CN113120919B - 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
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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, guiding agent, sodium hydroxide solution and water into metakaolin powder to prepare Na with the mixture ratio of (1-2.5) 2 O：Al 2 O 3 ：(4～9)SiO 2 ：(40～100)H 2 O, 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) The reaction raw material B is crystallized under the stirring of 88 to 98 ℃ and the product is recovered.
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 far-reaching revolution in petroleum industry. In the 70 s, the oil refining industry faced the problems of residual oil processing and high-octane gasoline production, and the FCC catalyst had to have the characteristics of high hydrothermal stability, heavy metal pollution resistance, carbon deposit reduction, hydrogen transfer reaction inhibition and the like, which put new requirements on the research of Y-type molecular sieves. Optimum silicon-aluminum ratio n (SiO) of Y-type molecular sieve as active component of cracking catalyst 2 )/n(A1 2 O 3 ) 9-10, but the silicon-aluminum ratio of the directly synthesized Y-type molecular sieve is lower at present, generally about 5, and the search for a new method for 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 silicon-aluminum ratio of the directly synthesized Y-type molecular sieve is lower, the framework silicon-aluminum ratio is improved by adopting a secondary dealumination method in industry, the cost and the loss are increased, more importantly, because the deep dealumination can cause the instability of a zeolite framework, the distribution of surface and bulk silicon-aluminum and active centers is not uniform, and the properties, the functions and the service life of the catalyst are greatly influenced. 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 material 2 )/n(A1 2 O 3 ) The increase in (b) requires a lower alkalinity in the system, which in turn results in loss of product crystallinity and the generation of heterocrystals. In addition, the optimum n (Na) is present in the reaction system 2 O)/n(SiO 2 ) When n (Na) is contained in the material 2 O)/n(SiO 2 ) Greater than optimum n (Na) 2 O)/n(SiO 2 ) When the ratio is higher, the crystallinity of the crystal is basically unchanged, and the silicon-aluminum ratio is sharply reduced; when n (Na) is in the material 2 O)/n(SiO 2 ) Less than optimum n (Na) 2 O)/n(SiO 2 ) 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.
In the method disclosed in CN201110312397.4, natural kaolin minerals and natural diatomite minerals are used to provide all silicon sources and aluminum sources for molecular sieve synthesis, and are used as substrates for molecular sieve growth, and crystal products are formed through in-situ crystallization. In the composite material, the mass percentage content 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, its method uses water glass and sodium metaaluminate as silicon source and aluminum source respectively to prepare Si-Al gel, spray ball with kaolin, then synthesize, the silicon-aluminum ratio of the synthesized product reaches 5.1, but the silicon-aluminum ratio of the feeding material reaches 12, the utilization ratio of the feeding silicon 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 which uses the same silicon source and is obtained by one-time charging of synthesis raw materials, and which can finally synthesize a product with a high silica-alumina ratio, 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, guiding agent, sodium hydroxide solution and water into metakaolin powder to prepare Na with the mixture ratio of (1-2.5) 2 O：Al 2 O 3 ：(4～9)SiO 2 ：(40～100)H 2 O, 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) The reaction raw material B is crystallized under the stirring of 88 to 98 ℃ and the product is recovered.
In the invention, sodium silicate and silica-alumina gel are supplemented to enter 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) 2 O)/SiO 2 ) 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 material 2 )/A1 2 O 3 ) Simultaneously, the sodium-silicon ratio (Na) in the material is reduced 2 O/SiO 2 ) 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 by peak height method and a ratio to a crystallinity by peak area method of K1, K1=0.76 to 0.89, preferably 0.80 to 0.89, more preferably 0.80 to 0.85, when measured by X-ray diffraction method; by unit cell constant a 0 The measured silicon-aluminum ratio is 5.0 to 5.5, preferably 5.2 to 5.5, and the ratio to the chemically measured silicon-aluminum ratio is K2, K2=0.87 to 0.93, preferably 0.87 to 0.92, more preferably 0.88 to 0.90.
