CN116212849A - Method for preparing catalytic cracking catalyst by ammonium-free method - Google Patents

Method for preparing catalytic cracking catalyst by ammonium-free method Download PDF

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CN116212849A
CN116212849A CN202111468024.6A CN202111468024A CN116212849A CN 116212849 A CN116212849 A CN 116212849A CN 202111468024 A CN202111468024 A CN 202111468024A CN 116212849 A CN116212849 A CN 116212849A
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catalytic cracking
preparing
cracking catalyst
silicon
catalyst
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张莉
刘宏海
王久江
胡清勋
刘涛
赵红娟
刘超伟
赵晓争
王宝杰
熊晓云
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, which comprises the following steps: (1) Mixing a magnesium source solution with a silicon source solution to obtain a silicon-magnesium material, adding a rare earth compound, and aging to obtain the silicon-magnesium material containing rare earth; (2) Mixing rare earth-containing silicon-magnesium material with kaolin, a dispersing agent and/or a reinforcing agent and deionized water, pulping, spraying into microspheres, roasting, mixing with sodium silicate, a guiding agent, an alkali solution and water, and crystallizing to obtain a crystallized product; (3) Exchanging and modifying the crystallized product with ammonia water and boric acid, and roasting to obtain a primary roasting material; (4) And (3) carrying out countercurrent contact on the primary roasting material and silicon tetrachloride in a downward bed type isomorphous substitution reactor to carry out isomorphous substitution reaction so as to obtain the catalyst. The invention prepares the in-situ crystallization catalyst with excellent performance and simple process flow by utilizing the modification of rare earth aged silicon-magnesium material, ammonia water and boric acid and combining with isomorphous substitution process.

Description

Method for preparing catalytic cracking catalyst by ammonium-free method
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for catalytic cracking of a catalyst without ammonium.
Background
Low cost and high performance have been one of the important directions of catalytic cracking catalyst preparation, and for heavy oil catalytic cracking catalysts, as FCC unit raw oil becomes increasingly heavier, inferior and environmentally friendly, catalytic cracking catalysts are required to have more excellent reactivity and efficient preparation process.
In order to ensure that the catalytic cracking catalyst has a smooth pore canal, good acidity and very low sodium oxide, substances such as ammonium salt, rare earth and the like are used for carrying out post-modification treatment exchange in the post-modification process, and serious ammonia nitrogen pollution is caused while good performance is obtained. Severely restricting the sustainable development of the catalyst. Therefore, development of a low-cost and high-performance post-catalyst modification process is an important point for improving quality and enhancing efficiency.
For a long time, people perform a great deal of work on converting and removing nitrogen in sewage, but ammonia nitrogen in the water is removed and converted after the sewage is generated, and the methods often have the defects of large investment, complex operation, high operation cost and the like, and even some processes bring secondary pollution while ammonia nitrogen is removed, so that the production cost of the catalyst is obviously increased. At the same time, ammonia nitrogen exchanged or adsorbed on the molecular sieve and the catalyst may enter the atmosphere during the subsequent treatment process, thereby causing pollution to the air. The optimal idea is to reduce the ammonium salt consumption in the catalyst preparation process, relieve ammonia nitrogen pollution from the source, develop a brand-new exchange technology and catalyst preparation process, improve the modified ion utilization rate, and ensure the sustainable development of the catalytic cracking catalyst.
CN202010059891.3 discloses a method for preparing mesoporous molecular sieve by ammonia-free method, which comprises the steps of contacting molecular sieve raw material with dealumination pore-forming agent in water to perform chemical dealumination pore-forming treatment without ammonium exchange, thus obtaining secondary mesoporous molecular sieve product, although the method can prepare certain mesopores, the difficulty of industrial implementation is relatively high; the CN201711117556.9 describes in detail a preparation method of a pollution-free high-stability catalytic cracking catalyst, and the specific method comprises the steps of contacting NaY molecular sieve raw powder with chlorine-containing gas to carry out gas-phase ion exchange reaction, completing sodium reduction and superstabilization of the NaY molecular sieve raw powder in one step to prepare a low-sodium high-silicon-aluminum ratio molecular sieve, compounding clay raw ores of different types, carrying out high-concentration acid treatment to prepare acid-activated composite clay, mixing and pulping the low-sodium high-silicon-aluminum ratio molecular sieve and the acid-activated composite clay with binder, rare earth and deionized water, spraying and granulating, roasting, solidifying, and obtaining a catalytic cracking catalyst finished product without washing and drying. The catalytic cracking catalyst can obviously reduce the content of olefin in gasoline, improve the light oil yield, and has short preparation flow and no ammonia nitrogen emission. The patent improves two aspects of NaY molecular sieve gas phase ultrastable process implementation and matrix modification. CN201711074372.9 and CN201611117946.1 adopt a gas phase ultrastable method to realize the exchange without ammonium; the CN201611116722.9 is characterized by short operation flow, no ammonia nitrogen pollution, less sewage, low production cost, good reaction control, high reaction degree, low sodium content, high silicon-aluminum ratio, adjustable silicon-aluminum ratio, uniform product property and capability of carrying out large-scale continuous automatic operation.
In patent CN101850239a, molecular sieve is manufactured into molecular sieve paper, then the molecular sieve paper is hot-pressed into corrugated shape, and then is alternately stacked or rolled up with the molecular sieve paper to form a honeycomb body, and the honeycomb body is placed in a closed container to react with mixed gas of nitrogen and silicon tetrachloride gas, and after the reaction is finished, the molecular sieve honeycomb body is repeatedly cleaned and then is pickled. The product prepared by the method has uniform properties, avoids the problem of blocking of the molecular sieve, but increases the manufacturing cost and labor intensity because the molecular sieve paper and the honeycomb body are manufactured and the honeycomb body is broken if the powder product is obtained. Patent CN1286721C discloses a method for supplementing silicon by extracting aluminum from a molecular sieve in a gas phase, wherein the reaction of aluminum removal and silicon supplementation in a gas phase is carried out in a reaction kettle with stirring. The method ensures that the contact reaction of the silicon tetrachloride gas and the molecular sieve solid particles is more uniform, avoids the phenomenon that the molecular sieve solid particles are coalesced into compact blocks, reduces the labor intensity, reduces the environmental pollution and obviously reduces the production cost. However, stirring also brings the adverse effect that the molecular sieve is taken away along with the lifting of the airflow, and has the defects of long production period, incapability of infinitely amplifying a stirred tank reactor, difficulty in large-scale continuous production and the like. In the patent CN102049315A, CN102049316A, CN102050459A, CN102050460A, CN102451655A, CN102451656A, CN102451657A, CN102451658A, CN102451729A, CN102451730A, the gas phase dealumination and silicon supplementing reaction is carried out in a horizontal tubular reactor with a length of 50-95 m and a diameter of 0.1-1.4 m and a horizontal pushing flow type heating tubular reactor, and the reactor also comprises a gas mixer, a raw material mixing unit, a gas-solid separator, an absorption tower and a beating machine. The molecular sieve and the gaseous silicon tetrachloride flow along with inert carrier gas in a tubular reactor and are contacted for reaction, the contact time is 10s-100min, and the molecular sieve after the gaseous dealumination and silicon supplement is mixed with binder, clay and water for pulping and granulating to obtain the catalytic cracking catalyst. The method avoids the adhesion of molecular sieve particles, and can realize the continuous contact reaction of the molecular sieve and silicon tetrachloride. In addition, different reaction conditions and reaction degrees are controlled by controlling different reaction temperatures, so that molecular sieve products with different dealumination depths are obtained; by controlling the flow rate of the carrier gas and the length of the tubular reactor, the contact time of the molecular sieve and the silicon tetrachloride can be controlled. However, in order to achieve the purposes of carrying molecular sieve particles to flow and avoiding blocking pipelines by the molecular sieve particles, the method needs to increase the flow rate of carrier gas, so that the defects of difficult improvement of reaction depth, low silicon-aluminum ratio of products and the like are caused; in addition, in order to achieve the reaction depth, the introducing amount of silicon tetrachloride is required to be increased, so that the load of a tail gas treatment system is necessarily increased; the contact time is controlled by controlling the length of the tubular reactor, so that the occupied area of the device is increased, and a plurality of inconveniences exist in actual production. In patent CN103769193A, CN103785436A, CN103785437A, CN103785438A, CN103787352A, CN104549445a, the above-mentioned gas phase dealumination and silicon make-up reactor is optimized.
