CN113120919A - Preparation method of Y-type molecular sieve composite material with high silica-alumina ratio - Google Patents
Preparation method of Y-type molecular sieve composite material with high silica-alumina ratio Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
Abstract
A preparation method of a Y-type molecular sieve composite material with a high silica-alumina ratio is characterized by comprising the following steps: (1) roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, crushing the metakaolin, and then preparing metakaolin powder with the particle size of less than 10 microns; (2) adding sodium silicate, a directing agent, a sodium hydroxide solution and water into metakaolin powder to prepare Na with the mixture ratio of (1-2.5)2O：Al2O3：(4～9)SiO2：(40～100)H2O, wherein the mass ratio of the directing agent to the metakaolin is 0.01-1.0; (3) crystallizing the reaction raw material A under stirring at 88-98 ℃, and supplementing silica-alumina gel after the crystallization time reaches 1-70h to obtain a reaction raw material B, wherein the silica-alumina gel accounts for 0.1-10 wt% of the total silicon amount of the feed; (4) and crystallizing the reaction raw material B under stirring at 88-98 ℃, and recovering the product.
Description
Technical Field
The invention relates to a preparation method of a composite material, in particular to a preparation method of a Y-type molecular sieve composite material.
Background
At the end of the 50's of the 20 th century, Milton and Breck successfully synthesized Y-type molecular sieves. The guide agent synthesized NaY molecular sieve was developed in the 70 s w.R. oraee, and the expensive silica sol was replaced by the cheap water glass, so that the process was simple and the production cycle was short, thereby the molecular sieve can be rapidly and widely applied to the field of petrochemical industry, especially the field of petroleum catalytic cracking, and becomes the molecular sieve with the largest industrial dosage so far. It is used as the active component of fluid catalytic cracking catalyst and has important value in the industrial fields of petroleum refining, heavy oil and residual oil processing to produce high quality gasoline and diesel oil. The application of Y-type molecular sieve, especially high-silicon Y-type zeolite catalyst in the field of catalytic cracking is a revolution in the petroleum industry. In the 70 s, the oil refining industryIn the process of residual oil processing and high octane gasoline production, the FCC catalyst must have the characteristics of high hydrothermal stability, heavy metal pollution resistance, carbon deposit reduction, hydrogen transfer reaction inhibition and the like, which puts new requirements on the research of the Y-type molecular sieve. Optimum silicon-aluminum ratio n (SiO) of Y-type molecular sieve as active component of cracking catalyst2)/n(A12O3) 9-10, but the silicon-aluminum ratio of the directly synthesized Y-type molecular sieve at present is lower, generally about 5, and the method for searching and synthesizing the high-silicon Y-type molecular sieve has extremely important industrial value.
The synthesis method of the Y-type molecular sieve is divided into direct synthesis and secondary synthesis (dealumination), because the directly synthesized Y-type molecular sieve has lower silica-alumina ratio, the secondary dealumination method is generally adopted in industry to improve the framework silica-alumina ratio, which not only increases the cost and the loss, but also has more important influence on the property, the function and the service life of the catalyst because the deep dealumination can cause the instability of a zeolite framework and the uneven distribution of surface and bulk silica-alumina and active centers. For more than 30 years, effective methods for increasing the silica-alumina ratio of the Y-type molecular sieve suitable for industrial production are searched, and Elliott indicates that even increasing the silica-alumina ratio of the Y-type molecular sieve from 4.9 to 6.0 has great industrial significance.
