CN111434611B - NaY molecular sieve synthesis method for improving single-kettle yield - Google Patents
NaY molecular sieve synthesis method for improving single-kettle yield Download PDFInfo
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Abstract
A synthetic method for improving single-kettle yield of NaY molecular sieve is characterized by comprising the following steps: na in precursor of NaY molecular sieve2O/SiO2The mol ratio is increased by 5 to 60 percent to obtain a gel mixture A, the gel mixture A is stirred for at least 0.1 hour at normal temperature to obtain a gel mixture B, inorganic acid is added to obtain a gel mixture C, the gel mixture C is hydrothermally crystallized and a product is recovered, wherein the precursor of the NaY molecular sieve is obtained by mixing a guiding agent, water glass, aluminate, aluminum salt and water, and Na is counted by mol in the precursor of the NaY molecular sieve2O：SiO2＝0.2～0.45、SiO2：Al2O3＝5～18、H2O：Al2O3100 to 200. The method can improve the single kettle yield of the synthetic NaY molecular sieve by 40-60 percent compared with the conventional industrial method.
Description
Technical Field
The invention relates to a method for synthesizing a NaY molecular sieve. More specifically, the invention relates to a method for synthesizing NaY molecular sieve, which can improve the yield of a single kettle.
Background
The Y-type molecular sieve is used as a catalyst active component or a catalyst carrier, is widely applied to oil refining chemical processes such as catalytic cracking, hydrocracking, isomerization and the like, and is a zeolite material with the largest consumption at present. The NaY molecular sieve used as the raw material of the petroleum cracking catalyst is generally required to have a silicon-aluminum ratio of more than 5.0 in order to maintain sufficient hydrothermal stability during use. The current industrial production method of NaY zeolite is basically a guiding agent method (US3639099, US3671191) proposed by GRACE company in the united states, i.e. an alkaline silica-alumina gel is prepared under the condition of adding a guiding agent, and then a NaY molecular sieve is prepared by a hydrothermal crystallization method. According to the preparation method provided by USP3639099, the silicon-aluminum ratio of the prepared NaY molecular sieve is generally 4.0-4.5 due to the high feeding alkalinity; when the silica-alumina ratio is increased by using a lower alkalinity, stirring is difficult due to a lower water content and a more viscous gel. The GRACE company improves the method in US3671191, namely, the silicon-aluminum ratio of the feeding is increased, the water amount of the feeding is increased, so that NaY products with the silicon-aluminum ratio of more than 5.0 are obtained, and most of the methods are commercially available at present. However, in order to avoid the problem of viscosity and difficulty in stirring during the gelatinization of the silica-alumina source, the water content of the system is still high, so that the single-kettle yield of the product is low, and is generally only about 10%.
Therefore, it is a direction of people's efforts to reduce the water input of the synthesis system, to improve the single-pot yield of NaY molecular sieve synthesis, and to reduce the energy consumption in the synthesis process.
CN1185996A discloses a method for improving the synthesis efficiency of NaY molecular sieve. The method improves the temperature of the raw material water glass, reduces the viscosity of colloid in the gel preparation process, can reduce the water input amount, and improves the single kettle yield. However, the method has a complex preparation process, and increases the operation difficulty and the preparation cost.
Disclosure of Invention
The inventor finds that the silicon-aluminum gel system can form gel under higher alkalinity, has lower viscosity, can form gel smoothly without adding water for viscosity reduction, and can improve the yield of a single kettle. Based on this, the present invention was made.
The invention aims to provide a simple method for synthesizing NaY molecular sieve, which is different from the prior art and can improve the yield of a single kettle, aiming at the defects of the prior art.
