CN112108171A - Preparation method of anti-heavy metal catalytic cracking catalyst - Google Patents

Preparation method of anti-heavy metal catalytic cracking catalyst Download PDF

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CN112108171A
CN112108171A CN201910547780.4A CN201910547780A CN112108171A CN 112108171 A CN112108171 A CN 112108171A CN 201910547780 A CN201910547780 A CN 201910547780A CN 112108171 A CN112108171 A CN 112108171A
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catalytic cracking
cracking catalyst
heavy metal
acid
microspheres
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CN112108171B (en
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张莉
王久江
孙雪芹
廖翼涛
刘宏海
胡清勋
杨周侠
赵红娟
熊晓云
赵晓争
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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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Abstract

A preparation method of a heavy metal resistant catalytic cracking catalyst. The kaolin is used as a raw material, chemical water, a structural assistant, a dispersing agent and/or a reinforcing agent and boric phosphoric acid are added, the slurry is fully mixed, the pH value of the slurry is adjusted to 3-4 by acid, and then the slurry is sprayed into microspheres; roasting the spray microspheres, mixing the roasted microspheres with a guiding agent, water glass and sodium hydroxide, and carrying out crystallization reaction under a hydrothermal condition to obtain a crystallized product which has a good pore structure and wear resistance and contains 40-50% of NaY molecular sieve, wherein the in-situ crystallized microspheres can be used as a precursor for preparing a catalytic cracking catalyst. The in-situ crystallized microsphere is subjected to aluminum salt, acid exchange and rare earth impregnation to prepare the heavy metal resistant catalytic cracking catalyst.

Description

Preparation method of anti-heavy metal catalytic cracking catalyst
Technical Field
The invention relates to the field of catalytic materials, in particular to a preparation method of a heavy metal resistant catalyst.
Background
With the increasing weight and deterioration of crude oil in the world, refineries in various countries have been vigorously developing the Fluidized Catalytic Cracking (FCC) technology for blending or refining heavy oil and residual oil, so as to broaden the source of FCC raw oil, meet the requirements of global markets for light oil products, and improve economic benefits to the maximum extent. Along with the fluctuation of the current oil price, the situation of transformation from oil refining to chemical engineering is that the primary conversion rate of raw oil is very important. Compared with the conventional FCC raw oil (such as AGO and VGO), the residual oil or heavy oil has obviously higher metal content such as Ni, V, Fe, Cu and the like, and seriously pollutes the FCC catalyst, wherein the most influential is nickel and vanadium which are deposited on the catalyst, so that the cracking activity of the catalyst is reduced, the selectivity of the product is deteriorated, and when the content of vanadium is very high, the molecular sieve structure can be damaged, so that the catalyst is completely deactivated; in addition, nickel and vanadium can also cause gas compressor and blower overload of the FCC unit, increased regenerator temperature, increased fresh catalyst make-up rate, increased energy consumption, and reduced FCC unit per pass conversion. At present, methods for solving heavy metal pollution mainly include methods of using a catalyst for resisting heavy metal pollution, pretreating raw materials (such as hydrofining, solvent deasphalting and the like) and passivating polluted metals on a balancing agent (such as using a metal passivator) and the like, and a magnetic separation technology is used for removing an aging agent with serious pollution abroad. Compared with other methods, the development and use of the heavy metal resistant FCC catalyst fundamentally solve the pollution problem of high heavy metal cracking feed, can greatly reduce the investment cost of equipment, improve the product distribution and improve the yield of light oil, and is a necessary trend for the development of the FCC catalyst in future. Therefore, the development of a novel catalytic cracking catalyst which has independent intellectual property rights and strong capabilities of processing high-proportion residual oil and heavy oil conversion and resisting heavy metal pollution has very important practical significance for improving the overall technical level of the Chinese petroleum refining industry.
Early heavy metal resistant technologies relied mostly on the use of passivating agents such as: the nickel passivation agent, the vanadium passivation agent and the like use a large amount of harmful substances such as antimony, bismuth and the like, and along with the development of the technology, the development of the heavy metal resistant catalyst with low toxicity and flexible operation becomes the key point of research and development.
In the research and development of foreign countries, among the cracking catalysts containing alkaline earth metal compounds, the catalysts containing strontium carbonate and calcium carbonate have better vanadium pollution resistance compared with magnesium salt and barium salt in US 4824815 and US 4944864 of Exxon company. The MAT and hydrogen yields for the 2 catalysts were the same, but the coke yield for the strontium agent was significantly lower than for the calcium agent. In conclusion, the strontium agent has better vanadium capturing effect than other alkaline earth metal vanadium capturing agents.
The vanadium trap developed by Phillips company in US4750988 is prepared by soaking a magnesium compound on A12O3 by taking MgO as a vanadium trapping active substance, drying and roasting, and can improve the conversion rate and selectivity of feeding materials and the yield of gasoline. US 4377494, US 4473463 describe vanadium traps for barium containing compounds from Phillips company, which when the vanadium content on the catalyst is 6mg/g, the conversion is improved by 2% compared to before the vanadium trap is added, the gasoline yield is increased by 7.5%, while the hydrogen and coke yields are reduced by 30% and 12%, respectively.
US 5141624 also discloses a process for cracking a vanadium-containing feedstock oil wherein the vanadium-resistant catalyst is a mechanical mixture of molecular sieves embedded in an inorganic matrix and magnesium oxide supported on alumina, which may be replaced by other magnesium compounds such as magnesium nitrate, bicarbonate, formate, acetate, etc., provided that it decomposes to magnesium oxide during calcination. Experiments show that the existence of the magnesium oxide diluent obviously improves the conversion rate of the raw materials and the yield of the gasoline.
US5071806 teaches a sulfur-resistant highly efficient vanadium trap CVP-3 with a vanadium trapping coefficient of 17 when the vanadium content of the catalyst is 6 mg/g. US4465779 also discloses a vanadium resistant catalyst which is composed of a solid cracking catalyst and a diluent which is a magnesium compound or a mixture of a magnesium compound and other metal compounds with good thermal stability, wherein the magnesium compound can be magnesium oxide, sepiolite, chrysotile and the like. The catalyst is especially suitable for the condition of serious vanadium pollution, the reaction conversion rate is improved by 6.8-l to 0.0 percent compared with the original FCC catalyst, the light oil yield is improved by 7-9.7 percent, and the yields of hydrogen and coke are reduced by 1.2 percent and 0.28 percent. US26551681A adopts an in-situ crystallization technology, and the catalyst capable of resisting nickel and vanadium is finally obtained through phosphorus source impregnation modification.