The silicon-aluminum ratio of the Y-type molecular sieve synthesized by the prior direct synthesis method is lower, and the industrial requirement can not be met. There have been many studies on the direct synthesis of Y-type molecular sieves with higher framework silica-alumina ratio, and it is generally difficult to obtain products with good crystallization and higher framework silica-alumina ratio. Research shows that the framework Si/Al ratio of the directly synthesized Y-type molecular sieve is less than 6 and mixed crystals are easy to generate. The TannouS et al study showed that good crystallinity and high Si/Al ratio are two incompatible parameters, the main reason for this being n (SiO) in the material2)/n(A12O3) The increase of (A) requires lower alkalinity in the system, and the low system alkalinity can cause the loss of the crystallinity of the product and the generation of mixed crystals. In addition, the optimum n (Na) is present in the reaction system2O)/n(SiO2) When n (Na) is contained in the material2O)/n(SiO2) Greater than optimum n (Na)2O)/n(SiO2) When the ratio is within the range, the crystallinity of the crystal is substantially notThe silicon-aluminum ratio is sharply reduced; when n (Na) is contained in the material2O)/n(SiO2) Less than optimum n (Na)2O)/n(SiO2) In the case of the crystal, the Si/Al ratio increases and the crystallinity decreases sharply. Therefore, it is not a radical effective way to increase the framework silica-alumina ratio of the Y-type zeolite crystal by merely adjusting the mixture ratio of materials.
Since the synthesis of zeolite molecular sieves with the introduction of organic templating agents (templates) by Barrer and Dnney in 1961, the role of the templating agents has been more and more widely regarded. The introduction of the template agent, particularly the application of organic amine in zeolite synthesis, can synthesize a plurality of medium and high silicon (even pure silicon) zeolite molecular sieves. In the synthesis of the Y-type molecular sieve, the silica-alumina ratio of the Y-type molecular sieve is also improved by adding a template agent, such as adding a traditional organic amine template in a hydrothermal system. However, the organic template is added to synthesize the Y-type molecular sieve with higher silica-alumina ratio, so that the problems of industrial application cost and environmental pollution caused by the organic template exist, and the effect is not very ideal.
The method disclosed in CN201110312397.4 provides all silicon sources and aluminum sources for molecular sieve synthesis with natural kaolin minerals and natural diatomite minerals, and uses them as the substrates for molecular sieve growth, and forms crystal products through in-situ crystallization. In the composite material, the mass percentage of the NaY molecular sieve is 25-50%, and the silicon-aluminum ratio of the NaY molecular sieve is 3-5.5.
Zhengshuqin (Si-Al gel, kaolin hydrothermal crystallization synthesis hierarchical pore channel catalytic material, petroleum institute (petroleum processing), V30(1), 32-37) reports that Si-Al gel and kaolin hydrothermal synthesis hierarchical pore channel catalytic material, the method uses water glass and sodium metaaluminate as silicon source and aluminum source respectively to prepare Si-Al gel, spray the Si-Al gel with kaolin to form balls, then synthesize, the silicon-aluminum ratio of the synthesized product reaches 5.1, but the silicon-aluminum ratio of the fed material reaches 12:1, the utilization ratio of the fed material is only 42.5%.
The silica-alumina ratio of the Y-type molecular sieve synthesized by kaolin in-situ crystallization is generally less than 4.9.
CN101746778A is a product having a high silica-alumina ratio, which can be finally synthesized by using the same silicon source and adding the synthesis raw material at one time, but the synthesis time is long, the crystallinity of the synthesized product is low, and P-type mixed crystals are easily generated.
Disclosure of Invention
The invention aims to provide a preparation method of a Y-type molecular sieve composite material, which not only ensures the crystallinity but also improves the silicon-aluminum ratio of a product on the premise of shortening the crystallization time.
The invention provides a preparation method of a Y-type molecular sieve composite material with a high silicon-aluminum ratio, which is characterized by comprising the following steps: 1. a preparation method of a Y-type molecular sieve composite material with a high silica-alumina ratio is characterized by comprising the following steps: (1) roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, crushing the metakaolin, and then preparing metakaolin powder with the particle size of less than 10 microns; (2) adding sodium silicate, a directing agent, a sodium hydroxide solution and water into metakaolin powder to prepare Na with the mixture ratio of (1-2.5)2O：Al2O3：(4～9)SiO2：(40～100)H2O, wherein the mass ratio of the directing agent to the metakaolin is 0.01-1.0; (3) crystallizing the reaction raw material A under stirring at 88-98 ℃, and supplementing silica-alumina gel after the crystallization time reaches 1-70h to obtain a reaction raw material B, wherein the silica is used as the basis, and the dry basis of the silica-alumina gel accounts for 0.1-10 wt% of the total silicon amount of the feed; (4) and crystallizing the reaction raw material B under stirring at 88-98 ℃, and recovering the product.