Therefore, the method for synthesizing the NaY molecular sieve for improving the yield of the single kettle is characterized by comprising the following steps: na in precursor of NaY molecular sieve2O/SiO2Stirring the gel mixture A obtained by increasing the molar ratio by 5-60% for at least 0.1 hour at normal temperature to obtain a gel mixture B, adding inorganic acid to obtain a gel mixture C, carrying out hydrothermal crystallization on the gel mixture C, and recovering a product, wherein a precursor of the NaY molecular sieve is obtained by mixing a guiding agent, water glass, aluminate, aluminum salt and water, and Na is added into the precursor of the NaY molecular sieve in terms of mol 2O：SiO2＝0.2～0.45、SiO2：Al2O3＝5～18、H2O：Al2O3＝100～200。
The method of the invention cancels the visbreaking water which is added when the silicon-aluminum gel is prepared, improves the solid content of the synthesized gel (the solid content of the gel reaches 20 to 30 percent), and can lead the single kettle yield of the synthesized NaY molecular sieve to be improved by 40 to 60 percent compared with the conventional industrial method. I.e. the method is on the optimized feeding SiO2/Al2O3Ratio of Na to Na2O/SiO2Under specific conditions, the relative content of aluminum sulfate and sodium metaaluminate is adjusted to ensure that the precursor of the NaY molecular sieve is higher than the commonly controlled Na2O/SiO2Gelling under specific alkalinity, then neutralizing excessive alkali with inorganic acid to restore the system to the required Na2O/SiO2And (3) specific alkalinity, and then directly heating and crystallizing the synthesized gel by a conventional method to obtain the NaY molecular sieve.
The method of the invention improves the existing synthesis process and uses the conventional industrial raw materials to prepare the NaY molecular sieve on the premise of not changing the existing industrial equipment, thereby improving the single-kettle yield. Meanwhile, the method can save energy consumption during temperature rise crystallization.
Drawings
FIG. 1 is an XRD spectrum of a NaY molecular sieve synthesized by the invention.
FIG. 2 is a Scanning (SEM) electron micrograph of a NaY molecular sieve synthesized by the present invention.
Detailed Description
A method for synthesizing NaY molecular sieve for improving single-kettle yield is characterized by comprising the following steps: na in precursor of NaY molecular sieve 2O/SiO2Stirring the gel mixture A obtained by increasing the molar ratio by 5-60% for at least 0.1 hour at normal temperature to obtain a gel mixture B, adding inorganic acid to obtain a gel mixture C, carrying out hydrothermal crystallization on the gel mixture C, and recovering a product, wherein a precursor of the NaY molecular sieve is obtained by mixing a guiding agent, water glass, aluminate, aluminum salt and water, and Na is added into the precursor of the NaY molecular sieve in terms of mol2O：SiO2＝0.2～0.45、SiO2：Al2O3＝5～18、H2O：Al2O3＝100～200。
In the invention, the precursor of the NaY molecular sieve is obtained by uniformly mixing a crystallization guiding agent with water glass, aluminate and aluminum salt. The crystallization directing agent is prepared according to the prior art (US3639099 and US 3671191). Can be prepared by mixing silicon source, aluminum source, alkali liquor and deionized water according to (15-18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of room temperature to 70 ℃. In the precursor of the NaY molecular sieve, Al in the guiding agent2O3The content of Al accounts for the precursor of the NaY molecular sieve2O33 to 10%, preferably 4 to 9% of the total; the silicon source used for preparing the guiding agent is water glass, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.
In the precursor of the NaY molecular sieve, the molar ratio of Na2O：SiO2＝0.2～0.45、SiO2：Al2O3＝5～18、H2O：Al2O3100-200 of Na under the preferable condition 2O：SiO2＝0.25～0.35、SiO2：Al2O3＝6～10、H2O：Al2O3120-180. In the precursor of the NaY molecular sieve, the aluminum source can be one or a mixture of aluminum sulfate, aluminum chloride, aluminum nitrate or aluminum phosphate.