The domestic CN99109680.0 and CN00122001.2 both adopt rare earth oxide as an anti-vanadium component. The addition amount of RE2O3 in CN00122001.2 is 3-12%, the assistant has the advantages of high cracking activity, strong vanadium resistance, stable structure, flexible use and the like, and the reaction activity of the FCC catalyst can be obviously improved by adopting the assistant, so that the assistant is particularly suitable for a catalytic cracking device with high vanadium feed. In the preparation method of the heavy metal resistant FCC catalyst introduced in CN00122003.9, 1-25% of metal trapping component is added, the metal trapping component is rare earth oxide such as rare earth oxalate, and the catalyst has excellent heavy metal resistant performance and is suitable for cracking heavy oil with high Ni, V and the like. Under the condition that the catalyst is polluted by 5000ppmV, the retention rate of 800 ℃/4h micro-reverse activity of the catalyst is still more than 93 percent, and meanwhile, the catalyst is high in activity and good in cracking reactivity and is suitable for heavy oil with higher contents of Ni, V and the like. CN200510068179.5 prepares a cracking catalyst which can resist heavy metal pollution by adding alkaline earth metal compounds and rare earth metal compounds, the cracking catalyst prepared by the method has good capability of resisting nickel and vanadium pollution (containing Ni 6000ppm and V1000 ppm), and when the content of nickel on the catalyst is higher, high conversion rate and light oil yield can be still maintained. The invention discloses CN200510076790.2, which relates to a novel solid heavy metal resistant FCC auxiliary agent and a preparation method thereof. The assistant has the advantages of large specific surface area and pore volume, stable structure, strong heavy metal resistance, flexible use and the like. CN201210219566.4, CN201210220785.4 and CN201210217714.9 describe a series of catalytic cracking catalysts which reduce the coke yield and produce more propylene, more diesel oil and gasoline. CN102050434A adopts a phosphorus modified aluminum sol to improve the gasoline yield; CN102019195A discloses a molecular sieve modified by mixing phosphorus and rare earth to improve the conversion capability of heavy oil.
It is known from the research and development on the anti-heavy metal catalyst or the auxiliary agent at home and abroad that the in-situ crystallization catalyst plays an important role in the anti-heavy metal performance due to the special pore structure and the distribution of the active components, and the patent achieves a certain effect in the aspect of modulating the pore structure of the catalyst and the functional components to improve the anti-heavy metal performance, but most of the patent focuses on the addition of the functional components such as magnesium and aluminum, and the effect in the aspect of modulating the pore structure is not obvious.
In the invention, the boric acid is added in the pulping stage, the spraying slurry is adjusted to be acidic, which is more beneficial to the dissolution of boron, and the dissolved boric acid and soluble zinc salt or soluble alkaline earth metal salt in the slurry form borophosphate in the subsequent high-temperature roasting stage. Borophosphates contain both phosphorus-and boron-oxygen containing groups. The compound not only has a zeolite-like structure and can change the pore structure of the catalyst, but also has a boron-phosphorus combination structure which can effectively change the acidity of the catalyst, so that an in-situ crystallization product with adjustable molecular sieve content of 40-50% and good pore structure is prepared by an in-situ crystallization process. Higher molecular sieve content enhances the heavy metal resistance of the catalyst. On the basis, by using the post-modification exchange of aluminum salt, acid and rare earth, the pore structure is modulated, the acidity of the catalyst is further changed from the source, and the heavy metal resistance performance is more excellent.
Disclosure of Invention
The invention provides a preparation method of a heavy metal resistant catalytic cracking catalyst, which comprises the steps of adding one or more of kaolin, boron phosphoric acid, soluble zinc salt, soluble alkaline earth metal salt and soluble rare earth compound in a spray pulping link, adjusting the pH value of slurry to 3-4 by using acid, and then preparing a crystallization product containing 40-50% of NaY molecular sieve through spraying and hydrothermal crystallization. Then the catalytic cracking catalyst is prepared by aluminum salt and acid exchange, roasting and rare earth impregnation. Calculated by taking the mass of the catalytic cracking catalyst as 100 percent, Na20.1-0.7% of O, and Al2O3The content is 0.1-15%, and the content of rare earth is 0.1-6%.
The invention discloses a preparation method of a catalytic cracking catalyst capable of resisting heavy metals, which adopts the technical scheme that: 1) dissolving boric acid into a solution according to the liquid-solid mass ratio of 2-10, slowly adding a phosphoric acid (85%) solution, fully mixing, treating for 10-120 minutes at the pH of 1-4.0 to obtain borophosphoric acid; mixing the obtained borophosphate with chemical water containing a structural assistant, a dispersing agent and/or a reinforcing agent, pulping, wherein the solid content of the slurry is 30-50%, adjusting the pH value of the slurry to 3-4 by using acid for the mixed slurry, then spraying, drying, roasting at 600-1000 ℃, mixing with sodium silicate, a guiding agent, a sodium hydroxide solution and water, crystallizing at 85-95 ℃ for 16-36 hours, filtering, washing and drying the crystallized product to obtain the NaY molecular sieve; the structural auxiliary agent comprises one or more of soluble zinc salt, soluble alkaline earth metal salt and soluble rare earth compound, the addition amount of the structural auxiliary agent is 0.1-8% of the total mass of the kaolin, the preferable addition amount is 0.1-5%, and the addition amount of the boron phosphoric acid is 0.1-20% of the mass of the kaolin, the preferable addition amount is 0.1-15%. 2) Carrying out aluminum salt, acid exchange, roasting and rare earth impregnation on the crystallized product prepared in the step 1) to prepare the heavy metal resistant catalytic cracking catalyst.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, which is characterized in that a structural auxiliary agent, a dispersing agent and/or a reinforcing agent are added into mixed and beaten slurry, the adding sequence of the dispersing agent and the reinforcing agent is not limited, and the dispersing agent and the reinforcing agent can be added simultaneously with the structural auxiliary agent or in batches; the dispersing agent comprises one of sodium silicate and sodium pyrophosphate, the adding amount of the dispersing agent is 2-10% of the mass of kaolin, and the reinforcing agent comprises one of silica sol and aluminum sol, the adding amount of the reinforcing agent is 2-10% of the mass of kaolin, and the preferable adding amount is 2-8%.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, which comprises the step of adding boric acid and phosphoric acid mixture into boric acid and phosphoric acid, wherein the molar ratio of B to P in the boric acid is 0.1-10.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, wherein structural auxiliaries are soluble zinc salt, soluble alkaline earth and soluble rare earth compound metal salt, the soluble zinc salt is zinc chloride and zinc nitrate, the soluble alkaline earth metal salt is magnesium chloride and magnesium nitrate, and the soluble rare earth compound is lanthanum nitrate, cerium chloride, lanthanum chloride and cerium nitrate.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, wherein acid for adjusting the pH value of slurry is one of hydrochloric acid, sulfuric acid, nitric acid, citric acid and oxalic acid, and the pH value of the slurry is controlled to be 3-4 after the acid is added.