In the invention, sodium silicate and silica-alumina gel are supplemented into a synthesis system in different processes, and particularly, the silica-alumina gel is added in the crystal growth period.
The method combines a method of adding different silicon sources at different stages in the crystallization process to control a synthesis ratio technology and a kaolin in-situ crystallization synthesis technology (natural minerals are used as main aluminum sources and silicon sources), and changes the crystal growth environment through the silicon sources. In the invention, two completely different material proportions are adopted in the two stages of the crystal nucleation period and the crystal growth period. During the crystal nucleation period, the material adopts a larger sodium-silicon ratio (Na)2O)/SiO2) The rapid nucleation of the Y-type molecular sieve is facilitated; during the crystal growth period, adding low-sodium or sodium-free silica-alumina gel to raise the silica-alumina ratio (SiO) in the synthesized material2)/A12O3) Simultaneously, the sodium-silicon ratio (Na) in the material is reduced2O/SiO2) On the premise of shortening the crystallization time, the method is beneficial to improving the silicon-aluminum ratio of the product, and the silicon-aluminum ratio is improved to more than 5.0.
The method of the invention adopts the technical means of silicon source sectional addition, and the obtained Y-type molecular sieve composite material has unique physicochemical characterization characteristics, namely: a crystallinity of 60% or more, preferably 80% or more in the peak height method and a ratio of the crystallinity to the crystallinity in the peak area method of K1, K1 of 0.76 to 0.89, preferably 0.80 to 0.89, more preferably 0.80 to 0.85, when measured by the X-ray diffraction method; by unit cell constant a0The measured Si/Al ratio is 5.0 to 5.5, preferably 5.2 to 5.5, and the ratio to the chemically measured Si/Al ratio is K2, K2 is 0.87 to 0.93, preferably 0.87 to 0.92, more preferably 0.88 to 0.90.
In the method of the present invention, the directing agent described in step (2) can be synthesized according to a conventional method, for example, according to the preparation method of USP3574538, 3639099, USP3671191, USP4166099, EUP 0435625. The guiding agent comprises the following components: (10-17) SiO2：(0.7-1.3)Al2O3：(11-18)Na2O：(200-350)H2And O. During synthesis, raw materials are aged at 4-35 ℃, preferably 4-20 ℃ to obtain the guiding agent.
In the method, the silica-alumina gel adopted in the step (3) is from the Y-type molecular sieve mother liquor in industrial production. The method for obtaining the silica-alumina gel from the Y-type molecular sieve mother liquor comprises the following steps: the silica-alumina gel is prepared by adding aluminum sulfate into NaY synthesis mother liquor, wherein the silica-alumina gel can be solid silica-alumina gel or a silica-alumina gel filter cake, the solid content is 5-40%, preferably 30-40%, the mass percentage of silicon dioxide in the silica-alumina gel is 30-70%, and the mass percentage of sodium oxide is 0.3-20%; preferably, the mass percent of sodium oxide is less than 5%. The silicon and the aluminum in the silica-alumina gel are taken into account of the synthesis proportion of the total composite material.
Calculated by silicon oxide, the silica-alumina gel accounts for 0.1-10 wt%, preferably 4-10 wt% of the total silicon amount of the feed.