According to the invention, the gel mixture A can adjust the system alkalinity of the gel mixture A by adjusting the dosage of the acidic aluminum salt and the alkaline aluminate according to the proportioning requirement, so that the system can form gel under higher alkalinity. In order to realize the Na in the precursor of the NaY molecular sieve2O/SiO2The aim of increasing the molar ratio by 5% to 60% is to obtain the gel mixture A by adjusting the relative contents of aluminate and aluminum salt.
In the invention, the inorganic acid is added into the gel mixture B and is used for neutralizing the excessive alkali in the system to ensure that the alkalinity of the gel mixture C reaches Na required to be controlled2O/SiO2In comparison with Na as the same as the precursor of NaY molecular sieve2O/SiO2And (4) the ratio. The inorganic acid may be concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid or their respective aqueous solutions, with concentrated sulfuric acid being preferred.
In the invention, the gel mixture C is crystallized at 70-120 ℃, preferably 90-105 ℃, and the crystallization time is 10-50 h. The procedures for recovering the product are well known to those skilled in the art and will not be described in detail herein. Generally comprises the process of filtering, washing and drying after hydrothermal crystallization is finished to obtain the NaY molecular sieve. For example, the drying process can be carried out in an oven at 80-150 ℃ for 8-24 h, and can also be carried out in a flash drying mode.
The NaY molecular sieve synthesized by the method provided by the invention has the crystallinity of more than 85 percent, the framework silicon-aluminum ratio of more than 5.0 and the crystal grain size of 500 nm-800 nm.
The following examples further illustrate the invention but are not intended to limit the scope of the invention.
In the examples, the crystallinity of the synthesized NaY molecular sieve was determined by the RIPP 146-90 standard method.
The framework silica-alumina ratio is determined by the following formula:
SiO2/Al2O3＝2×(25.8575-a0)/(a0-24.191), wherein, a0Is the unit cell parameter of the molecular sieve, and is determined by the RIPP 145-90 standard method. The RIPP standard method mentioned here can be found in petrochemical analysis methods, ed by Yangcui et al, 1990 edition.
Scanning (SEM) electron microscopy analysis of NaY molecular sieves was performed on an ISI-60A electron microscope, Inc. of ISI in USA. The test conditions are as follows: acceleration voltage 20kV and sample inclination angle 30 deg.
The directing agents used in the examples and comparative examples were prepared by the following procedure: 629 water glass (available from Qilu catalyst Co., Ltd., SiO)2250.6g/L, modulus 3.36, density 1258g/L) were placed in a beaker, and 469g of high-alkali sodium metaaluminate (Al, available from Zinlu catalyst Co.) was added with vigorous stirring2O341g/L，Na2O297 g/L, density 1353g/L) and aging at 30 ℃ for 18 hours on standing, a directing agent was obtained. The mol ratio of the guiding agent is 16.4Na 2O:Al2O3:15SiO2:326H2O。
Example 1
This example illustrates the synthesis provided by the present invention.
Stirring to 350g water glass (Qilu)Catalyst Co., Ltd., SiO2250.6g/L, modulus 3.36, density 1258g/L) are added with 59g of directing agent and 50g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 82g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) to obtain SiO2/Al2O3＝8.5、Na2O/SiO2Gel mixture a was stirred for 0.5h to give gel mixture B. Adding 23g of concentrated sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO in the feeding ratio2/Al2O3＝8.5、Na2O/SiO2＝0.310、H2O/Al2O3Gel blend C of 137. And directly placing the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 26 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.7%. The XRD spectrum of the molecular sieve is shown in figure 1, which shows that the molecular sieve is NaY molecular sieve, the crystallinity is 95.7 percent, and the framework silicon-aluminum ratio is 5.6. The Scanning (SEM) electron micrograph is shown in figure 2, and the crystal grain size of the molecular sieve is concentrated between 500nm and 800 nm.
Example 2
This example illustrates the synthesis provided by the present invention.