CN103240113a discloses a preparation method of an in-situ crystallization catalyst for reducing ammonia nitrogen pollution, which comprises adding polydimethyl diallyl ammonium chloride capable of modulating a kaolin inter-stacking mode during spraying to obtain an in-situ crystallization product, cleaning an exchange environment of exchange ions by an acidic solution, and then performing exchange and roasting in other steps to obtain the catalytic cracking catalyst. The method can reduce the ammonium salt consumption by more than 15%, effectively relieve the ammonia nitrogen pollution problem in the preparation process of the in-situ crystallization catalyst, reduce the production cost and improve the reaction performance of the catalyst. CN100404432C discloses a method for reducing ammonia nitrogen pollution in zeolite modification process, which comprises exchanging sodium in zeolite with potassium compound in zeolite modification process, and further carrying out zeolite exchange modification treatment with ammonium salt. The method does not increase zeolite modification cost, and reduces the ammonium salt usage amount by about 50%.
CN103028431a discloses a clean production process of a molecular sieve catalytic cracking catalyst, the method adopts a conventional in-situ crystallization method to prepare a modified molecular sieve or a molecular sieve catalytic cracking catalyst, and mixes molecular sieve crystallization filtration mother liquor and/or crystallization material water washing water with ammonia nitrogen wastewater generated in a molecular sieve exchange process to be used as spray washing liquid of a spray washing tower of catalyst spray granulation tail gas, and adds acidified aluminum salt or acid liquor into the spray recovery liquid to form gel, filter, discharges filtrate, and filter residues are used as raw materials of synthesizing the molecular sieve. The method reduces the cost while preparing a qualified catalytic cracking catalyst product. After NaY molecular sieve microspheres are prepared by CN102553630A, the NaY molecular sieve microspheres are contacted with silicon tetrachloride gas according to the weight ratio of 0.1-0.9:1, and react for 10 minutes to 6 hours at the temperature of 150-500 ℃, and the catalytic cracking catalyst containing the small-grain Y molecular sieve with high silicon-aluminum ratio is prepared by washing with water. The in-situ crystallization catalyst prepared by the method has a pore structure and performance which are inferior to those of the traditional hydrothermal ultra-stable catalyst due to the overlong reaction time.
Through the analysis of the patent, although the dosage of ammonium salt is obviously reduced in the preparation process and the generation of ammonia nitrogen wastewater is reduced by a plurality of catalysts, ammonium ions are still more or less introduced, and thorough ammonia-free production cannot be achieved.
There are also some patents that realize the exchange without ammonium method by gas-phase superstable process, but because gas-phase superstable is isomorphous substitution process, after gas-phase superstable, catalyst or molecular sieve lacks abundant pore canal structure, resulting in poor selectivity and reactivity of catalyst.
Disclosure of Invention
The invention aims to provide a method for preparing a catalytic cracking catalyst by an ammonium-free method, which aims to solve the problem of environmental pollution caused by ammonia nitrogen emission in the exchange process due to underdeveloped catalyst pore structure in the existing preparation method.
In order to achieve the above object, the present invention provides a method for preparing a catalytic cracking catalyst by an ammonium-free method, comprising the steps of:
(1) Mixing a magnesium source solution with a silicon source solution to obtain a silicon-magnesium material, adding a rare earth compound, and aging to obtain the silicon-magnesium material containing rare earth;
(2) Mixing rare earth-containing silicon-magnesium material with kaolin, a dispersing agent and/or a reinforcing agent and deionized water, pulping, spraying into microspheres, roasting, mixing with sodium silicate, a guiding agent, an alkali solution and water, and crystallizing to obtain a crystallized product;
(3) Exchanging and modifying the crystallized product with ammonia water and boric acid, and roasting to obtain a primary roasting material;
(4) And (3) carrying out countercurrent contact on the primary roasting material and silicon tetrachloride in a downward bed type isomorphous substitution reactor to carry out isomorphous substitution reaction so as to obtain the catalyst.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein in the step (1), a magnesium source solution and a silicon source solution are mixed, the pH value is adjusted to 8-12, and then a rare earth compound is added.
The method for preparing the catalytic cracking catalyst by the ammonium-free method comprises the steps of (1) aging for 5-300 minutes at the temperature of 80-120 ℃, wherein the aging temperature is preferably 80-100 ℃, and the aging time is preferably 30-200 minutes.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein in the step (1), a rare earth compound is prepared by a rare earth oxide RE 2 O 3 Meter, RE 2 O 3 The mass ratio of the Si to Mg material is 1-10%, and the molar ratio of Si to Mg in the Si to Mg material is 0.1-15: 1.
the invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein a silicon source in the step (1) is one or more of water glass, silica sol and white carbon black; the magnesium source is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the mass ratio of rare earth-containing silicon-magnesium material to kaolin in the step (2) is 0.1-20:100, the mass ratio of dispersant to kaolin is 1-20:100, preferably 1-15:100, the mass ratio of reinforcing agent to kaolin is 1-20:100, preferably 2-8:100, and the solid content of slurry after mixing and pulping is 30-50%.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the particle size of microspheres obtained by spraying in the step (2) is 20-110 mu m.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the roasting temperature in the step (2) is 600-1000 ℃, the roasting time is 1-3 h, and the crystallization condition is 85-95 ℃ for 16-36 h.
Specifically, when the microspheres are roasted in the step (2), the microspheres can be roasted at 600-1000 ℃ for 1-3 hours to obtain low-temperature roasted microspheres, or can be roasted at 600-850 ℃ for 1-3 hours to obtain high-temperature roasted microspheres, or can be a mixture of the low-temperature roasted microspheres and the high-temperature roasted microspheres. After crystallization, filtering to remove mother liquor, washing filter cake with deionized water until pH is below 10.5, and drying to obtain a crystallized product with good pore structure and wear resistance and containing 20-60% NaY molecular sieve.
The method for preparing the catalytic cracking catalyst by the ammonium-free method is characterized in that the dispersing agent is sodium silicate and/or sodium pyrophosphate, the reinforcing agent is silica sol and/or aluminum sol, and the adding sequence of the dispersing agent and the reinforcing agent is not limited and can be added simultaneously or in batches.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein kaolin in the step (2) is one or more of soft kaolin, hard kaolin and coal gangue, wherein the bit diameter is 1.5-3.0 mu m, the content of crystalline kaolinite is higher than 80%, the content of ferric oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the concentration of ammonia water in the step (3) is 1-25%.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the mass ratio of boron element to crystallized product in the step (3) is 0.01-0.50: 1.
specifically, the step (3) includes that the crystallized product is firstly treated with ammonia water at 20-60 ℃ for 30-120 min, and the exchanged product is exchanged with boric acid, wherein the exchanged process conditions are as follows: the pH value is 3-6, and the temperature is 90-110 ℃. The exchange modification of the ammonia water and the boric acid can change the exchange sequence, namely, the boric acid can be preceded by ammonia water and then the boric acid can be carried out, and the boric acid can be preceded by ammonia water and then the boric acid is not particularly limited.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein after roasting in the step (3), the burning loss is less than 3%, and a microspherical primary roasting material containing 5-60% of Y-type molecular sieve is obtained.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the specific surface of the catalyst is 200-500 m 2 Per gram, pore volume of 0.40-0.55 mL/g。
The composition of the guiding agent in the present invention is not particularly limited, and a general guiding agent may be used, for example, the guiding agent is prepared according to the composition of the guiding agent in example 1 of CN1232862a, and the molar ratio of the guiding agent recommended in the present invention is as follows: (14-16) SiO 2 :(0.7～1.3)Al 2 O 3 :(14～16)Na 2 O:(300～330)H 2 O。
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the pretreatment furnace comprises a feeding section, a roasting section and a discharging section, the total length of the pretreatment furnace is 0.5-5 m, the inner diameter of the pretreatment furnace is 0.01-1 m, and the roasting temperature is 100-1000 ℃.
The invention discloses a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the pretreatment furnace comprises a heating system and a ventilation system, the heating system is arranged on the outer layer of the pretreatment furnace in a furnace tile jacket mode, the ventilation system is arranged on the inner wall of the pretreatment furnace, and the ventilation system can input dry gas, nitrogen or water vapor into the pretreatment furnace.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein an included angle alpha between a feed section of a pretreatment furnace and a main body of the pretreatment furnace is more than 10 degrees and less than 90 degrees, and an included angle beta between the main body of the pretreatment furnace and a horizontal position is more than 10 degrees and less than 90 degrees.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein a shaft rotating device is arranged at the top of a pretreatment furnace to control the rotation of a furnace body of the pretreatment furnace, and the rotation frequency is 10-80 Hz/min.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the downward bed type isomorphous substitution reactor is divided into a buffer zone and a reaction zone from top to bottom, the top of the buffer zone is provided with a catalyst inlet, the upper part of the buffer zone is provided with an atomizer communicated with the catalyst inlet, the bottom of the reaction zone is provided with a nitrogen inlet carrying silicon tetrachloride, the upper part of the reaction zone is provided with a discharge hole, and the inner diameter ratio of the buffer zone to the reaction zone is 1:1 to 4:1, preferably 1:1 to 3:1, the height of the buffer zone and the reaction zone being each independently 0.2 to 1 meter.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein the inner diameter ratio of a buffer zone to a reaction zone is 1:1-3:1; preferably, a heating sleeve or a heating belt is arranged on the outer wall of the downer isomorphous substitution reactor; preferably, the diameter of the cavity of the reaction zone is 0.05-0.5 m.