The invention discloses a preparation method of a catalytic cracking catalyst capable of resisting heavy metals, wherein kaolin comprises soft kaolin, hard kaolinite and coal gangue, the bit diameter of the soft kaolin is 1.5-3.0 mu m, the content of crystal kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
The composition of the directing agent in the method disclosed by the invention is not particularly limited, and a common directing agent can be prepared, for example, according to the directing agent composition in example 1 of CN1232862A, and the molar ratio composition of the directing agent recommended by the invention is as follows: (14-16) SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2O。
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, which comprises the step of spray drying mixed slurry to prepare spray microspheres TS with the particle size of 20-110 mu m. Roasting the microspheres at 600-1000 ℃, wherein the roasting can be carried out at 600-850 ℃ for 1-3 h to obtain low-temperature roasted microspheres, or at 860-1000 ℃ for 1-3 h to obtain high-temperature roasted microspheres, or a mixture of the low-temperature roasted microspheres and the high-temperature roasted microspheres.
The method preferably selects a mixture of low-temperature roasted microspheres and high-temperature roasted microspheres, namely, spraying microspheres TS are divided into two parts, wherein one part is roasted at 860-1000 ℃ for 1-3 h to obtain high-temperature roasted microspheres TM (called high soil for short), and the other part is roasted at 600-850 ℃ for 1-3 h to obtain low-temperature roasted microspheres TP (called partial soil for short); the mass ratio of TM to TP is preferably 9: 1-1: 9. mixing two types of roasted microspheres, sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water, crystallizing for 16-36 hours at 85-95 ℃, filtering to remove mother liquor, washing a filter cake with deionized water until the pH value is below 10.5, and drying to obtain a crystallized product which has a good pore structure and wear resistance and contains 50-60% of NaY molecular sieve.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, which comprises the steps of filtering, washing and drying a crystallized product, wherein the washing of the crystallized product refers to washing a crystallized product filter cake with deionized water until the pH value is below 10.5.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, wherein a crystallized product is subjected to exchange, roasting and rare earth impregnation by adopting aluminum salt and acid. In the exchange process, the introduction mode of the exchange substances can be simultaneous introduction or separate introduction; the exchange substance is one or more of aluminum salt and acid; the exchange times are not limited, and single or multiple exchanges can be carried out, and when multiple exchanges are carried out, the exchange substances in each exchange can be the same or different; the roasting process can be one-time roasting or multiple roasting; the exchange and calcination processes are only required to meet the requirements of the final catalyst. The preparation method of the catalyst disclosed by the invention has the following recommended process conditions of exchange and roasting: the exchange is carried out at a pH of 3.0-6.0 and a temperature of 80-95 ℃; the roasting temperature is 500-850 ℃, and the roasting time is 0.5-2 hours.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, wherein aluminum salt is one or more of aluminum chloride and aluminum sulfate, and Al is additionally added2O3The content is 0.1-15%, preferably 0.1-10%(ii) a The acid is one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, preferably hydrochloric acid and sulfuric acid, the concentration is 0.01-15 mol/L, and the exchange conditions are as follows: the temperature is 20-100 ℃, the liquid-solid mass ratio is 4-15, the pH value is 2.8-6.0, and the treatment is carried out for 10-60 minutes.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, wherein rare earth is one or more of rare earth chloride and rare earth nitrate, the addition mode is impregnation, and the addition amount is not more than 6%, preferably 0.1-4%.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, and the specific surface area of the prepared catalyst is 400-500 m2The pore volume is 0.42-0.47 mL/g, and the rare earth content is not more than 6%.
The invention discloses a preparation method of a heavy metal resistant catalytic cracking catalyst, which mainly comprises the steps of pulping kaolin, boron phosphoric acid, a structural auxiliary agent, a dispersing agent and/or a reinforcing agent, adjusting the pH value of the slurry with acid, preparing spray microspheres, roasting, and carrying out hydrothermal crystallization to prepare a crystallization product containing 40-50% of NaY molecular sieve. The crystallized product contains borophosphate, so the pore structure is developed and the acidity is more ideal. On the basis, the catalyst is rich in macropores by a post-modification mode of aluminum salt, acid and rare earth impregnation, so that the pollution of heavy metals such as iron is reduced, the acidity of the molecular sieve can be modulated, and the pollution and damage of the heavy metals to the catalyst are reduced.