320g of water glass (SiO, available from Qilu catalyst Co.) was stirred 2250.6g/L, modulus 3.36, density 1258g/L) were added with 54g directing agent, 55g aluminium sulphate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 70g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) to obtain SiO2/Al2O3＝8.5、Na2O/SiO2Gel mixture a of 0.464. After stirring for 0.5h, a gel mixture B was obtained. 17.6g of concentrated sulfuric acid was added to the gel Compound BContinuously stirring for 0.5h to obtain feeding material ratio SiO2/Al2O3＝8.5、Na2O/SiO2＝0.310、H2O/Al2O3Gel mixture C of 147. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.5%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 94.4%, the ratio of framework Si to Al is 5.6, and the grain size is concentrated in 500-800 nm.
Example 3
This example illustrates the synthesis provided by the present invention.
304g of water glass (SiO, available from Ziru catalyst Co.) was stirred2250.6g/L, modulus 3.36 and density 1258g/L) were added with 51.4g of directing agent and 61g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al) 2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 62g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, the density 1416g/L) are evenly mixed to obtain the feeding material ratio SiO2/Al2O3＝8.5、Na2O/SiO2Gel mixture a of 0.434. After stirring for 0.5h, a gel mixture B was obtained. Adding 13.5g of concentrated sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO in the feeding ratio2/Al2O3＝8.5、Na2O/SiO2＝0.310、H2O/Al2O3149 gel mix C. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 35 hours at 90 ℃, filtering and washing a crystallized product, and drying overnight in an oven at 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.3%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 93.8%, the ratio of skeleton Si to Al is 5.6, and the grain size is 500-800 nm.
Example 4
This example illustrates the synthesis provided by the present invention.
336g of water glass (SiO, available from Qilu catalyst Co.) was supplied with stirring2250.6g/L, modulus 3.36 and density 1258g/L) were added with 47.5g of directing agent and 36g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 68g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al) 2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) to obtain SiO2/Al2O3＝10.0、Na2O/SiO2Gel mixture a of 0.477. After stirring for 0.5h, a gel mixture B was obtained. Adding 17.5g of concentrated sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO in the feeding ratio2/Al2O3＝10.0、Na2O/SiO2＝0.330、H2O/Al2O3156 gel blend C. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 14.5%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 92.2%, the ratio of framework Si to Al is 5.7, and the grain size is concentrated in 500-800 nm.
Example 5
This example illustrates the synthesis provided by the present invention.
268g of water glass (SiO, available from Qilu catalyst Co.) was supplied with stirring2250.6g/L, modulus 3.36 and density 1258g/L) were added with 38g of directing agent and 37g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 50g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, the density 1416g/L) are mixed evenly to obtain the feedProportioning SiO2/Al2O3＝10.0、Na2O/SiO2Gel mixture a of 0.445. After stirring for 0.5h, a gel mixture B was obtained. Adding 10.9g of concentrated sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO in the feeding ratio 2/Al2O3＝10.0、Na2O/SiO2＝0.330、H2O/Al2O3159 g gel blend C. And directly filling the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 33 hours at 95 ℃, filtering and washing a crystallized product, and drying overnight in an oven at 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 14.7%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve respectively have the characteristics of figure 1 and figure 2. The crystallinity of NaY molecular sieve is 91.3%, the silicon-aluminium ratio of skeleton is 5.7, and the grain size is centralized in 500-800 nm.
Example 6
This example illustrates the synthesis provided by the present invention.
248g of water glass (SiO, available from Qilu catalyst Co.) was stirred2250.6g/L, modulus 3.36 and density 1258g/L) were added with 52g of directing agent and 105g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 40g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) to obtain SiO2/Al2O3＝7.0、Na2O/SiO2Gel mixture a of 0.287. After stirring for 0.5h, a gel mixture B was obtained. Adding 7g of 30% dilute sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO2/Al2O3＝7.0、Na2O/SiO2＝0.264、H2O/Al2O3136 gel mixture C. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.4%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 98.0%, the ratio of skeleton Si to Al is 5.2, and the grain size is 500-800 nm.