The invention relates to a method for preparing a catalytic cracking catalyst by an ammonium-free method, wherein an atomizer is made of stainless steel and comprises a plurality of symmetrically distributed gas holes, the diameter of each gas hole is 80-200 mu m, and the internal gas pressure of the atomizer is 0.1-6 MPa.
In the step (4), the isomorphous substitution reaction temperature is 200-900 ℃, preferably 300-600 ℃, the time for contacting the primary roasting material with the silicon tetrachloride gas is 0.1-60 min, nitrogen is taken as carrier gas to carry the silicon tetrachloride into the reactor, and the proportion of the silicon tetrachloride to the total carrier gas is as follows: 0.1 to 100 percent.
The invention is characterized in that rare earth modified silicon-magnesium materials are added in the construction process of the pore structure of the catalyst precursor, so that the catalyst precursor has rich pore structures and higher specific surface according to different preparation conditions, a cross-linked structure is formed in the microsphere precursor, the interweaving structure of the microsphere is changed, and the growth point of the molecular sieve is increased, thereby obtaining higher molecular sieve content. In addition, in the post-modification step, through exchange modification of ammonia water and boric acid, polymers such as silicon aluminum and the like, of which the intermediate product is adhered to the surface, are effectively cleaned, and the pore canal is further communicated; the heavy oil conversion and heavy metal resistance of the catalyst can be further enhanced by introducing boron and combining rare earth modification.
In addition to the above technology, the invention adopts a downer type isomorphous substitution reactor to carry out isomorphous substitution reaction in countercurrent contact with silicon tetrachloride in the post-modification stage. In the design of the reactor, the flow speed of the catalyst can be changed and the contact efficiency with silicon tetrachloride can be improved through the design of the partition reducing reaction and the feeding atomizer, so that the uniformity of the reaction of materials and silicon tetrachloride is ensured and the reaction efficiency is improved.
In summary, the invention utilizes the modification of rare earth aged silicon-magnesium material, ammonia water and boric acid to make up for the defects of undeveloped mesopores and non-ideal pore structure distribution caused by the traditional isomorphous substitution process, and then prepares the in-situ crystallization catalyst with excellent performance and simple process flow by the isomorphous substitution process.
The beneficial effects of the invention are as follows:
1. the catalyst has developed pore volume and increased molecular sieve content. The introduced magnesium-silicon material forms a cross-linking structure in the microsphere precursor, improves the pore structure and the specific surface of the microsphere precursor, changes the synthesis microenvironment, combines the seed crystal and crystallization synthesis conditions, thereby effectively improving the number of growth points of the molecular sieve and obviously improving the content of the molecular sieve.
2. The isomorphous substitution reaction efficiency is improved. In the design of the reactor, the flow speed of the catalyst can be changed and the contact efficiency with silicon tetrachloride can be improved through the design of the partition reducing reaction and the feeding atomizer, so that the uniformity of the reaction of materials and silicon tetrachloride is ensured and the reaction efficiency is improved.
3. The materials are more fully contacted, and the reaction efficiency is high. According to the characteristics of catalytic cracking catalyst microsphere particles, a gas-solid phase reaction principle of a downward bed mode is adopted, materials downward flow along a gravity field, and SiCl is adopted 4 And reversely contacting with the materials from bottom to top under the action of carrier gas. The contact mode can effectively solve the problems of back mixing of the catalyst and uneven distribution of catalyst particles along the radial direction caused by the reverse gravity operation of the ascending riser, and can realize the short-circuit contact operation of materials and reactants due to the improvement of the flow rate of gas-solid phases, and the reaction is uniform, so that the reaction effect is outstanding, and the method is very suitable for the rapid processing reaction process of gas and solid phases.
4. No ammonia nitrogen is generated in the modification process. The isomorphous substitution reaction greatly improves the reduction efficiency of sodium oxide without using ammonium salt exchange.
Drawings
FIG. 1 is a schematic diagram of a downer isomorphous substitution reactor.
FIG. 2 is a schematic structural diagram of an apparatus for preparing a catalytic cracking catalyst by an ammonium-free method according to the present invention.
FIG. 3 shows the angles between the pretreatment sections and the pretreatment furnaces.
Fig. 4 is a schematic structural view of the pretreatment furnace.
FIG. 5 is a graph showing the adsorption curves of the catalysts obtained in example 1 and comparative example 2 according to the present invention, which were tested using naphthalene as a probe molecule;
FIG. 6 is a graph showing the adsorption curves of the catalysts obtained in example 1 and comparative example 2 according to the present invention, which were tested using quinoline as a probe molecule.
Wherein:
1. the pretreatment furnace, 2, a down bed isomorphous substitution reactor, 3, an absorption tower, 4, an exchange, a filter and flash evaporation drying equipment;
11. a feeding section, 12, a roasting section, 13, a discharging section, 14, a shaft rotating device, 15, a heating system, 16 and a ventilation system,
21. buffer zone 22, reaction zone 23, catalyst inlet 24, atomizer 25, nitrogen inlet with silicon tetrachloride, 26, discharge port 27, heating jacket.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
Referring to fig. 1, the downer isomorphous substitution reactor 2 provided by the invention is divided into a buffer zone 21 and a reaction zone 22 from top to bottom, wherein a catalyst inlet 23 is arranged at the top of the buffer zone 21, an atomizer 24 communicated with the catalyst inlet 23 is arranged at the upper part of the buffer zone 21, a nitrogen inlet 25 carrying silicon tetrachloride is arranged at the bottom of the reaction zone 22, a discharge port 26 is arranged at the upper part of the reaction zone 22, and the inner diameter ratio of the buffer zone 21 to the reaction zone 22 is 1:1 to 4:1, the heights of the buffer zone 21 and the reaction zone 22 are respectively and independently 0.2-1 m, and the weight ratio of silicon tetrachloride to the catalyst in the reaction zone 22 is 0.01-0.5:1.
Also, referring to fig. 1, a heating jacket 27 is provided on the outer wall of the downer type isomorphous substitution reactor 2, and of course, in other embodiments, the heating jacket 27 may be replaced by other heating structures, such as a heating belt.
In some embodiments, the reaction zone 22 preferably has a cavity diameter of 0.05 to 0.5 meters in size, and a height of 0.2 to 1 meter in size.
In some embodiments, the inner diameter ratio of buffer zone 21 to reaction zone 22 is preferably 1:1 to 3:1.
In some embodiments, the atomizer 24 is made of stainless steel, and comprises a plurality of symmetrically distributed air holes, wherein the diameter of each air hole is 80-200 um, and the pressure of air in the atomizer 24 is 0.1-6 MPa.
Referring to fig. 2, the device for preparing a catalytic cracking catalyst by an ammonium-free method provided by the invention comprises:
a pretreatment furnace 1 for roasting or hydrothermally treating the catalyst to obtain a pretreated catalyst;
the downstream bed type isomorphous substitution reactor 2 is used for carrying out isomorphous substitution reaction on the pretreated catalyst to obtain a reacted catalyst;
the absorption tower 3 is used for blowing the reacted catalyst into the absorption tower from a feed opening, and then carrying out tail gas neutralization reaction to obtain a catalyst intermediate;
exchange, filter and flash drying equipment 4, including exchange filters, for exchange and filtration of catalyst intermediates; flash drying equipment is used for flashing and drying the catalyst intermediate.
And, referring to fig. 3, the pretreatment furnace 1 comprises a feeding section 11, a roasting section 12 and a discharging section 13, the total length of the pretreatment furnace 1 is 0.5-5 m, the inner diameter is 0.01-1 m, and the roasting temperature is 100-1000 ℃.
Further, referring to fig. 4, the pretreatment furnace 1 includes a heating system 15 and a ventilation system 16, the heating system 15 is provided on the outer layer of the pretreatment furnace 1 in a furnace tile jacket manner, the ventilation system 16 is provided on the inner wall of the pretreatment furnace 1, and the ventilation system 16 is capable of supplying dry gas, nitrogen gas or water vapor into the interior of the pretreatment furnace 1.