Drawings
FIG. 1-Compound Na (B)2P3O13) Phase diagram of (a);
FIG. 2-Compound Zn3(BO3)(PO4) Phase diagram of (a);
FIG. 3-Compound Na2(BP2O7(OH)) phase diagram.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The raw material sources are as follows:
1) kaolin: industrial products, from catalyst works of petrochemical company, Lanzhou
2) Sodium silicate: industrial products, from catalyst works of petrochemical company, Lanzhou
3) High alkali sodium metaaluminate: industrial products, from catalyst works of petrochemical company, Lanzhou
4) NaOH solution: industrial products, from catalyst works of petrochemical company, Lanzhou
5) Aluminum salt: chemically pure, commercially available
6) Hydrochloric acid: chemically pure, commercially available
7) Citric acid: chemically pure, commercially available
8) Nitric acid: chemically pure, commercially available
9) Sulfuric acid: chemically pure, commercially available
10) Phosphoric acid: chemically pure, commercially available
11) Rare earth elements: analytically pure, commercially available
The analysis method comprises the following steps:
the crystallinity of NaY molecular sieve is measured by X-ray diffraction method on a D/max-3C type X-ray powder diffractometer manufactured by Rigaku corporation, the crystallinity and the silicon-aluminum ratio of the sample are measured, a ZSX-Primus type fluorescence spectrometer manufactured by Rigaku corporation is used for measuring the content of elements such as sodium oxide, rare earth oxide, aluminum and the like, the IR acidity characterization is carried out on a Bruk TENSOR27 type infrared spectrum, and the sample pore distribution is measured by an Autosorb-3B specific surface determinator manufactured by Quantachrome corporation, USA through an N2The specific surface area, pore size distribution and pore volume of the sample are measured by a low-temperature (77.3K) adsorption-desorption experimental method. (see "analytical test methods in petrochemical analysis methods (RIPP laboratory methods)", Yan Cui et al, published by scientific Press, 1990). The abrasion index of the sample is determined by a gas lift method, a certain amount of the sample is put into a fixing device and is blown and milled for 5 hours under constant air flow, the average abrasion percentage of the last four hours except the first hour is called the abrasion index of the catalyst, and the unit is% per hour, and the method and the standard are as follows: airlift Q/SYLS 0518-2002. Sample wellThe distribution test adopts an Autosorb-3B specific surface determinator of Quantachrome company in the United states and passes through N2The specific surface area, pore size distribution and pore volume of the sample are measured by a low-temperature (77.3K) adsorption-desorption experimental method. Evaluation of Microreflective Activity (MA): according to the method, an ASTM-D3907 method is adopted, a catalyst is treated for 17 hours at 800 ℃ in advance under the condition of 100% of water vapor, Hongkong light diesel oil is used as reaction raw oil, the reaction temperature is 460 ℃, the oil inlet time is 70s, the catalyst loading is 2.5-5 g, and the yield of gasoline after reaction is analyzed by GC 7890.
Examples 1 to 9 are methods for preparing catalysts.
Example 1
133.55g of boric acid is dissolved by 267.2mL of distilled water, 92.21g of phosphoric acid is slowly injected into a boric acid solution and mixed for 40 minutes, the final pH value is 2.4, then 180g of boron phosphoric acid, 1800g of kaolin (pyro), 2.5% of sodium pyrophosphate, 4.5% of silica sol, 7.5% of structural assistant zinc chloride and chemical water are prepared into mixed slurry with the solid content of 46%, the pH value of the slurry is adjusted to 3.4 by hydrochloric acid, and spray drying is carried out, so that 1300g of spray microspheres P1 with the particle size of 20-110 mu m are obtained.
Roasting one part of P1 spray soil balls for 1.7h at 960 ℃ to obtain roasted microspheres G1, roasting the other part of the P1 spray soil balls for 3.0h at 630 ℃ to obtain roasted microspheres B1, then mixing 200G G1 and 300G B1, adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water, carrying out hydrothermal crystallization for 30h at 95 ℃, filtering to remove mother liquor, washing and drying to obtain a crystallized product J1.
Adding 500g of J1, aluminum chloride and deionized water into a stainless steel kettle while stirring, wherein the concentration of aluminum chloride/crystallized product is 0.02 and the concentration of aluminum sulfate/crystallized product is 0.03, exchanging for 1.5 hours at the temperature of 90 ℃ under the condition that the pH value is 3.0-3.5, filtering to remove filtrate, washing filter cakes with deionized water, and drying to obtain a first-handed material; roasting the first-handed material for 2 hours at 560 ℃ under the condition that the water vapor introduction amount is 95 percent to obtain a first-roasted material; the primary baked material is exchanged once with 0.8mol/L hydrochloric acid under the following conditions: the pH is 3.5, the temperature is 90 ℃, the processing time is 1 hour, the exchanged materials are filtered, washed and dried, and then are impregnated with 0.3 percent of rare earth chloride, so that the catalyst cat-1 with 0.58 percent of Na2O and 0.28 percent of rare earth is obtained.
Example 2
468.86g of boric acid is dissolved by 572mL of distilled water, 237.44g of phosphoric acid is slowly injected into the boric acid solution and mixed for 25 minutes, the final pH value is 2.8, then 160g of borophosphoric acid, 2560g of kaolin (firing), 9% of sodium silicate, 6% of alumina sol, 0.5% of structural assistant magnesium nitrate and chemical water are prepared into mixed slurry with the solid content of 33%, the pH value of the slurry is adjusted to 3.8 by citric acid, and spray drying is carried out, so that 2230g of spray microspheres P2 with the particle size of 20-110 mu m are obtained.
And roasting the P2 sprayed soil balls for 1.5h at 990 ℃ to obtain roasted microspheres G2. 100g G2 is added with sodium silicate, guiding agent, sodium hydroxide solution and chemical water, hydrothermal crystallization is carried out for 20 hours at 85 ℃, mother liquor is removed by filtration, and then washing and drying are carried out to obtain crystallized product J2.
Adding 1300g of J2, aluminum chloride and deionized water into a stainless steel kettle under stirring, wherein the concentration of the aluminum chloride/crystallized product is 0.050, exchanging for 1.5 hours under the conditions that the pH value is 4.0-4.5 and the temperature is 93 ℃, filtering to remove filtrate, washing filter cakes with deionized water, and drying to obtain a first-handed material; roasting the primary mixed material at 680 ℃ for 2 hours to obtain a primary roasted material; exchanging the primary baked material once with aluminum chloride, wherein the exchange conditions are as follows: the aluminum chloride/one-baking material is 0.085, the pH is 3.5-4.2, the temperature is 89 ℃, the time is 1 hour, the exchanged material is exchanged by 3mol/L sulfuric acid, and the exchange conditions are as follows: the pH is 3.8, the temperature is 80 ℃, the processing time is 30min, and the catalyst cat-2 with 0.45 percent of Na2O and 3.95 percent of rare earth is obtained by filtering, washing, drying and impregnating with 4.2 percent of rare earth chloride.
Example 3
155.81g of boric acid is dissolved by 630mL of distilled water, 968.18g of phosphoric acid is slowly injected into a boric acid solution and mixed for 45 minutes, the final pH value is 1.2, 546g of boron phosphoric acid, 2730g of kaolin (firing base), 6% of sodium silicate, 8% of silica sol, 2% of lanthanum nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 41%, the pH value of the slurry is adjusted to 3.8 by sulfuric acid, and 782g of spray microspheres P3 with the particle size of 20-110 microns are obtained by spray drying.