In the process of the present invention, the directing agent of step (2) may be synthesized according to conventional methods, for example, according to USP3574538, 3639099, USP3671191, USP4166099 and EUP0435625. The guiding agent comprises the following components: (10-17) SiO 2 ：(0.7-1.3)Al 2 O 3 ：(11-18)Na 2 O：(200-350)H 2 And O. During synthesis, raw materials are aged at 4-35 ℃, preferably 4-20 ℃ to obtain the directing 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.
The silica-alumina gel accounts for 0.1-10 wt%, preferably 4-10 wt% of the total silicon charge.
In the method of the invention, the Y-type molecular sieve composite material product with hierarchical pores and certain mesopores (10-20%) is obtained by crystallization under stirring, but the crystallization stirring speed is 150-1000 r/min, preferably 300-500 r/min, 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 a 0 Determined according to the RIPP145-90 standard method. The framework Si/Al ratio is determined by the unit cell constant a 0 Calculated according to the following formula:
SiO 2 /Al 2 O 3 (molar ratio) =2 × (25.858-a) 0 )/(a 0 -24.191)
The specific surface area was measured by nitrogen adsorption method (GB/T5816-1995), the pore volume was measured by nitrogen adsorption method (RIPP 151-90), 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 -V Micro-pores )/V General 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) 2 6.41% by weight of Na 2 O), 120 g of sodium metaaluminate solution (containing 3.15% by weight of Al) is slowly added with rapid stirring at 30 DEG C 2 O 3 21.1% by weight of Na 2 O), stirring for 1 hour, and aging for 48 hours at 20 ℃ to obtain the guiding agent. The guiding agent is 16Na 2 O：Al 2 O 3 ：15SiO 2 ：320H 2 O。
Example 1
100 kg of pulverized metakaolin powder, 400 kg of sodium silicate solution (containing 20.05% by weight of SiO) was added with stirring 2 6.41% by weight of Na 2 O), 60 kg of directing agent, 100 kg of 5% strength by weight sodium hydroxide 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 gel 2 62％,Al 2 O 3 15％,Na 2 O13 percent, recrystallizing for 12 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 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 a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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 stirring 2 6.41% by weight of Na 2 O), 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 gel 2 62％,Al 2 O 3 15％,Na 2 And O13 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, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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 1 2 6.41% by weight of Na 2 O), 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, crystallinity by Peak height method, K1 value of ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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 the pulverized metakaolin powder was added with 400 kg of a sodium silicate solution (containing 20.05% by weight of SiO) under stirring in the same manner as in example 1 2 6.41% by weight of Na 2 O), 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 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 deg.C for 2 hr to obtain zeolite DGY-3.
X-ray diffraction measurement of DGY-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 a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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
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 stirring 2 6.41% by weight of Na 2 O), 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 SiO 2 62％,Al 2 O 3 15％,Na 2 O13 percent, 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 for 2 hours at 120 ℃ 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 a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon/aluminum ratio to the chemically measured silicon/aluminum 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 1 2 6.41% by weight of Na 2 O), 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 SiO 2 62％,Al 2 O 3 15％,Na 2 O13 percent, recrystallizing for 16 hours, and stirring at the rotating speed of 400 revolutions per minute during feeding and crystallization. After crystallization is finished, the crystallization tank is quenched, filtered and washed by water until the pH value of 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 a cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum ratio are shown in table 1.