And, referring to fig. 3, the angle α between the feed section 11 of the pretreatment furnace 1 and the main body of the pretreatment furnace 1 is greater than 10 ° and less than 90 °; referring to fig. 4, the included angle beta between the main body of the pretreatment furnace 1 and the horizontal position is more than 10 degrees and less than 90 degrees. The top of the pretreatment furnace 1 is provided with a shaft rotating device 14, the furnace body can rotate, the overturning of materials is realized through rotation, and the rotating frequency is 10-80 Hz/min.
The raw material sources are as follows:
1) Kaolin: industrial products, obtained from catalyst factories of Lanzhou petrochemical company
2) Magnesium chloride, chemical purity, national medicine group chemical reagent Co., ltd
3) Sodium silicate solution: industrial products, obtained from catalyst factories of Lanzhou petrochemical company, (SiO) 2 :19.75％，Na 2 O：6.95％，H 2 O:73.30％)
4) Alkaline silica sol: industrial products, hengtai Hengxin chemical engineering Co., ltd, (SiO) 2 ：30％)
5) Guiding agent: industrial agents, taken from catalyst factories of Lanzhou petrochemical company, the ratio: 16SiO 2 :0.8Al 2 O 3 :15.7Na 2 O:312H 2 O
6) NaOH solution: industrial products, obtained from catalyst works of Lanzhou petrochemical Co (NaOH: 24%)
7) Sodium pyrophosphate: analytically pure, tianjin, denko chemical industries, ltd
8) Aluminum sol: industrial products, obtained from catalyst factories of Lanzhou petrochemical company (Al 2 O 3 :21.22％)
9) Hydrochloric acid: chemical purity
10 Ammonium nitrate): chemical purity
11 Ammonium chloride): chemical purity
12 Ammonium sulfate, chemical purity
13 Ammonia water): chemical purity
14 Boric acid): chemical purity
The specific analysis method comprises the following steps:
crystallinity of NaY molecular sieves the crystallinity of the samples was measured by X-ray diffraction method on a D/max-3C X-ray powder diffractometer manufactured by Rigaku corporation, japan, and the method standard was Q/SYLS 0596-2002. X-ray powder is adopted for testing the Si/Al ratio of NaY molecular sieveThe method standard of the final diffraction method is Q/SYLS 0573-2002. Sample attrition index by airlift method, placing a certain amount of sample into a fixing device, blowing and grinding for 5 hours under constant air flow, wherein the average attrition percentage of the last four hours is called attrition index of the catalyst except the first hour, the unit is% per hour, and the method and standard are as follows: airlift Q/SYLS0518-2002. Sample well distribution testing Autosorb-3B specific surface Analyzer, quantachrome, inc., USA, was performed by N 2 The specific surface area, pore size distribution and pore volume of the sample are measured by a low-temperature (77.3K) adsorption-desorption experimental method. Microreaction Activity (MA) evaluation: the method of ASTM-D3907 is adopted, the catalyst is treated for 17 hours under the conditions of 800 ℃ and 100% water vapor in advance, the light diesel oil in large harbor is used as reaction raw oil, the reaction temperature is 460 ℃, the oil inlet time is 70 seconds, the catalyst loading amount is 2.5-5 g, and the yield of the gasoline after the reaction is analyzed by GC 7890.
A dynamic adsorption rate curve test system and a matched data acquisition and analysis system workstation are utilized to detect the adsorption process of a model probe and heavy oil macromolecules on a porous catalyst material, a matched data analysis software is initially developed based on Fick's law, maxwell-Stefan equation, dobbins empirical formula and other adsorption models, and a diffusion coefficient diagram of probe molecules in the catalyst material in the adsorption process is obtained through a reasonable algorithm.
Example 1
84 g of alkaline silica sol is measured, 20g of magnesium chloride is dissolved by 100mL of distilled water, the alkaline silica sol is slowly injected into the dissolved magnesium chloride solution, the mixture is mixed for 30 minutes, a magnesium silicate material is obtained, the final pH value is 8.2, lanthanum nitrate rare earth is added, lanthanum nitrate (calculated by cerium oxide)/magnesium silicate material=20% (mass ratio), the material after the rare earth addition is aged for 5 minutes at 80 ℃, 100g of aged material, 800g of kaolin (burning base), 40g of sodium silicate solution, 160g of alkaline silica sol and deionized water are prepared into mixed slurry with the solid content of 46%, and 600g of spray microsphere P1 with the particle size of 20-110 mu m is obtained through spray drying. Roasting one part of the P1 spray soil ball for 2.7 hours at 980 ℃ to obtain a roasted microsphere G1, roasting the other part of the P1 spray soil ball for 2.5 hours at 650 ℃ to obtain a roasted microsphere B1, mixing 100G of G1 with 300G of B1, adding a sodium silicate solution, a guiding agent, a sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization for 30 hours at 95 ℃, filtering to remove mother liquor, washing with water, and drying to obtain a product J1.
200g of the product J1 prepared in example 1 is put into a stainless steel kettle under stirring, 25% ammonia water solution is added for treatment for 100min at normal temperature, the washed first mixture is filtered, boric acid is adopted for the first mixture for exchange, and the exchange process conditions are as follows: pH 3.5, temperature 90 ℃, B: exchanging materials (dry basis) =0.50 (mass ratio), introducing dry gas into a pretreatment furnace after 100min, and roasting the materials for 2 hours at 500 ℃ and 100% of water vapor to obtain a baked material. 200g of a baked material with the burning loss of 2.8% is slowly added to the top end of a downer reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 200 mu m and the pressure of 6MPa, catalyst particles are dispersed in the reactor through the spraying of the atomizer and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 100% of carrier gas, and the reaction temperature is as follows: the contact time with the gas is 0.1min at 900 ℃, the flow rate of the gas is controlled, and the ratio of silicon tetrachloride to a baked material is 0.5:1. The inner diameters of the buffer zone and the reaction zone are: 0.05 meter, the heights are respectively: 0.2 and 0.3 meters. After the reacted materials enter an absorption tower to be purged for 30min, the reacted gas is discharged through a gas outlet pipe by a pump, enters a recovery system which is 10% sodium hydroxide solution, and is subjected to acid-base neutralization and collection. The catalyst is collected by a collector at the bottom of the absorption tower, washed for 0.5h by 19 times of water at 85 ℃, and dried to obtain Na 2 Catalyst C-1 having an O content of 0.43%.
Example 2
120g of magnesium nitrate was dissolved in 320mL of distilled water, and the dissolved solution was slowly poured into 2092 g of a solution containing 20% SiO 2 Mixing for 50 minutes to obtain a silicon-magnesium material, wherein the final pH value is 13.1, adding cerium chloride rare earth, wherein cerium chloride (calculated by cerium oxide)/silicon-magnesium material=2.3% (mass ratio), aging the material after adding the rare earth at 120 ℃ for 300 minutes, preparing mixed slurry with solid content of 32% by 10g of the aged material, 1000g of kaolin (burning base), 70g of sodium pyrophosphate, 10g of aluminum sol and deionized water, and spray-drying to obtain 600g of mixed slurry with particle size of 20%110 μm spray microsphere P2. And roasting the P2 spray soil ball at 990 ℃ for 1.5h to obtain a roasted microsphere G2. 100g of G2 is added into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 26 hours, mother liquor is removed by filtration, and the product J2 is obtained by washing and drying.
80g of the product J2 prepared in example 2 are put into a stainless steel kettle under stirring, and are exchanged by boric acid, wherein the exchange process conditions are as follows: pH 4.5, temperature 95 ℃, B: exchanging materials (dry basis) =0.15 (mass ratio), filtering and washing after 40min, adding 10% ammonia water solution at 20 ℃ to obtain a liquid-solid ratio of 8, treating for 100min, and roasting the materials in a pretreatment furnace at 700 ℃ and 80% steam for 0.5 h to obtain a roasted material with a burning loss of 1.8%; 80g of roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 50 mu m and the pressure of 0.1MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 10% of carrier gas, the gas-solid phase reaction temperature is 200 ℃, the gas contact time is 3min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.01:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.5 meter and 0.125 meter, and the heights are 1 meter. The reacted material was purged in the absorber for 15min. The gas is pumped and discharged through a gas outlet pipe, and enters a recovery system, wherein the recovery system is 20% sodium carbonate solution, and acid-base neutralization and collection are carried out on the reacted gas. The catalyst is collected by a collector at the bottom of the absorption tower, washed for 1h by 5 times of water at 95 ℃, and dried to obtain Na 2 Catalyst C-2 with O content of 0.34%.