Roasting one part of P3 at 920 ℃ for 2.6h to obtain roasted microsphere G3, roasting the other part at 730 ℃ for 2.8h to obtain roasted microsphere B3, adding 50G G3 and 150G B3 into sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water, performing hydrothermal crystallization at 93 ℃ for 36h, filtering to remove mother liquor, washing with water and drying to obtain a crystallized product J3.
200g of J3, 5mol/L hydrochloric acid and deionized water are added into a stainless steel kettle under stirring, and the exchange conditions are as follows: the pH value is 4.0, the temperature is 85 ℃, the processing time is 45min, the exchanged material is exchanged by aluminum sulfate, the aluminum sulfate/exchanged material is 0.05, the exchange is carried out for 0.5 hour under the conditions that the pH value is 4.0-4.5 and the temperature is 93 ℃, the filtrate is filtered and removed, and the filter cake is washed by deionized water and dried to obtain a first exchanged material; exchanging the first material with aluminum sulfate under the following conditions: aluminum sulfate/first-handed material is 0.05, pH is 3.7-4.0, temperature is 91 ℃, time is 0.5 hour, and the exchanged material is filtered, washed and dried to obtain second-handed material; roasting the secondary suspension at 660 ℃ for 2 hours under the condition that the water vapor introduction amount is 50 percent to obtain a primary roasted material; exchanging the primary baked material once by using 5mol/L hydrochloric acid rare earth, wherein the exchange conditions are as follows: the pH is 3.3, the temperature is 80 ℃, the processing time is 30min, and the exchanged materials are filtered, washed and dried to obtain a three-way material; the triple cross-linked material is roasted for 2 hours at the temperature of 600 ℃ and the steam input amount of 100 percent, and then is dipped in 2.1 percent of rare earth nitrate to obtain the catalyst cat-3 with the Na2O content of 0.55 percent and the rare earth content of 2.0 percent.
Example 4
Dissolving 508g of boric acid in 3120mL of distilled water, slowly injecting 119.9g of phosphoric acid into the boric acid solution, mixing for 100 minutes to obtain a final pH value of 3.6, preparing 135.2g of borophosphoric acid, 1664g (pyroxylin) of kaolin, 7.8% of sodium pyrophosphate, 1.5% of a structural assistant magnesium chloride and chemical water into mixed slurry with the solid content of 40%, adjusting the pH value of the slurry to 3.8 by using nitric acid, and performing spray drying to obtain 2634g of spray microspheres P4 with the particle size of 20-110 microns.
Roasting one part of P4 at 1000 ℃ for 13h to obtain roasted microsphere G4, roasting the other part at 800 ℃ for 2h to obtain roasted microsphere B4, then adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water into 800G G4 and 200G B4, performing hydrothermal crystallization at 89 ℃ for 30h, filtering to remove a mother solution, washing with water and drying to obtain a crystallized product J4.
500g of J4 was added to a stainless steel kettle with stirring, and 9.9mol/L nitric acid and deionized water were added under the following exchange conditions: the pH value is 4.2, the temperature is 40 ℃, the processing time is 1h, the exchanged materials are exchanged by aluminum sulfate, the aluminum sulfate/exchanged product is 0.04, the aluminum chloride/exchanged product is 0.04, the materials are exchanged for 1h under the conditions that the pH value is 3.0-3.5 and the temperature is 90 ℃, the filtrate is filtered and removed, and the filter cake is washed by deionized water and dried to obtain a first-exchanged material; roasting the first-handed material for 2 hours at 500 ℃ under the condition that the steam introduction amount is 85 percent to obtain a first-roasted material; exchanging the primary baked material once by 3mol/L phosphoric acid, wherein the exchange conditions are as follows: the pH is 3.8, the temperature is 90 ℃, the time is 1 hour, the exchanged material is filtered, washed and dried, and then is dipped in rare earth nitrate with the concentration of 3 percent, thus obtaining the catalyst cat-4 with the Na2O content of 0.52 percent and the rare earth content of 2.94 percent.
Example 5
272.67g of boric acid is dissolved by 1350mL of distilled water, 103.77g of phosphoric acid is slowly injected into a boric acid solution and mixed for 100 minutes, the final pH value is 3.2, then 132.08g of borophosphoric acid, 870.35g of kaolin (pyrobase), 2g of alumina sol, 3% of cerium nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 45%, the pH value of the slurry is adjusted to 3.2 by oxalic acid, and spray drying is carried out, so that 764g of spray microspheres P5 with the particle size of 20-110 mu m are obtained.
Roasting one part of P5 at 970 ℃ for 2.2h to obtain roasted microsphere G5, roasting the other part of P5 at 850 ℃ for 1.8h to obtain roasted microsphere B5, adding sodium silicate, directing agent, sodium hydroxide solution and chemical water into 400G G5 and 400G B5, performing hydrothermal crystallization at 87 ℃ for 16h, filtering to remove mother liquor, washing with water and drying to obtain crystallized product J5.
350g of J5 are added into a stainless steel kettle with stirring, 8mol/L sulfuric acid and deionized water are added, and the exchange conditions are as follows: the pH value is 3.6, the temperature is 34 ℃, the processing time is 1h, the exchanged material is exchanged by aluminum chloride, the aluminum chloride/crystallized product is 0.03, the exchange is carried out for 1h under the conditions that the pH value is 3.0-3.5 and the temperature is 90 ℃, the filtrate is removed by filtration, and the filter cake is washed by deionized water and dried to obtain a first-exchange material; roasting the first-handed material for 2 hours at 500 ℃ under the condition that the steam introduction amount is 85 percent to obtain a first-roasted material; exchanging the primary baked material once by using aluminum sulfate, wherein the exchange conditions are as follows: the aluminum sulfate/one-baking material is 0.02, pH is 4.2, temp. is 90 deg.C, time is 1 hr, the exchanged material is filtered, washed, dried and impregnated with 6% rare earth chloride to obtain catalyst cat-5 whose Na2O content is 0.56% and rare earth content is 5.97%.
Example 6
204.21g of boric acid is dissolved by 840mL of distilled water, 242.05g of phosphoric acid is slowly injected into the boric acid solution and mixed for 82 minutes, the final pH value is 1.8, then 57.8g of borophosphoric acid, 1155g of kaolin (firing base), 2% of sodium silicate, 3% of sodium pyrophosphate, 7% of lanthanum chloride as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 38%, the pH value of the slurry is adjusted to 3.9 by citric acid, and the slurry is spray-dried to obtain 815g of spray microspheres P6 with the particle size of 20-110 microns.