In the method, the hierarchical porous Y-type molecular sieve composite material product containing a certain amount of mesopores and macropores (10-20%) is obtained by crystallization under stirring, but the crystallization stirring speed is 150-1000 rpm, preferably 300-500 rpm, and the time is 16-48 hours, preferably 24-32 hours. The drying temperature of the crystallized zeolite is 100-120 ℃.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the examples, the content of NaY zeolite in the composite material was measured by the RIPP146-90 standard method (the RIPP standard method is described in "analysis of petrochemical industry (RIPP test method)", Yanggui et al, published by scientific publishers, 1990, the same applies hereinafter), and was obtained from the relative crystallinity.
Unit cell constant a0Determined according to the RIPP145-90 standard method. The framework Si/Al ratio is determined by the unit cell constant a0Calculated according to the following formula:
SiO2/Al2O3(molar ratio) 2 × (25.858-a)0)/(a0-24.191)
The specific surface area was measured by nitrogen adsorption method (GB/T5816-1995), the pore volume was measured by nitrogen adsorption method (RIPP151-90), the pores larger than 0.8nm in nitrogen adsorption method were defined as mesopores and macropores, and the mesopore/macropore ratio was calculated by the following formula (V)General hole-VMicro-pores)/VGeneral hole╳100％。
In the examples and comparative examples, the preparation of directing agents: 250 g of sodium silicate solution (containing 20.05% by weight of SiO)26.41% by weight of Na2O), slowly adding 120 g of sodium metaaluminate solution (containing 3.15 weight percent of Al) under rapid stirring at 30 DEG C2O321.1% by weight of Na2O), stirring for 1 hour, and aging for 48 hours at 20 ℃ to obtain the guiding agent. The guiding agent has the composition of 16Na2O：Al2O3：15SiO2：320H2O。
Example 1
100 kg of pulverized metakaolin powder, 400 kg of sodium silicate solution (containing 20.05% by weight of SiO) was added with stirring26.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight hydrogen and oxygenDissolving sodium into solution. Heating to 94 ℃, stirring at constant temperature, adding 60 kg of solid silica-alumina gel after 8 hours, and adding aluminum sulfate into NaY synthetic mother liquor to prepare the silica-alumina gel, wherein the SiO contained in the silica-alumina gel262％,Al2O315％,Na2O13%, and recrystallizing for 12 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-1.
X-ray diffraction measurement of GY-1, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
Comparative example 1
This comparative example illustrates the case where two silicon sources were added to the reaction system at once.
100 kg of pulverized metakaolin powder, 400 kg of sodium silicate solution (containing 20.05% by weight of SiO) was added with stirring26.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5 wt% sodium hydroxide solution, 60 kg of solid silica-alumina gel, and is prepared by adding aluminum sulfate into NaY synthetic mother liquor, wherein the SiO contained in the solid silica-alumina gel262％,Al2O315％,Na2O13 percent. Heating to 94 ℃, stirring at constant temperature, crystallizing for 24 hours, and stirring at the rotating speed of 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the DGY-1 of the comparative composite material.
X-ray diffraction measurement of DGY-1, the crystallinity by peak height method, the K1 value of the ratio of the crystallinity by peak height method to the crystallinity by peak area method, and the cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1. Low crystallinity and mixed crystal.
Comparative example 2
This comparative example illustrates the case of increasing the charge silica-alumina ratio.
100 kg of pulverized metakaolin powder were added 480 kg of sodium silicate solution (containing 20.05% by weight of SiO) with stirring as in example 126.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 94 ℃, stirring at constant temperature, crystallizing for 38 hours, and stirring at the rotating speed of 400 revolutions per minute during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the DGY-2 of the comparative composite material.
X-ray diffraction measurement of DGY-2, the crystallinity by peak height method, the K1 value of the ratio of the crystallinity by peak height method to the crystallinity by peak area method, and the cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1. The crystallinity is low, mixed crystals exist, and the preparation time is long.
Comparative example 3
This comparative example illustrates the case where no second silicon source was added.