Example 3
Dissolving 80g of magnesium sulfate with 300mL of distilled water, dissolving 139g of white carbon black into 300mL of distilled water to form a turbid solution, slowly injecting the magnesium sulfate solution into the white carbon black solution, mixing for 80 minutes to obtain a silicon magnesium material, adding yttrium carbonate, wherein the yttrium carbonate (calculated by yttrium oxide)/the silicon magnesium material is=9.7% (mass ratio), aging the material after adding rare earth for 200 minutes at 115 ℃, preparing mixed slurry with solid content of 40% by 100g of aged material, 1250g of kaolin, 187.5g of sodium silicate solution, 187.5g of alumina sol and deionized water, and spray-drying to obtain 1200g of spray microspheres P3 with particle size of 20-110 mu m. And roasting the P3 spray soil ball at 780 ℃ for 1.5h to obtain a roasted microsphere G3. 500g of G3 is added with sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 38 hours, mother liquor is removed by filtration, and the product J3 is obtained by washing and drying.
400g of the product J3 prepared in example 3 is put into a stainless steel kettle under stirring, 5% ammonia water solution is added at 40 ℃, the liquid-solid ratio is 10, the treatment is carried out for 120min, boric acid is adopted for exchange after filtration and washing, and the exchange process conditions are as follows: pH 5.8, temperature 92 ℃, B: exchange material (dry basis) =0.38 (mass ratio), roasting the material for 0.5 hours at 900 ℃ under the condition of 30% water vapor in a pretreatment furnace after 45min, and obtaining a roasting material with the burning loss of 0.8%. And a baking material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 80 mu m and the pressure of 4MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 30% of carrier gas, the gas-solid phase reaction temperature is 400 ℃, the contact time with the gas is 60min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.4:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.4 meter and 0.2 meter, the heights are 0.5 meter and 0.2 meter respectively. The reacted material is purged for 40min, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 12% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. The catalyst is collected by a collector at the bottom of the absorption tower, washed for 1h by 15 times of water at 65 ℃, and dried to obtain Na 2 Catalyst C-3 with O content of 0.25%.
Example 4
130g of magnesium carbonate is dissolved by 500mL of distilled water, the dissolved magnesium carbonate solution is slowly added into 4643g of alkaline silica sol and mixed for 90 minutes to obtain a magnesium silicate material, the final pH value is 7.3, cerium nitrate (calculated by cerium oxide) is added, the cerium nitrate/magnesium silicate material=1.4% (mass ratio) is added, the material after rare earth addition is aged for 150 minutes at 100 ℃, 200g of the aged material, 1818g (burning base) of kaolin, 345.42g of sodium silicate solution, 290.88g of aluminum sol and deionized water are prepared into a mixed slurry with the solid content of 47%, and 1600g of spray microspheres P4 with the particle size of 20-110 mu m are obtained through spray drying. Roasting one part of P4 at 1000 ℃ for 1.5 hours to obtain roasted microsphere G4, roasting the other part of P4 at 600 ℃ for 2 hours to obtain roasted microsphere B4, adding 1000G of G4 and 250G of B4 into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 89 ℃ for 30 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J4.
600g of the crystallized product J4 prepared in example 4 is put into a stainless steel kettle under stirring, 8% ammonia water solution with a liquid-solid ratio of 1.5 is added at 60 ℃, the treatment is carried out for 50min, boric acid is adopted for exchange after filtration and washing, and the exchange process conditions are as follows: pH 3.9, temperature 88 ℃, B: exchange material (dry basis) =0.22 (mass ratio), after 120min, bake the material in a pretreatment furnace at 600 ℃ and 50% water vapor for 1 hour, and obtain baked material with burning loss of 1.2%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 150 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 50% of carrier gas, the gas-solid phase reaction temperature is 500 ℃, the contact time with the gas is 30min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.05:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 2 times of water at 35 ℃ for 2 hours, and drying to obtain Na 2 Catalyst C-4 with O content of 0.49%.
Example 5
Dissolving 50g of magnesium nitrate with 200mL of distilled water, gradually dissolving 132g of white carbon black in 300mL of distilled water to form a turbid solution, slowly adding the dissolved magnesium nitrate solution into the turbid solution of white carbon black, mixing for 30 minutes to obtain a silicon-magnesium material, adding lanthanum chloride, wherein lanthanum chloride (calculated by lanthanum oxide)/silicon-magnesium material=13.7% (mass ratio), aging the rare earth-added material at 95 ℃ for 250 minutes, preparing 200g of aged material, 1053g (burning base) of kaolin, 136.89g of sodium silicate solution, 136.89g of alkaline silica sol and deionized water into a mixed slurry with the solid content of 43%, and spray-drying to obtain 900g of spray microspheres P5 with the particle size of 20-110 mu m. Roasting one part of P5 at 970 ℃ for 2.3 hours to obtain roasted microsphere G5, roasting the other part of P5 at 830 ℃ for 1.9 hours to obtain roasted microsphere B5, adding 400G of G5 and 400G of B5 into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 87 ℃ for 16 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J5.
600g of the crystallized product prepared in example 5 was put into a stainless steel kettle with stirring, and boric acid was used for exchange, and the exchange process conditions were: pH 3.6, temperature 85 ℃, B: exchange material (dry basis) =0.01 (mass ratio), filtering and washing after 15min, adding 15% ammonia water solution at 40 ℃ to obtain a liquid-solid ratio of 4, treating for 80min, and roasting the material in a pretreatment furnace for 1.5h with 100% water vapor at 800 ℃ to obtain a roasted material with a burning loss of 1.9%. 400g of roasting material is slowly added to the top end of a downer reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 180 mu m and the pressure of 5MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 80% of carrier gas, the gas-solid phase reaction temperature is 600 ℃, the contact time with the gas is 50min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.45:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.45 m and 0.3 m, the heights are 0.7 m and 0.5 m respectively. The reacted gas is pumped and discharged through a gas outlet pipe, enters a recovery system, the recovery system is 10% sodium hydroxide solution, and after the reacted material is purged for 25min in an absorption tower, the gas is subjected to acid-base neutralization and collection. The catalyst is collected by a collector at the bottom of the absorption tower, washed for 1.5h by 8 times of water at 75 ℃, and dried Drying to obtain Na 2 Catalyst C-5 with O content of 0.42%.
Example 6
80g of magnesium sulfate is dissolved by 300mL of distilled water, the dissolved solution is slowly added into 1860 g of sodium silicate solution, and mixed for 40 minutes to obtain a magnesium silicate material, the final pH value is 12.3, lanthanum carbonate (calculated by lanthanum oxide)/magnesium silicate material=4.8% (mass ratio) is added, the material after rare earth addition is aged for 50 minutes at 90 ℃, 300g of aged material, 5000g of kaolin (burning base), 450g of sodium pyrophosphate, 450g of silica sol and deionized water are prepared into mixed slurry with the solid content of 38%, and 4500g of spray microsphere P6 with the particle size of 20-110 mu m is obtained through spray drying. Roasting one part of P6 at 960 ℃ for 1.4 hours to obtain roasted microsphere G6, roasting the other part of P6 at 880 ℃ for 2 hours to obtain roasted microsphere B6, adding 600G of G6 and 400G of B6 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 92 ℃ for 34 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J6.
820g of the crystallized product J6 prepared in example 6 is put into a stainless steel kettle under stirring, boric acid is adopted for exchange, and the exchange process conditions are as follows: pH 4.0, temperature 93 ℃, B: exchange material (dry basis) =0.45 (mass ratio), filtering and washing after 60min, adding 20% ammonia water solution at 60 ℃, treating for 90min with a liquid-solid ratio of 7, and roasting the material in a pretreatment furnace at 650 ℃ and water vapor content of 10% for 1.5 h to obtain a roasted material with a burning loss of 1.1%. 750 g of roasting material is slowly added to the top end of a downer reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 130 mu m and the pressure of 2.2MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 90% of carrier gas, the gas-solid phase reaction temperature is 300 ℃, the gas contact time is 20min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to the in-situ crystallization catalyst is 0.36:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.2 m and 0.1 m, the heights are 0.4 m and 0.6 m respectively. Purging the reacted material in an absorption tower for 30min, exhausting the gas through a gas outlet pipe by a pump, and entering a recovery system And (3) carrying out acid-base neutralization and collection on the reacted gas by using a 5% sodium carbonate solution. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 5 times of water at 85 ℃ for 0.6h, and drying to obtain Na 2 Catalyst C-6 with O content of 0.38%.