Roasting one part of P6 at 945 ℃ for 1.5h to obtain roasted microsphere G6, roasting the other part at 870 ℃ for 1.5h to obtain roasted microsphere B6, adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water into 300G G6 and 200G B6, performing hydrothermal crystallization at 92 ℃ for 34h, filtering to remove mother liquor, washing with water, and drying to obtain a crystallized product J6.
Adding 650g of J6, 4mol/L hydrochloric acid, aluminum chloride and deionized water into a stainless steel kettle while stirring, wherein the concentration of the aluminum chloride/crystallized product is 0.01, exchanging for 1.5 hours at the temperature of 93 ℃ under the condition that the pH value is 4.0-4.5, filtering to remove filtrate, washing a filter cake with deionized water, and drying to obtain a first-phase material; roasting the primary mixed material at 680 ℃ for 2 hours to obtain a primary roasted material; exchanging the primary baked material once with aluminum chloride, wherein the exchange conditions are as follows: and (2) filtering, washing and drying the exchanged material, and then soaking the material in 5% of rare earth chloride to obtain the catalyst cat-6 with the Na2O content of 0.59% and the rare earth content of 4.97%, wherein the aluminum chloride/calcined material is 0.01, the pH is 3.5-4.2, the temperature is 89 ℃, and the time is 1 hour.
Example 7
299.26g of boric acid is dissolved by 660mL of distilled water, 63.39g of phosphoric acid is slowly injected into the boric acid solution and mixed for 65 minutes, the final pH value is 3.6, then 115.5g of borophosphoric acid, 3850g (pyrobase) of kaolin, 10% of silica sol, 1% of magnesium nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 40%, the pH value of the slurry is adjusted to 3.1 by hydrochloric acid, and 2900g of spray microspheres P7 with the particle size of 20-110 mu m are obtained by spray drying.
Roasting one part of P7 at 860 deg.c for 2.6 hr to obtain roasted microsphere G7, roasting the other part at 680 deg.c for 3.0 hr to obtain roasted microsphere B7, adding sodium silicate, directing agent, sodium hydroxide solution and chemical water to 900G G7 and 300G B7, hydrothermal crystallizing at 92 deg.c for 32 hr, filtering to eliminate mother liquid, water washing and drying to obtain crystallized product J7.
Adding 800g of J7, aluminum sulfate and deionized water into a stainless steel kettle under stirring, wherein the concentration of aluminum sulfate/crystallization product is 0.05, exchanging is carried out for 1.5 hours under the conditions that the pH value is 4.0-4.5 and the temperature is 93 ℃, filtering to remove filtrate, washing filter cakes with deionized water, and drying to obtain a first-handed material; roasting the primary cross-linked material at 660 ℃ for 2 hours to obtain a primary roasted material; exchanging the primary baked material once by using aluminum sulfate, wherein the exchange conditions are as follows: aluminum sulfate/one-baking material is 0.05, pH is 3.5-4.2, the temperature is 89 ℃, the time is 1 hour, the exchanged material is exchanged by 12mol/L nitric acid, and the exchange conditions are as follows: treating for 50min at the temperature of 60 ℃ and the pH value of 3.0-3.5, filtering, washing, drying, and then impregnating with 3.5% of rare earth nitrate to obtain the catalyst cat-7 with the Na2O content of 0.59% and the rare earth content of 3.47%.
Example 8
244.42g of boric acid is dissolved by 1089mL of distilled water, 46.49g of phosphoric acid is slowly injected into the boric acid solution, the mixture is mixed for 92 minutes, the final pH value is 3.9, 181.5g of borophosphoric acid, 968g of kaolin (pyrobase), 5% of alumina sol, 4.3% of structural assistant zinc nitrate and chemical water are prepared into mixed slurry with the solid content of 40%, the pH value of the slurry is adjusted to 3.6 by sulfuric acid, and spray drying is carried out, so that 897g of spray microspheres P8 with the particle size of 20-110 mu m are obtained.
P8 is roasted for 3.0h at 610 ℃ to obtain roasted microsphere B8, then 500g B8 is added with sodium silicate, guiding agent, sodium hydroxide solution and chemical water, hydrothermal crystallization is carried out for 36h at 94 ℃, mother liquor is removed by filtration, and washing and drying are carried out to obtain crystallized product J8.
Adding 400g of J8, 14.5mol/L sulfuric acid, aluminum sulfate and deionized water into a stainless steel kettle while stirring, wherein the concentration of aluminum sulfate/crystallized product is 0.04, exchanging for 1 hour under the conditions that the pH value is 3.3-3.9 and the temperature is 90 ℃, filtering to remove filtrate, and washing a filter cake with deionized water to obtain a first-phase material; roasting the first-handed material for 2 hours at 500 ℃ under the condition that the steam introduction amount is 85 percent to obtain a first-roasted material; exchanging the primary baked material once with aluminum chloride, wherein the exchange conditions are as follows: and (2) filtering, washing and drying the exchanged material, and then soaking the material in 4.5% of rare earth nitrate to obtain the catalyst cat-8 with 0.57% of Na2O and 4.46% of rare earth, wherein the aluminum chloride/one-baking material is 0.02, the pH is 3.5-4.2, the temperature is 90 ℃, the time is 1 hour.
Example 9
938.65g of boric acid is dissolved in 1696mL of distilled water, 244.35g of phosphoric acid is slowly injected into a boric acid solution and mixed for 75 minutes, the final pH value is 3.5, then 233.2g of borophosphoric acid, 1802g (pyroxylyl) of kaolin, 4.7% of sodium pyrophosphate, 5.5% of lanthanum nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 40%, the pH value of the slurry is adjusted to 3.6 by nitric acid, and spray drying is carried out, so that 1476g of spray microspheres P9 with the particle size of 20-110 mu m are obtained.
Roasting one part of P9 at 890 ℃ for 1.5h to obtain roasted microspheres G9, roasting the other part of P9 at 770 ℃ for 1.8h to obtain roasted microspheres B9, adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water into 400G G9 and 600G B9, performing hydrothermal crystallization at 88 ℃ for 28h, filtering to remove mother liquor, washing with water, and drying to obtain a crystallized product J9.