100 kg of pulverized metakaolin powder were added 400 kg of sodium silicate solution (containing 20.05% by weight of SiO) with stirring as in example 126.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 94 ℃, stirring at constant temperature, crystallizing for 24 hours, and stirring at the rotating speed of 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 deg.C for 2 hr to obtain zeolite DGY-3.
X-ray diffraction measurement of DGY-3, the crystallinity by peak height method, the K1 value of the ratio of the crystallinity by peak height method to the crystallinity by peak area method, and the cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1. The crystallinity of the product is not poor, but the silicon-aluminum ratio of the product is low.
Example 2
100 kg of the pulverized metakaolin powder were added with stirring as in example 1380 kg of sodium silicate solution (containing 20.05% by weight of SiO)26.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 93 deg.C, stirring at constant temperature, adding 75 kg of solid silica-alumina gel after 8 hr, and adding aluminum sulfate into NaY synthetic mother liquor to obtain the final product containing SiO262％,Al2O315％,Na2O13%, and recrystallizing for 14 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-2.
X-ray diffraction measurement of GY-2, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
Example 3
100 kg of pulverized metakaolin powder were added 360 kg of sodium silicate solution (containing 20.05% by weight of SiO) with stirring as in example 126.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 95 deg.C, stirring at constant temperature, adding 90 kg of solid silica-alumina gel after 8 hr, and adding aluminum sulfate into NaY synthetic mother liquor to obtain the final product containing SiO262％,Al2O315％,Na2O13%, and recrystallizing for 16 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-3.
X-ray diffraction measurement of GY-3, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
Example 4
According to the method of example 1Method, 100 kg of pulverized metakaolin powder, 400 kg of sodium silicate solution (containing 20.05% by weight of SiO) was added with stirring26.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 93 deg.C, stirring at constant temperature, adding 200 kg of silica-alumina gel filter cake after 8 hr, and adding aluminum sulfate into NaY synthetic mother liquor to obtain the final product, wherein the solid content is 31%, and the solid content contains SiO261.7％,Al2O314.6％,Na2O13%, and recrystallizing for 14 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-4.
X-ray diffraction measurement of GY-4, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
Example 5
380 kg of sodium silicate solution (containing 20.05% by weight of SiO) were added to 100 kg of the pulverized metakaolin powder in the same manner as in example 1, while stirring26.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 94 ℃, stirring at constant temperature, adding 240 kg of silica-alumina gel filter cake after 12 hours, and adding aluminum sulfate into NaY synthetic mother liquor to prepare the silica-alumina gel filter cake, wherein the solid content is 31 percent, and the solid content contains SiO261.7％,Al2O314.6％,Na2O13%, and recrystallizing for 14 hours, wherein the stirring speed during feeding and crystallizing is 400 r/min. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-5.
X-ray diffraction measurement of GY-5, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The determined silicon-aluminum ratio and the silicon-aluminum ratio determined by a chemical methodThe K2 value and the mesopore ratio of the ratio are shown in Table 1.
Example 6
100 kg of pulverized metakaolin powder were added 360 kg of sodium silicate solution (containing 20.05% by weight of SiO) with stirring as in example 126.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 92 ℃, stirring at constant temperature, adding 280 kg of silica-alumina gel filter cake after 14 hours, and adding aluminum sulfate into NaY synthetic mother liquor to prepare the silica-alumina gel filter cake, wherein the solid content is 31 percent, and the solid content contains SiO261.7％,Al2O314.6％,Na2O13%, and recrystallizing for 16 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-6.
X-ray diffraction measurement of GY-6, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
Example 7
100 kg of pulverized metakaolin powder were added 360 kg of sodium silicate solution (containing 20.05% by weight of SiO) with stirring as in example 126.41% by weight of Na2O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide solution. Heating to 92 ℃, stirring at constant temperature, adding 300 kg of silica-alumina gel filter cake after 16 hours, and adding aluminum sulfate into NaY synthetic mother liquor to prepare the silica-alumina gel filter cake, wherein the solid content is 31 percent, and the solid content contains SiO261.7％,Al2O314.6％,Na2O13%, and recrystallizing for 16 hours, wherein the stirring speed is 400 r/min during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed by water until the pH value of the washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-7.