Example 7
Slowly adding 242g of alkaline silica sol solution into 70g of magnesium chloride solution dissolved by 300mL of distilled water, mixing for 55 minutes to obtain a magnesium silicate material, adding cerium nitrate, cerium nitrate (calculated by cerium oxide)/magnesium silicate material=8.2% (mass ratio), aging the rare earth added material at 98 ℃ for 90 minutes, preparing 100g of aged material, 2500g of kaolin (burning base), 50g of sodium silicate solution, 75g of aluminum sol and deionized water into mixed slurry with the solid content of 36%, and spray-drying to obtain 1500g of spray microspheres P7 with the particle size of 20-110 mu m. Roasting one part of P7 at 850 ℃ for 2.3 hours to obtain roasted microspheres G7, roasting the other part of P7 at 680 ℃ for 2.6 hours to obtain roasted microspheres B7, adding 750G of G7 and 250G of B7 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J7.
550g of the crystallized product J7 prepared in example 7 is added into a stainless steel kettle under stirring, 23% ammonia water solution is added at 20 ℃, the liquid-solid ratio is 3, the treatment is carried out for 40min, boric acid is adopted for exchange after filtration and washing, and the exchange process conditions are as follows: pH 4.2, temperature 95 ℃, B: exchange material (dry basis) =0.09 (mass ratio), after 90min, the material was baked in a pretreatment furnace at 750 ℃ and water vapor content of 60% for 0.5 hours, to obtain a baked material with burning loss of 2.4%. 500g of roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 70 mu m and the pressure of 3.5MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 60% of carrier gas, the gas-solid phase reaction temperature is 800 ℃, the gas contact time is 10min, the flow rate of the gas is controlled, and the ratio of silicon tetrachloride to in-situ crystallization catalyst is 0.25:1. the inner diameters of the buffer zone and the reaction zone are: 0.25 m, respectively 0.6 in height Rice and 0.9 meter. After the reacted materials are purged for 20min through an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 13% sodium hydroxide solution, and acid-base neutralization and collection are carried out on the reacted gas. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 13 times of water at 85 ℃ for 2 hours, and drying to obtain Na 2 Catalyst C-7 with O content of 0.43%.
Example 8
Dissolving 90g of magnesium nitrate with 300mL of distilled water, slowly adding the dissolved solution into 948 g of sodium silicate solution, mixing for 25 minutes to obtain a magnesium silicate material, adding cerium chloride with the final pH value of 10.5, adding cerium chloride (calculated by cerium oxide)/magnesium silicate material=11% (mass ratio), aging the rare earth added material at 93 ℃ for 120min, preparing mixed slurry with the solid content of 42% by using 120g of aged material, 750g of kaolin (burning base), 60g of sodium silicate solution, 52.5g of alumina sol and deionized water, and spray-drying to obtain 750g of spray microspheres P8 with the particle size of 20-110 mu m. Roasting P8 at 630 ℃ for 2.1h to obtain roasted microspheres B8, adding 700g of B8 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 94 ℃ for 36h, filtering to remove mother liquor, washing with water, and drying to obtain a product J8.
450g of the crystallized product J8 prepared in example 8 is put into a stainless steel kettle under stirring, boric acid is adopted for exchange, and the exchange process conditions are as follows: pH 3.7, temperature 90 ℃, B: exchange material (dry basis) =0.32 (mass ratio), after 30min, filter wash. Adding 18% ammonia water solution at 30deg.C, treating for 60min, and roasting the material in a pretreatment furnace at 750deg.C with water vapor amount of 60% for 0.5 hr to obtain roasted material with burning loss of 2.2%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 85 mu m and the pressure of 4.7MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 20% of carrier gas, the gas-solid phase reaction temperature is 700 ℃, the contact time with the gas is 2min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.14:1. bufferingThe inner diameters of the zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.8 meter and 1 meter respectively. And (3) purging the reacted material in the absorption tower for 50min, exhausting the gas through a gas outlet pipe by a pump, and entering a recovery system which is 10% sodium carbonate solution, and neutralizing and collecting the reacted gas by acid and alkali. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 8 times of water at 95 ℃ for 2 hours, and drying to obtain Na 2 Catalyst C-8 with O content of 0.38%.
Example 9
170g of magnesium nitrate is dissolved by 600mL of distilled water, 933g of white carbon black is gradually dissolved in 1000mL of distilled water to form a turbid solution, the dissolved magnesium nitrate solution is slowly added into the turbid solution of white carbon black, and is mixed for 90 minutes to obtain a silicon magnesium material, the final pH value is 7.3, yttrium carbonate (calculated by yttrium oxide)/silicon magnesium material=15.6% (mass ratio) is added, the material after rare earth addition is aged for 30 minutes at 83 ℃, 120g of the aged material, 4000g of kaolin (burning base), 600g of sodium pyrophosphate, 720g of alkaline silica sol and deionized water are prepared into a mixed slurry with the solid content of 42%, and 750g of spray microspheres P9 with the particle size of 20-110 mu m are obtained through spray drying. Roasting one part of P9 at 890 ℃ for 1.5 hours to obtain roasted microspheres G9, roasting the other part of P9 at 770 ℃ for 1.8 hours to obtain roasted microspheres B9, adding 200G of G9 and 400G of B9 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization at 88 ℃ for 28 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J9.
550g of the crystallized product J9 prepared in example 9 is added into a stainless steel kettle under stirring, 6% ammonia water solution with the liquid-solid ratio of 9 is added at 50 ℃, the treatment is carried out for 50min, boric acid is adopted for exchange after filtration and washing, and the exchange process conditions are as follows: pH 3.9, temperature 89 ℃, B: exchange material (dry basis) =0.28 (mass ratio), after 15min, the material was baked in a pretreatment furnace 880 ℃ for 0.5 hours with water vapor amount of 20%, and a baked material with a burning loss of 0.8% was obtained. The roasting material is slowly added into the top end of a descending bed reactor through a feeder, the top end of the reactor is provided with an atomizer with the gas eye diameter of 160 mu m and the pressure of 5.5MPa, and catalyst particles are dispersed in the reactor, run downwards and are mixed with silicon tetrachloride through the spraying of the atomizer The gases meet, the proportion of the silicon tetrachloride is 40% of the carrier gas, the gas-solid phase reaction temperature is 450 ℃, the contact time with the gases is 1min, the flow rate of the gases is controlled, and the proportion of the silicon tetrachloride to the in-situ crystallization catalyst is 0.30:1. The inner diameters of the buffer zone and the reaction zone are: 0.5 m, and heights of 0.9 m and 0.4 m respectively. After the reacted materials are purged for 35min through an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 8% sodium carbonate solution, and the reacted gas is subjected to acid-base neutralization and collection. Collecting the catalyst by a collector at the bottom of the absorption tower, washing with 10 times of water at 95 ℃ for 1h, and drying to obtain Na 2 Catalyst C-9 with O content of 0.36%.
Example 10
Dissolving 60g of magnesium chloride with 200mL of distilled water, slowly adding the dissolved solution into 191g of alkaline silica sol solution, mixing for 70 minutes to obtain a magnesium silicate material, adding cerium nitrate, cerium nitrate (calculated by cerium oxide)/magnesium silicate material=5.7% (mass ratio), aging the rare earth-added material at 89 ℃ for 280 minutes, preparing mixed slurry with solid content of 36% from 300g of aged material, 6000g of kaolin (burning base), 660g of sodium pyrophosphate, 900g of alkaline silica sol and deionized water, and spray-drying to obtain 2100g of spray microsphere P10 with particle size of 20-110 mu m. Roasting one part of P10 at 830 ℃ for 2.8 hours to obtain roasted microsphere G10, roasting the other part of P10 at 670 ℃ for 3.6 hours to obtain roasted microsphere B10, adding 900G of G10 and 300G of B10 into sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water and drying to obtain a product J10.