Adding 450g of J9, aluminum sulfate and deionized water into a stainless steel kettle while stirring, wherein the aluminum sulfate/crystallization product is 0.06, exchanging for 1.5 hours under the conditions that the pH value is 4.0-4.5 and the temperature is 93 ℃, filtering to remove filtrate, and washing a filter cake with deionized water to obtain a first-phase material; roasting the first-handed material for 2 hours at 700 ℃ under the condition that the steam introduction amount is 25 percent to obtain a first-roasted material; exchanging the primary baked material once with aluminum chloride, wherein the exchange conditions are as follows: the aluminum chloride/one-baking material is 0.06, the pH value is 3.5-4.2, the temperature is 86 ℃, the time is 1 hour, the exchanged material is treated by 6mol/L nitric acid at 50 ℃ and the pH value is 4.0-4.5 for 1 hour, and the catalyst cat-9 with 0.48 percent of Na2O and 5.17 percent of rare earth content is obtained after filtration, washing, drying and impregnation of 5.2 percent of rare earth chloride.
Examples 10 to 12 are comparative examples.
Example 10
Compared with the example 1, 1800g of kaolin (causticity), 2.5% of sodium pyrophosphate, 4.5% of silica sol, 7.5% of structural assistant zinc chloride and chemical water are prepared into mixed slurry with the solid content of 46%, and the mixed slurry is subjected to spray drying to obtain 1500g of spray microspheres P10 with the particle size of 20-110 microns.
Roasting one part of P10 spray soil balls for 1.7h at 960 ℃ to obtain roasted microspheres G10, roasting the other part of the P10 spray soil balls for 3.0h at 630 ℃ to obtain roasted microspheres B10, then mixing 200G G10 and 300G B10, adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water, carrying out hydrothermal crystallization for 30h at 95 ℃, filtering to remove mother liquor, washing and drying to obtain a crystallized product J10.
500g of J10 was added to a stainless steel kettle with stirring, and the mixture was treated with hydrochloric acid under the following conditions: the temperature is 60 ℃, the liquid-solid mass ratio is 8, the pH value is 2.8, the treatment is carried out for 60 minutes, the treated materials are exchanged by aluminum chloride, and the exchange conditions are as follows: exchanging the aluminum chloride/crystallized product at the pH value of 3.8-4.0 for 40 hours at the temperature of 90 ℃, filtering to remove filtrate, and washing filter cakes with deionized water to obtain a first exchange material; roasting the first batch at 750 deg.c for 30min, and soaking in 0.3% RE chloride to obtain cat-10 with Na2O content of 0.59% and RE content of 0.27.
Example 11
Compared with example 7, 299.26g of boric acid is dissolved in 660mL of distilled water, 63.39g of boric acid, 3850g of kaolin (pyroxylin), 10% of silica sol, 1% of magnesium nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 40%, and 2900g of spray microspheres P11 with the particle size of 20-110 μm are obtained through spray drying.
Roasting one part of P11 at 860 deg.c for 2.6 hr to obtain roasted microsphere G11, roasting the other part at 680 deg.c for 3.0 hr to obtain roasted microsphere B11, adding sodium silicate, guiding agent, sodium hydroxide solution and chemical water to 900G G11 and 300G B11, hydrothermal crystallizing at 92 deg.c for 34 hr, filtering to eliminate mother liquid, water washing and drying to obtain crystallized product J11.
Adding 300g of J11, aluminum sulfate and deionized water into a stainless steel kettle under stirring, wherein the aluminum sulfate/crystallization product is 0.09, exchanging for 1.5 hours under the conditions that the pH value is 3.0-3.3 and the temperature is 92 ℃, filtering to remove filtrate, and washing a filter cake with deionized water to obtain a first-phase material; roasting the first-handed material for 2 hours at 700 ℃ under the condition that the steam introduction amount is 25 percent to obtain a first-roasted material; treating the calcined material with 10mol/L nitric acid at 45 ℃ and pH of 3.8-4.2 for 1h, filtering, washing, drying, and then impregnating with 3.5% of rare earth nitrate to obtain the catalyst cat-11 with 0.59% of Na2O and 3.48% of rare earth.
Example 12
Compared with the example 5, 103.77g of phosphoric acid, 870.35g of kaolin (pyrobase), 2g of alumina sol, 3% of cerium nitrate as a structural assistant and chemical water are prepared into mixed slurry with the solid content of 45%, and spray drying is carried out to obtain 764g of spray microspheres P12 with the particle size of 20-110 μm.
Roasting one part of P12 at 970 ℃ for 2.2h to obtain roasted microsphere G12, roasting the other part of P12 at 850 ℃ for 1.8h to obtain roasted microsphere B12, adding sodium silicate, a guiding agent, a sodium hydroxide solution and chemical water into 300G G12 and 300G B12, performing hydrothermal crystallization at 87 ℃ for 16h, filtering to remove mother liquor, washing with water and drying to obtain a crystallized product J12.
Adding 200g of J12 aluminum chloride and deionized water into a stainless steel kettle under stirring, wherein the aluminum chloride/crystallization product is 0.10, exchanging for 1.5 hours under the conditions that the pH value is 4.0-4.5 and the temperature is 93 ℃, filtering to remove filtrate, washing filter cakes with deionized water, and drying to obtain a first-handed material; roasting the first batch at 630 ℃ for 2 hours to obtain a first roasted material; exchanging the primary baked material once by using aluminum sulfate, wherein the exchange conditions are as follows: aluminum sulfate/one-baking material is 0.055, pH is 3.5-4.2, temperature is 89 ℃, time is 1 hour, exchanged material is exchanged by 14mol/L nitric acid, exchange condition is: treating at 50 ℃ and pH of 3.0-3.5 for 80min, filtering, washing, drying, and impregnating with 6% rare earth chloride to obtain Na20.36 percent of O and 5.96 percent of rare earth, namely cat-12.
The crystallization conditions, crystallization results, addition amounts of the structural aids and retention rates of the crystallization products of examples 1 to 12 are shown in Table 1, and the X-ray diffraction patterns of the boron phosphate compounds in the crystallization products of examples 1, 3 and 6 are shown in FIGS. 1 to 3. The results of FIGS. 1-3 show that: the synthetic method can be used for preparing the borophosphate compound with good crystal form.
As can be seen from table 1, during the preparation of the clay mixed slurry, due to the introduction of the borophosphate, a solid phase transition to borophosphate occurs during the subsequent activation process, forming a zeolite-like structure. Compared with the method of simply using phosphate or borate, the crystallization product structure auxiliary agent prepared by the scheme is not easy to run off.