X-ray diffraction measurement of GY-7, crystallinity by Peak height method, and ratio of crystallinity by Peak height method to crystallinity by Peak area methodK1 value of (a) in terms of unit cell constant a0Measured Si/Al ratio in terms of unit cell constant a0The K2 value and the mesopore ratio of the measured Si/Al ratio to the chemically measured Si/Al ratio are shown in Table 1.
TABLE 1
Claims (13)
1. A preparation method of a Y-type molecular sieve composite material with a high silica-alumina ratio is characterized by comprising the following steps: (1) roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, crushing the metakaolin, and then preparing metakaolin powder with the particle size of less than 10 microns; (2) adding sodium silicate, a directing agent, a sodium hydroxide solution and water into metakaolin powder to prepare Na with the mixture ratio of (1-2.5)2O：Al2O3：(4～9)SiO2：(40～100)H2O, wherein the mass ratio of the directing agent to the metakaolin is 0.01-1.0; (3) crystallizing the reaction raw material A under stirring at 88-98 ℃, and supplementing silica-alumina gel after the crystallization time reaches 1-70h to obtain a reaction raw material B, wherein the silica-alumina gel accounts for 0.1-10 wt% of the total silicon amount of the feed; (4) and crystallizing the reaction raw material B under stirring at 88-98 ℃, and recovering the product.
2. The process according to claim 1, wherein the directing agent consists of: (10-17) SiO2：(0.7-1.3)Al2O3：(11-18)Na2O：(200-350)H2O。
3. The preparation method according to claim 1, wherein the silica-alumina gel contains 30-70% by mass of silica and 0.3-20% by mass of sodium oxide.
4. The method according to claim 1, wherein the sodium oxide is less than 1% by mass.
5. The preparation process of claim 1, wherein the silica-alumina gel is prepared with Y-type molecular sieve mother liquor and aluminum sulfate.
6. The preparation method according to claim 1, wherein the silica-alumina gel accounts for 4-10 wt% of the total silicon charge on a dry basis.
7. The process according to claim 1, wherein the composite material has a crystallinity of 60% or more by peak height method and a ratio of crystallinity to peak area method of K1, K1 of 0.76 to 0.89, when measured by X-ray diffraction method; by unit cell constant a0The measured Si/Al ratio is 5.0 to 5.5, and the ratio to the chemically measured Si/Al ratio is K2 or K2 is 0.87 to 0.93.
8. The process according to claim 7, wherein the crystallinity by peak height method is 80% or more.
9. The method according to claim 7, wherein said K1 is 0.80-0.89.
10. The preparation method according to claim 7, wherein the K1 is 0.80-0.85;
11. the process according to claim 7, wherein the unit cell constant a is0The measured silicon-aluminum ratio is 5.2-5.5.
12. The method according to claim 7, wherein said K2 is 0.87-0.92.
13. The method according to claim 7, wherein said K2 is 0.88-0.90.
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| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN102050469A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing alumino silica gel from molecular sieve crystallized mother liquor |
| US20140008605A1 (en) * | 2011-01-19 | 2014-01-09 | Sogang University Research Foundation | Method for dispersing quantum dots or quantum wires in zeolite, method for stabilizing quantum dots or quantum wires in zeolite, and zeolite containing quantum dots or quantum wires dispersed by the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1533982A (en) * | 2003-03-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN102050469A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing alumino silica gel from molecular sieve crystallized mother liquor |
| US20140008605A1 (en) * | 2011-01-19 | 2014-01-09 | Sogang University Research Foundation | Method for dispersing quantum dots or quantum wires in zeolite, method for stabilizing quantum dots or quantum wires in zeolite, and zeolite containing quantum dots or quantum wires dispersed by the method |
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