550g of the crystallized product J10 prepared in example 10 was put into a stainless steel kettle with stirring, and boric acid was used for exchange, and the exchange process conditions were: pH 3.5, temperature 86 ℃, B: exchange material (dry basis) =0.40 (mass ratio), adding 13% ammonia water solution at 50 ℃ after 120min, wherein the liquid-solid ratio is 5.5, treating for 70min, filtering and washing, and roasting the material for 2 hours at 600 ℃ in a pretreatment furnace with 70% of water vapor to obtain a roasted material with the burning loss of 1.5%. The roasting material is slowly added to the top end of a descending bed type reactor through a feeder, the top end of the reactor is an atomizer with the gas eye diameter of 140 mu m and the pressure of 3MPa, catalyst particles are dispersed in the reactor and run downwards to meet silicon tetrachloride gas, the silicon tetrachloride accounts for 50% of carrier gas, the gas-solid phase reaction temperature is 500 ℃, the contact time with the gas is 30min, the flow rate of the gas is controlled, and the ratio of the silicon tetrachloride to an in-situ crystallization catalyst is 0.23:1. The inner diameters of the buffer zone and the reaction zone are respectively: 0.3 meter and 0.15 meter, the heights are 0.3 meter and 0.7 meter respectively. The reacted materials are purged for 60min in an absorption tower, the gas is pumped and discharged through a gas outlet pipe and enters a recovery system, the recovery system is 15% sodium hydroxide solution, and the reacted gas is subjected to acid-base neutralization and collection. After the catalyst is collected by a collector at the bottom of the absorption tower,
Washing with 16 times of water at 75deg.C for 1 hr, and drying to obtain Na 2 Catalyst C-10 with O content of 0.46%.
Comparative example 1
In contrast to example 3, 139g of white carbon black was dissolved in 300ml of distilled water to form a turbid solution, and aged at 115℃for 200 minutes, 100g of the aged material, 1250g of kaolin (burning group), 187.5g of sodium silicate solution, 187.5g of alumina sol, and deionized water were prepared into a mixed slurry having a solid content of 40%, and spray-dried to obtain 1200g of spray microspheres P11 having a particle size of 20 to 110. Mu.m. And roasting the P11 spray soil ball at 780 ℃ for 1.5h to obtain a roasted microsphere G11. 500g of G11 is added with sodium silicate solution, guiding agent, sodium hydroxide solution and deionized water, and is subjected to hydrothermal crystallization at 85 ℃ for 38 hours, mother liquor is removed by filtration, and the product J11 is obtained by washing and drying.
The product J11 produced in comparative example 1 was first calcined in a roaster at 900℃for 0.5 hours under 30% steam conditions to give a calcined material having a burn-down of 0.8%. The roasting material is slowly added to the top end of the reactor through a feeder, a silicon tetrachloride gas inlet is arranged at the top end of the reactor, silicon tetrachloride accounts for 30% of carrier gas, the roasting material and silicon tetrachloride react in the same direction in the reactor, the gas-solid phase reaction temperature is 400 ℃, the contact time with the gas is 60min, and the ratio of the silicon tetrachloride to the roasting material is 0.4:1. The reacted gas is discharged through a gas outlet pipe by a pump, enters a recovery system, The recovery system is 12% sodium hydroxide solution, and acid-base neutralization is carried out. The catalyst is collected by a collector at the bottom of the absorption tower, washed for 1h by 15 times of water at 65 ℃, and dried to obtain Na 2 Catalyst C-11 with O content of 0.46%.
Comparative example 2
In contrast to example 1, 20g of magnesium chloride was dissolved in 100mL of distilled water, aged at 80℃for 5 minutes, 100g of the aged material, 800g of kaolin (burning base), 40g of sodium silicate solution, 160g of alkaline silica sol, and deionized water were prepared into a mixed slurry having a solid content of 46%, and spray-dried to obtain 600g of spray microspheres P12 having a particle size of 20 to 110. Mu.m. Roasting one part of the P12 spray soil ball for 2.7 hours at 980 ℃ to obtain roasted microspheres G12, roasting the other part of the P12 spray soil ball for 2.5 hours at 650 ℃ to obtain roasted microspheres B12, mixing 100G of G12 and 300G of B12, adding sodium silicate, a guiding agent, a sodium hydroxide solution and deionized water, carrying out hydrothermal crystallization for 30 hours at 95 ℃, filtering to remove mother liquor, washing with water, and drying to obtain a product J12.
The product J12 prepared in comparative example 2 was baked in a baking oven at 500℃for 2 hours with 100% steam to obtain a baked material. A baked material reacts with silicon tetrachloride gas in the same direction in an inclined tube furnace, the silicon tetrachloride accounts for 100% of carrier gas, and the reaction temperature is as follows: the contact time with gas is 0.1min at 900 ℃, and the ratio of silicon tetrachloride to roasting material is 0.5:1. And (3) allowing the reacted gas to enter a recovery system, wherein the recovery system is 10% sodium hydroxide solution, and performing acid-base neutralization. Discharging the catalyst from the other end of the reaction tube, washing the catalyst for 0.5h at 85 ℃ with 19 times of water, and drying to obtain the catalyst C-12 with the Na2O content of 0.45%.
Comparative example 3
In comparison with example 7, 242g of an alkaline silica sol solution was slowly added to a magnesium chloride solution in which 70g of magnesium chloride was dissolved with 300mL of distilled water, and mixed for 55 minutes to obtain a magnesium silicate material, the final pH was 11.5, the material was aged at 100 ℃ for 90 minutes, cerium nitrate (calculated as cerium oxide)/magnesium silicate material=8.2% (mass ratio), 100g of rare earth-added material, 2500g of kaolin (burning group), 50g of sodium silicate solution, 75g of alumina sol, deionized water were added to prepare a mixed slurry having a solid content of 36%, and spray-dried to obtain 1500g of spray microspheres P13 having a particle size of 20 to 110 μm. Roasting one part of P13 at 850 ℃ for 2.3 hours to obtain roasted microspheres G13, roasting the other part of P13 at 680 ℃ for 2.6 hours to obtain roasted microspheres B13, adding 750G of G13 and 250G of B13 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 92 ℃ for 32 hours, filtering to remove mother liquor, washing with water, and drying to obtain a product J13.
The product J13 prepared in the comparative example 3 is firstly roasted for 0.5 hour in a roasting furnace at 750 ℃ under the condition that the water vapor quantity is 60%, then enters a reactor along the same direction with silicon tetrachloride, the silicon tetrachloride accounts for 30% of carrier gas, the roasted material and the silicon tetrachloride react in the reactor along the same direction, the gas-solid phase reaction temperature is 400 ℃, the contact time with the gas is 60min, and the ratio of the silicon tetrachloride to the roasted material is 0.4:1. And (3) the reacted gas enters a recovery system, wherein the recovery system is a 12% sodium hydroxide solution, and acid-base neutralization is performed. After the catalyst was collected, it was washed with 13 times of water at 85℃for 2 hours, and dried to obtain catalyst C-13 having a Na2O content of 0.45%.
Comparative example 4
In contrast to example 8, 90g of magnesium nitrate was dissolved in 300mL of distilled water, the dissolved solution was slowly added to 948 g of sodium silicate solution, and mixed for 25 minutes to obtain a magnesium silicate material, the final pH value was 10.5, the material was aged at 93℃for 120 minutes, 120g of the aged material, 750g of kaolin (burning group), 60g of sodium silicate solution, 52.5g of alumina sol, and deionized water were prepared into a mixed slurry having a solid content of 42%, and 750g of spray microspheres P14 having a particle size of 20 to 110 μm were obtained by spray drying. Roasting P14 at 630 ℃ for 2.1h to obtain roasted microspheres B14, adding 700g of B14 into sodium silicate solution, a guiding agent, sodium hydroxide solution and deionized water, performing hydrothermal crystallization at 94 ℃ for 36h, filtering to remove mother liquor, washing with water, and drying to obtain a product J14.
Adding 450g of the crystallized product J14 prepared in the comparative example 4 into a stainless steel kettle under stirring, adding ammonium chloride and deionized water, wherein the ammonium chloride/crystallized product is=0.20, the ammonium sulfate/crystallized product is=0.30, exchanging for 1.5 hours at the pH value of between 3.0 and 3.5 and 90 ℃, filtering to remove filtrate, washing a filter cake with deionized water, and drying to obtain a exchange material; the exchange material is treated with water at 560 DEG CRoasting for 2 hours under the condition that the steam inlet amount is 95% to obtain a roasted material; exchanging the baked material once by lanthanum chloride, wherein the exchanging conditions are as follows: lanthanum chloride/one baked material=0.034, pH=3.5-4.2, temperature 90 ℃ for 1 hour, baking the exchanged material at 700 ℃ for 1.5 hours to obtain two baked materials, and filtering, washing and drying the two baked materials to obtain Na through acid exchange 2 Catalyst C-14 with O content of 0.39%.