Example 7
This example illustrates the synthesis provided by the present invention.
284g of water glass (available from Qilu catalyst Co., Ltd., SiO) was supplied under stirring2250.6g/L, modulus 3.36 and density 1258g/L) are sequentially added with 59.3g of directing agent and 112g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 50g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) to obtain SiO2/Al2O3＝7.0、Na2O/SiO2Gel mixture a of 0.316. After stirring for 0.5h, a gel mixture B was obtained. Adding 18g of 30% dilute sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO2/Al2O3＝7.0、Na2O/SiO2＝0.264、H2O/Al2O3134 gel mix C. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.5%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 96.6%, the ratio of framework silicon to aluminum is 5.2, and the grain size is concentrated in 500-800 nm.
Example 8
This example illustrates the synthesis provided by the present invention.
270g of water glass (SiO, produced by Qilu catalyst Co., Ltd.) was stirred2250.6g/L, modulus 3.36, density 1258g/L) were added with 56.5g directing agent, 100g aluminium sulphate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 51g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, the density 1416g/L) are evenly mixed to obtain the feeding material ratio SiO2/Al2O3＝7.0、Na2O/SiO2Gel mixture a of 0.341. After stirring for 0.5h, a gel mixture B was obtained. Adding 25.3g of 30% dilute sulfuric acid into the gel compound B, and continuously stirring for 0.5h to obtain SiO2/Al2O3＝7.0、Na2O/SiO2＝0.264、H2O/Al2O3Gel mixture C of 132. And directly putting the obtained gel mixture C into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 98 ℃, filtering and washing a crystallized product, and drying overnight in an oven at the temperature of 120 ℃ to obtain the NaY molecular sieve.
The one pot yield was 15.7%. The XRD spectrum and Scanning (SEM) electron micrograph of the molecular sieve have the characteristics of figures 1 and 2 respectively. The crystallinity of NaY molecular sieve is 97.3%, the ratio of framework Si to Al is 5.2, and the grain size is concentrated in 500-800 nm.
Comparative example 1
This comparative example illustrates the effectiveness of a conventional industrial gel process (see US3671191) for synthesizing NaY molecular sieves.
182g of water glass (SiO, available from Qilu catalyst Co.) was stirred2250.6g/L, modulus 3.36 and density 1258g/L) were added with 31g of directing agent and 59g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 26g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, density 1416g/L) and 95g of water are mixed evenly to obtain SiO with the feeding proportion2/Al2O3＝8.5、Na2O/SiO2＝0.310，H2O/Al2O3Gel mixture of 222. And (3) putting the obtained gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The one pot yield was 10.0%. The crystallinity of NaY molecular sieve is 90.5%, and the ratio of framework Si to Al is 5.3.
As can be seen from comparative example 1, the single pot yield for the preparation of NaY molecular sieve by the conventional industrial gel process is low.
Comparative example 2
This comparative example illustrates the effectiveness of a conventional industrial gel process (see US3671191) for synthesizing NaY molecular sieves.
To 318g of water glass (SiO, available from Qilu catalyst Co.) under stirring2250.6g/L, modulus 3.36, density 1258g/L) were added with 45g of directing agent, 79g of aluminum sulfate solution (provided by Zilu catalyst Co., Ltd., Al)2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 41g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al) 2O3190.7g/L, Na2O 283.3g/L, density 1416g/L) and 90g of water are mixed evenly to obtain SiO with the feeding proportion2/Al2O3＝10.0、Na2O/SiO2＝0.330、H2O/Al2O3216 gel blend. And (3) putting the obtained gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The one pot yield was 9.6%. The crystallinity of NaY molecular sieve is 90.5%, and the ratio of framework Si to Al is 5.7.
It can also be seen from comparative example 2 that the conventional industrial gel process produces NaY molecular sieve with a lower one pot yield.
Comparative example 3
This comparative example illustrates the effect of synthesizing NaY molecular sieve with reference to CN 1185996A.
