the liquid product family was determined by chromatography-mass spectrometry. Comparative example 3 Catalyst evaluation and product analysis data are shown in Table 3.

Example 7

(2) The channel thickening treatment is the same as that in Example 1.

(3) Transition metal doping is the same as in Example 1.

(4) The surface modification treatment is the same as in Example 1.

(5) adopt rolling ball method to carry out catalyst molding, wherein active component metal salt is magnesium nitrate, magnesium oxide accounts for catalyst mass ratio 8wt%, kaolin accounts for catalyst mass ratio and is 35wt%, silicon dioxide accounts for catalyst mass ratio and is 38wt%, The silicon dioxide in the silica sol accounted for 19 wt% of the catalyst mass (other impurities in the silica sol were ignored), dried at 120° C. for 12 hours, and calcined at 550° C. for 4 hours to obtain a spherical catalyst with a diameter of 1 mm.

Table 3 Catalyst evaluation data table

Claims

A solid base catalyst, characterized in that it consists of an active component, an auxiliary agent, a forming aid, and a solid base catalyst carrier, and in terms of the total mass percentage of the catalyst, the active component is 0.02-70wt%, and the auxiliary agent is 0.02-5wt% %, forming aid 2-20wt%, solid alkali catalyst carrier is 20-95wt%; solid alkali catalyst carrier is made up of solid alkali catalyst structure carrier and solid alkali catalyst carrying heat carrier, solid alkali catalyst structure carrier and heat-carrying carrier mass ratio is (3:1)-(1:3);

Wherein, the active component is one or more of alkali metal or alkaline earth metal oxides, alkali metal or alkaline earth metal salts;

The auxiliary agent is one or several kinds of rare earth metals;

The forming aid is one or more of silica sol, aluminum sol, and water glass;

The solid base catalyst structure carrier has a ratio of mesoporous pore volume to total pore volume greater than 95%, and is prepared by the following preparation method:

1) Channel thickening treatment: the carrier precursor gel is first treated with an alcohol solvent, then treated with an alcohol solvent containing modified components, and finally treated with water, and dried to obtain a carrier precursor with thickened channels. The active component is one or more of tetraethyl orthosilicate, silicon tetrachloride, titanium tetrachloride, and n-butyl titanate, and the mass proportion of the modified component in the carrier is 0.05-10 wt %; The carrier precursor gel is one or more of silicon-containing composite oxide gel, high silicon molecular sieve gel, silica gel, alumina gel, and the alcohol solvent is methanol, ethanol One or more of , propanol, isopropanol and ethylene glycol;

2) Transition metal doping: Doping the transition metal skeleton on the carrier precursor with thickened channels, dissolving the transition metal salt in the inorganic acid solution, treating the carrier precursor with thickened channels, and washing the residual metal salt after treatment A transition metal doped carrier precursor is obtained; the transition metal salt is a soluble metal salt of manganese, tungsten, molybdenum, titanium, germanium, tin or zirconium; the inorganic acid solution is one of sulfuric acid solution, nitric acid solution, and hydrochloric acid solution species or several;

3) Surface modification treatment: modify the surface of the transition metal-doped carrier precursor with a modified solution, and then make it after drying, wherein the solvent of the modified solution is water, ethanol, acetone, cyclohexane One or more of them, and the solute is one or more of methylchlorosilane, dimethylchlorosilane and trimethylchlorosilane.
The solid base catalyst according to claim 1, characterized in that, the solid base catalyst is a microspherical solid base catalyst with a particle diameter of 10-200 μm.
The solid base catalyst according to claim 1, characterized in that, the solid base catalyst is a strip catalyst with a diameter of 0.8 to 2 mm, and its strip cross-sectional shape is cylindrical, clover, four-leaf clover or Raschig ring.
The solid base catalyst according to claim 1, characterized in that, the solid base catalyst is spherical with a diameter of 0.5-3.0 mm.
The solid base catalyst according to claim 1, wherein the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-titanium composite oxide, and silicon-magnesium composite oxide.
solid alkali catalyst according to claim 1, is characterized in that, described forming aid is one or more in large particle size silica sol, high viscosity silica sol, low sodium silica sol, water glass; The heat-carrying carrier of the solid base catalyst is kaolin.
The solid base catalyst according to claim 1, wherein the rare earth metal is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, One or more of Yb and Lu.
The solid base catalyst according to claim 1, wherein the active component is a metal oxide of the first main group, a metal oxide of the second main group, a metal salt of the first main group, a metal salt of the second main group One or several kinds of metal salts.
The solid base catalyst according to claim 8, wherein the active components are potassium oxide, magnesium oxide, calcium oxide, barium oxide, potassium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, potassium carbonate, carbonic acid One or more of magnesium and calcium carbonate.
A kind of preparation method of solid base catalyst is characterized in that, comprises the steps:

1) Preparation of solid base catalyst structure support

a) Pore thickening treatment: replace the water in the carrier precursor gel with an alcohol solvent, then replace it with an alcohol solvent containing a modified component, and finally replace the ethanol solution with water and catalyze the hydrolysis of the modified component After drying, the carrier precursor with thickened pores is obtained, and the modified component used is one or more of ethyl orthosilicate, silicon tetrachloride, titanium tetrachloride, and n-butyl titanate. The carrier precursor gel is one or more of silicon-containing composite oxide gel, high-silicon molecular sieve gel, silica gel, and alumina gel, and the alcohol solvent is methanol, ethanol, acrylic acid, etc. One or more of alcohol, isopropanol, and ethylene glycol;

b) Transition metal doping: dope the transition metal skeleton to the carrier precursor with thickened channels, dissolve the transition metal salt in the inorganic acid solution, and treat the carrier precursor with thickened channels at 10-90°C, after treatment After washing the residual metal salt, a transition metal-doped carrier precursor is obtained; the transition metal salt is a soluble metal salt of manganese, tungsten, molybdenum, titanium, germanium, tin or zirconium; the inorganic acid solution is sulfuric acid solution, nitric acid solution, hydrochloric acid One or several in the solution;

c) Surface modification treatment: modify the surface of the transition metal-doped carrier precursor with a modified solution, and then make it after drying, wherein the solvent of the modified solution is one of water, ethanol, acetone, and cyclohexane or several, the solute is one or more of methylchlorosilane, dimethylchlorosilane, and trimethylchlorosilane;

2) Preparation of solid base catalyst

The forming aid, the solid base catalyst structure carrier and the heat-carrying carrier are pulverized into powder, then mixed with the active component and the aid, and then shaped, dried and calcined to obtain the solid base catalyst.
An application of the solid base catalyst according to claim 2 in catalytic cracking of heavy oil.
An application of the solid base catalyst in heavy oil catalytic cracking according to claim 11, characterized in that the solid base catalyst is a microspherical solid base catalyst with a particle size of 20-200 μm, and the heavy oil The catalytic cracking reaction is a heavy oil fluidized catalytic cracking reaction.
An application of the solid base catalyst in heavy oil catalytic cracking according to claim 12, characterized in that, the solid base catalyst is used to treat residual oil, vacuum residual oil and crude oil with high residual carbon content.
An application of the solid base catalyst according to claim 3 in fixed-bed base-catalyzed reactions.
An application of the solid base catalyst according to claim 4 in a fixed bed or moving bed base catalytic reaction.