The crystallization conditions and crystallization results of examples 1 to 10 and comparative examples 1 to 4 are shown in Table 1, and the test results of the pore structure of the crystallized product are shown in Table 2. The pore structure results of table 2 show that: the synthetic method of the patent can prepare a crystallized product with a developed pore structure. The addition of the silicon-magnesium structural material brings about the change of the microsphere precursor structure in the synthesis system, thereby improving the pore structure of the crystallized product. The crystalline product prepared by the scheme of adding silicon magnesium and then directly ageing, but not ageing with rare earth has a pore structure and a specific surface which are not as same as those of the corresponding embodiment, which shows that the rare earth and the silicon magnesium are aged together, so that a better cross-linked structure can be formed, the growth of an in-situ molecular sieve is facilitated, and the remarkable specific surface and pore volume increase are brought. Compared with the material which simply uses silicon or magnesium, the crystallization product prepared by the scheme has more abundant pore structure. The results of FIGS. 1 and 2 show that the catalyst has a more abundant mesoporous structure in example 1, compared with comparative example 2, due to the exchange of ammonia and boric acid. The adsorption curves tested by using naphthalene as a probe molecule have no difference; however, when quinoline is used as a probe molecule, as the quinoline contains alkaline groups, the adsorption curves of the two agents are obviously different, so that the technology can bring more excellent acid distribution and activity accessibility to the catalyst, and provides a guarantee for realizing the high-efficiency conversion of the heavy oil and improving the gasoline yield.
Table 3 catalyst sodium oxide and 17h microreaction results show: the catalyst prepared by adopting the reaming material and the isomorphous substitution process has simpler process flow, lower sodium oxide content and more excellent 17-hour micro-reaction activity.
TABLE 1 in situ crystallization process conditions and preparation results
Figure BDA0003392346170000271
TABLE 2 pore structure characteristics of crystallized products
Figure BDA0003392346170000272
TABLE 3 sodium oxide content and microreaction of catalyst
Figure BDA0003392346170000281
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (24)

1. A method for preparing a catalytic cracking catalyst by an ammonium-free method, which is characterized by comprising the following steps:
(1) Mixing a magnesium source solution with a silicon source solution to obtain a silicon-magnesium material, adding a rare earth compound, and aging to obtain the silicon-magnesium material containing rare earth;
(2) Mixing rare earth-containing silicon-magnesium material with kaolin, a dispersing agent and/or a reinforcing agent and deionized water, pulping, spraying into microspheres, roasting, mixing with sodium silicate, a guiding agent, an alkali solution and water, and crystallizing to obtain a crystallized product;
(3) Exchanging and modifying the crystallized product with ammonia water and boric acid, and roasting to obtain a primary roasting material;
(4) And (3) carrying out countercurrent contact on the primary roasting material and silicon tetrachloride in a downward bed type isomorphous substitution reactor to carry out isomorphous substitution reaction so as to obtain the catalyst.
2. The method for preparing a catalytic cracking catalyst according to claim 1, wherein in step (1), the magnesium source solution and the silicon source solution are mixed, the pH is adjusted to 8 to 12, and then the rare earth compound is added.
3. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the aging conditions in step (1) are aging at 80 to 120 ℃ for 5 to 300 minutes, preferably 80 to 100 ℃ and aging time is preferably 30 to 200 minutes.
4. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the rare earth compound in step (1) is represented by rare earth oxide RE 2 O 3 Meter, RE 2 O 3 The mass ratio of the Si to Mg material is 1-10%, and the molar ratio of Si to Mg in the Si to Mg material is 0.1-15: 1.
5. the method for preparing a catalytic cracking catalyst by an ammonium-free method according to claim 1, wherein the silicon source in the step (1) is one or more of water glass, silica sol and white carbon black; the magnesium source is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate.
6. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the mass ratio of rare earth-containing silicon-magnesium material to kaolin in step (2) is 0.1-20:100, the mass ratio of dispersant to kaolin is 1-20:100, preferably 1-15:100, the mass ratio of reinforcing agent to kaolin is 1-20:100, preferably 2-8:100, and the solid content of the slurry after mixing and pulping is 30-50%.
7. The method for producing a catalytic cracking catalyst according to claim 1, wherein the particle size of the microspheres obtained by spraying in the step (2) is 20 to 110. Mu.m.
8. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the calcination temperature in step (2) is 600-1000 ℃, the calcination time is 1-3 hours, and the crystallization conditions are 85-95 ℃ and 16-36 hours.
9. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the dispersant is sodium silicate and/or sodium pyrophosphate; the reinforcing agent is silica sol and/or aluminum sol.
10. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the kaolin in step (2) is soft kaolin and/or hard kaolin, wherein the diameter of the kaolin is 1.5-3.0 μm, the content of crystalline kaolinite is higher than 80%, the iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
11. The method for producing a catalytic cracking catalyst according to claim 1, wherein the concentration of ammonia in step (3) is 1 to 25%.
12. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the mass ratio of boron element to crystallized product in the step (3) is 0.01-0.50: 1.
13. the method for preparing a catalytic cracking catalyst by an ammonium-free method according to claim 1, wherein the crystallization product in the step (3) is treated with ammonia water at 20-60 ℃ for 30-120 min, and the product exchanged with ammonia water is exchanged with boric acid under the following process conditions: the pH value is 3-6, and the temperature is 90-110 ℃.
14. The method for preparing a catalytic cracking catalyst by an ammonium-free method according to claim 1, wherein after roasting in the step (3), the burning loss is less than 3%, and a microspherical primary roasting material containing 5-60% of Y-type molecular sieve is obtained.
15. The method for preparing the catalytic cracking catalyst by the ammonium-free method according to claim 1, wherein the mass ratio of silicon tetrachloride to primary roasting material in the step (4) is 0.01-0.5: 1.
16. the method for preparing a catalytic cracking catalyst according to claim 1, wherein the specific surface area of the catalyst is 200-500 m 2 Per gram, the pore volume is 0.40-0.55 mL/g.
17. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the pretreatment furnace comprises a feeding section, a roasting section and a discharging section, the total length of the pretreatment furnace is 0.5-5 m, the inner diameter is 0.01-1 m, and the roasting temperature is 100-1000 ℃.
18. The method for preparing a catalytic cracking catalyst according to claim 17, wherein the pretreatment furnace comprises a heating system and a ventilation system, the heating system is arranged on the outer layer of the pretreatment furnace in a furnace tile jacket mode, the ventilation system is arranged on the inner wall of the pretreatment furnace, and the ventilation system can input dry gas, nitrogen or water vapor into the interior of the pretreatment furnace.
19. The method for preparing a catalytic cracking catalyst according to claim 17, wherein an included angle α between the feed section of the pretreatment furnace and the main body of the pretreatment furnace is greater than 10 ° and less than 90 °, and an included angle β between the main body of the pretreatment furnace and the horizontal position is greater than 10 ° and less than 90 °.
20. The method for preparing a catalytic cracking catalyst by an ammonium-free method according to claim 17, wherein a shaft rotating device is arranged at the top of the pretreatment furnace to control the rotation of the furnace body of the pretreatment furnace, and the rotation frequency is 10-80 Hz/min.
21. The method for preparing a catalytic cracking catalyst by an ammoniumless method according to claim 1, wherein the downer isomorphous substitution reactor is divided into a buffer zone and a reaction zone from top to bottom, a catalyst inlet is arranged at the top of the buffer zone, an atomizer communicated with the catalyst inlet is arranged at the upper part of the buffer zone, a nitrogen inlet carrying silicon tetrachloride is arranged at the bottom of the reaction zone, a discharge outlet is arranged at the upper part of the reaction zone, and the inner diameter ratio of the buffer zone to the reaction zone is 1:1 to 4:1, preferably 1:1 to 3:1, the height of the buffer zone and the reaction zone being each independently 0.2 to 1 meter.
22. The method for preparing a catalytic cracking catalyst according to claim 21, wherein the inner diameter ratio of said buffer zone to said reaction zone is 1:1-3:1; preferably, a heating sleeve or a heating belt is arranged on the outer wall of the downer isomorphous substitution reactor; preferably, the diameter of the cavity of the reaction zone is 0.05-0.5 m.
23. The method for preparing a catalytic cracking catalyst according to claim 21, wherein the atomizer is made of stainless steel and comprises a plurality of symmetrically distributed gas holes, the diameter of the gas holes is 80-200 um, and the internal gas pressure of the atomizer is 0.1-6 MPa.
24. The method for preparing the catalytic cracking catalyst by the ammonium-free method according to claim 1, wherein in the step (4), the isomorphous substitution reaction temperature is 200-900 ℃, preferably 300-600 ℃, the time for contacting the primary roasting material with the silicon tetrachloride gas is 0.1-60 min, nitrogen is taken as carrier gas to carry the silicon tetrachloride into the reactor, and the proportion of the silicon tetrachloride to the total carrier gas is as follows: 0.1 to 100 percent.
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