From the catalyst acidity results in table 2 it can be seen that: the crystallization product containing the boron phosphate compound adopts the processes of aluminum salt, acid exchange and final rare earth impregnation, so that the acidity is more excellent, and the medium-strength acid content is obviously increased compared with a contrast agent.
The table 3 shows the main physicochemical property results of the catalyst, and the table 4 shows the performance evaluation results of the catalyst prepared under the same heavy metal pollution condition, and the evaluation results show that the catalyst of the patent has better heavy metal resistance.
TABLE 1 in-situ crystallization Process conditions and preparation results
Figure BDA0002103275690000161
TABLE 2 catalyst acidity results
Figure BDA0002103275690000162
TABLE 3 main physicochemical Properties of the catalyst
Figure BDA0002103275690000163
Figure BDA0002103275690000171
TABLE 4 reactivity of the catalysts
(evaluation was made under the same heavy Metal contamination amount of 5000ppmV and 3000 ppmNi)
Figure BDA0002103275690000172

Claims (20)

1. A preparation method of a heavy metal resistant catalytic cracking catalyst is characterized by comprising the following steps: 1) dissolving boric acid into a solution according to the liquid-solid mass ratio of 2-10, slowly adding 85% phosphoric acid solution, fully mixing until the pH value is 1-4.0, and treating for 10-120 minutes to obtain borophosphoric acid; mixing the obtained borophosphate with kaolin, a structural assistant, a dispersing agent and/or a reinforcing agent and chemical water for pulping, wherein the solid content of the slurry is 30-50%, adjusting the pH value of the slurry to 3-4 by using acid for the mixed slurry, spraying the slurry into microspheres, drying, roasting at 600-1000 ℃, mixing with sodium silicate, a guiding agent, an alkali solution and water, crystallizing at 85-95 ℃ for 16-36 hours, filtering, washing and drying a crystallized product to obtain the in-situ crystallized NaY molecular sieve; the structural auxiliary agent is one or more of soluble zinc salt, soluble alkaline earth metal salt and soluble rare earth compound, and the adding amount of the structural auxiliary agent is 0.1-8% of the total mass of the kaolin; the adding amount of the boron phosphoric acid is 0.1-20% of the total mass of the kaolin; 2) performing aluminum salt and acid exchange, roasting and rare earth impregnation on the dried crystallized product to prepare the catalytic cracking catalyst, wherein the mass of the catalytic cracking catalyst is 100 percent, and Na is calculated20.1-0.7% of O, and Al2O3The content is 0.1-15%, and the content of rare earth is 0.1-6%.
2. The method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the pH of the mixed slurry in the step 1 is adjusted by using an acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, citric acid and oxalic acid.
3. The method for preparing the anti-heavy metal catalytic cracking catalyst of claim 1, wherein the soluble zinc salt in the structural auxiliary agent is zinc chloride or zinc nitrate, the soluble alkaline earth metal salt is magnesium chloride or magnesium nitrate, and the soluble rare earth compound is lanthanum nitrate, cerium chloride, lanthanum chloride or cerium nitrate.
4. The method for preparing the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the addition amount of the structural assistant is 0.1-8% of the total mass of kaolin.
5. The method for preparing the anti-heavy metal catalytic cracking catalyst according to claim 1, wherein the addition amount of the dispersant is 2-10% of the total mass of the kaolin, and the addition amount of the reinforcing agent is 2-10% of the total mass of the kaolin.
6. The method for preparing the heavy metal resistant catalytic cracking catalyst according to claim 5, wherein the reinforcing agent is added in an amount of 2-8% of the total mass of kaolin.
7. The method of claim 1, wherein the dispersant is sodium silicate or sodium pyrophosphate, and the reinforcing agent is silica sol or alumina sol.
8. The method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the borophosphate is a mixed compound of boric acid and phosphoric acid.
9. The method for preparing the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the amount of the added boron phosphoric acid is 0.1-15% of the total mass of the kaolin.
10. The method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 8, wherein the molar ratio of B to P in the borophosphoric acid is 0.1 to 10.
11. The preparation method of the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the kaolin is selected from soft kaolin, hard kaolin and coal gangue, wherein the particle size is 1.5-3.0 μm, the content of the crystalline kaolinite is higher than 80%, the content of iron oxide is lower than 1.7%, and the sum of sodium oxide and potassium oxide is lower than 0.5%.
12. The process for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the guiding agent comprises the following components in a molar ratio:
(14～16)SiO2:(0.7～1.3)Al2O3:(14～16)Na2O:(300～330)H2O。
13. the preparation method of the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the mixed slurry in the step 1) is sprayed into microspheres, dried and roasted at 600-850 ℃ for 1-3 hours to obtain low-temperature roasted microspheres.
14. The preparation method of the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the mixed slurry in the step 1) is sprayed into microspheres, dried and roasted at 860 to 1000 ℃ for 1 to 3 hours to obtain high-temperature roasted microspheres.
15. The preparation method of the heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the mixed slurry in the step 1) is spray-dried into microspheres, one part of the microspheres are roasted at 600-850 ℃ for 1-3 h to obtain low-temperature roasted microspheres, and the other part of the microspheres are roasted at 860-1000 ℃ for 1-3 h to obtain high-temperature roasted microspheres.
16. The method for preparing the heavy metal resistant catalytic cracking catalyst according to claim 15, wherein the mass ratio of the high-temperature roasted microspheres to the low-temperature roasted microspheres in the step 1) is 9: 1-1: 9.
17. the method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the Na is contained in an amount of 100% by mass based on the mass of the catalytic cracking catalyst2The content of O is 0.1-0.7%.
18. The method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the process conditions of the exchanging and calcining in the step 2) are as follows: carrying out exchange at the pH of 3-6 and the temperature of 80-95 ℃; the roasting temperature is 500-950 ℃, and the roasting time is 0.5-2 hours.
19. The process for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1, wherein the aluminum salt is one or more of aluminum chloride and aluminum sulfate; the acid is one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and the rare earth is one or more of rare earth nitrate, rare earth chloride and rare earth hydroxide.
20. The method for preparing a heavy metal resistant catalytic cracking catalyst according to claim 1 or2, wherein the prepared catalyst has a specific surface area of 400 to 450m2The pore volume is 0.42-0.47 mL/g.
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