Example 4
100 kg of the pulverized metakaolin powder was added with 400 kg of a sodium silicate solution (containing 20.05% by weight of SiO) under stirring in the same manner as in example 1 2 6.41% by weight of Na 2 O), 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 SiO 2 61.7％,Al 2 O 3 14.6％,Na 2 O13 percent, recrystallizing for 14 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 for 2 hours at 120 ℃ 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 a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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 stirring 2 6.41% by weight of Na 2 O), 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 SiO 2 61.7％,Al 2 O 3 14.6％,Na 2 O13 percent, 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-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 a cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum 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 1 2 6.41% by weight of Na 2 O), 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 SiO 2 61.7％,Al 2 O 3 14.6％,Na 2 O13 percent, recrystallizing for 16 hours, and stirring at the rotating speed of 400 r/min during feeding and crystallizing. After crystallization is finished, the crystallization tank is quenched, filtered and washed by water until the pH value of washing liquor is less than 10. Drying at 120 ℃ for 2 hours to obtain the composite material GY-6.
GY-6, peak height method Crystal by X-ray diffraction measurementK1 value of the ratio of the degree of crystallization by peak height method to the degree of crystallization by peak area method, and a unit cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum ratio are shown in table 1.
Example 7
100 kg of pulverized metakaolin powder was added 360 kg of sodium silicate solution (containing 20.05 wt% SiO) with stirring as in example 1 2 6.41% by weight of Na 2 O), 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 SiO 2 61.7％,Al 2 O 3 14.6％,Na 2 O13 percent, recrystallizing for 16 hours, and stirring at the rotating speed of 400 revolutions per minute during feeding and crystallization. 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, K1 value of the ratio of crystallinity by Peak height method to crystallinity by Peak area method, and cell constant a 0 Measured Si/Al ratio in terms of unit cell constant a 0 The K2 value and the mesopore ratio of the measured silicon-aluminum ratio to the chemically measured silicon-aluminum ratio are shown in table 1.
TABLE 1
Claims (9)
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 the metakaolin into metakaolin powder with the particle size of less than 10 microns; (2) Adding sodium silicate, a guiding agent, a sodium hydroxide solution and water into metakaolin powder to prepare a mixture with the mixture ratio of (1-2.5) Na2O: al2O3: (4 to 9) SiO2: (40-100) a reaction raw material A of H2O, wherein the guiding agent comprises the following components: (10-17) SiO2: (0.7-1.3) Al2O3: (11-18) Na2O: (200-350) H2O, wherein the mass ratio of the directing agent to the metakaolin is 0.01-1.0; (3) Stirring and crystallizing a reaction raw material A at 88-98 ℃, supplementing silica-alumina gel after the crystallization time reaches 1-70h to obtain a reaction raw material B, wherein in the silica-alumina gel, the mass content of silicon dioxide is 30-70%, the mass content of sodium oxide is 0.3-20%, the silica-alumina gel dry basis accounts for 0.1-10% of the total fed silicon weight; (4) And (2) crystallizing the reaction raw material B under stirring at 88-98 ℃, and recovering a product to obtain the composite material, wherein the crystallinity of the composite material is more than or equal to 60% by a peak height method when measured by an X-ray diffraction method, the ratio of the crystallinity to the crystallinity of a peak area method is K1, K1= 0.76-0.89, the ratio of silicon-aluminum ratio determined by a unit cell constant a0 is 5.0-5.5, and the ratio of the crystallinity to the silicon-aluminum ratio determined by a chemical method is K2, K2= 0.87-0.93.
2. The preparation method according to claim 1, wherein the silica-alumina gel is prepared by adding aluminum sulfate into industrially produced Y-type molecular sieve mother liquor.
3. The process of claim 1 wherein the silica alumina sol is present in a dry basis of from 4 to 10 weight percent based on the total silicon charge.
4. The process according to claim 1, wherein the crystallinity by peak height method is 80% or more.
5. The method according to claim 1, wherein K1=0.80 to 0.89.
6. The method according to claim 1, wherein K1= 0.80-0.85.
7. The process according to claim 1, wherein said Si/Al ratio measured by a unit cell constant a0 is 5.2 to 5.5.
8. The method according to claim 1, wherein K2= 0.87-0.92.
9. The method according to claim 1, wherein K2=0.88 to 0.90.
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