197g of water glass (supplied by Qilu catalyst Co., Ltd., SiO)2250.6g/L, modulus 3.36, density 1258g/L) was heated to 65 deg.C, and 41g of directing agent and 91g of aluminum sulfate solution (supplied by Ziru catalyst Co., Ltd., Al) were added thereto in this order with stirring2O3 89.7g/L，H2SO4259g/L, 1277g/L density), 28g of low alkali sodium metaaluminate solution (available from Ziru catalyst Co., Ltd., Al)2O3 190.7g/L，Na2O283.3 g/L, the density 1416g/L) and 90g of water are mixed evenly to obtain the SiO2/Al2O3＝7.0、Na2O/SiO2＝0.249，H2O/Al2O3Gel blend 186. And (3) putting the obtained gel mixture into a stainless steel reaction kettle, crystallizing for 29 hours at the temperature of 100 ℃, filtering and washing a crystallized product, and drying in an oven at the temperature of 120 ℃ overnight to obtain the NaY molecular sieve.
The one pot yield was 12.6%. The crystallinity of NaY molecular sieve is 89.5%, and the ratio of framework silicon to aluminum is 5.0.
As can be seen from the comparative example 3, although the yield of the single kettle of the method for preparing the NaY molecular sieve is improved compared with that of the single kettle of the conventional industrial gel method, the silicon-aluminum ratio of the NaY product is lower, and the raw material sodium silicate needs to be heated to a certain temperature before being gelatinized, so that the production cost and the operation difficulty are increased.
Claims (10)
1. A synthetic method for improving the yield of a NaY molecular sieve single kettle is characterized by comprising the following steps: na in precursor of NaY molecular sieve2O/SiO2Stirring a gel mixture A obtained by increasing the molar ratio by 5-60% for at least 0.1 hour at normal temperature to obtain a gel mixture B, adding an inorganic acid to obtain a gel mixture C, carrying out hydrothermal crystallization on the gel mixture C and recovering a product, wherein a precursor of the NaY molecular sieve is obtained by mixing a guiding agent with water glass, aluminate and aluminum salt without adding viscosity-reducing water, and the Na in the precursor of the NaY molecular sieve is calculated by the mol2O：SiO2＝0.2～0.45、SiO2：Al2O3＝5～18、H2O：Al2O3＝100～200。
2. The method of claim 1 wherein said precursor of NaY molecular sieve is Na on a molar basis2O：SiO2＝0.25～0.35、SiO2：Al2O3＝6～10、H2O：Al2O3＝120～180。
3. The process of claim 1 wherein said aluminate is sodium metaaluminate; the aluminum salt is one or a mixture of aluminum sulfate, aluminum chloride, aluminum nitrate or aluminum phosphate.
4. The method of claim 1 wherein said directing agent comprises Al2O3The content of (A) is Al in the precursor of the NaY molecular sieve2O33 to 10 percent of the total amount.
5. The method of claim 1 wherein said directing agent comprises Al2O3The content of (A) is Al in the precursor of the NaY molecular sieve2O34 to 9 percent of the total amount.
6. The method of claim 1, 4 or 5, wherein the directing agent is prepared by mixing a silicon source, an aluminum source, an alkali solution and deionized water in an amount of (15 to 18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2Mixing the components according to the molar ratio of O, uniformly stirring, standing and aging for 0.5-48 hours at the temperature of room temperature to 70 ℃ to obtain the product.
7. The method according to claim 1, wherein the amount of the inorganic acid is such that Na is present in the gel mixture C on a molar basis2O：SiO2＝0.2～0.35。
8. A process according to claim 1 or 7, wherein the mineral acid is sulfuric acid.
9. The method according to claim 1, wherein said hydrothermal crystallization is carried out at 90 ℃ to 105 ℃ for 10 hours to 50 hours.
10. The process of claim 1 wherein said aluminate is aluminum sulfate.
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