CN116409793B - Method for recovering organic template in molecular sieve synthesis mother liquor - Google Patents
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Abstract
本发明提供了一种分子筛合成母液中有机模板剂的回收方法，包括如下步骤：将复合萃取剂加入分子筛晶化产物中，液固分离，得到分子筛产物和富含模板剂的晶化母液；将所述晶化母液依次通过有机系微滤膜和中空纤维膜，回收得到模板剂和复合萃取剂；其中，所述复合萃取剂为醋酸盐和异丙醇的混合物，醋酸盐和异丙醇的质量比为1：(7～10)。本发明采用复合萃取剂萃取‑双膜分离技术，能够有效解决回收的模板剂中分解产物与杂质的富集问题，降低回收模板剂中的钠离子等无机盐离子的含量，使模板剂重复回收使用次数不少于4次，即第4次回收的模板剂还可以用来制备分子筛材料，不会存在因离子杂质富集导致的模板剂纯度降低，进而影响分子筛的品质的问题。
The present invention provides a method for recovering an organic template in a molecular sieve synthesis mother liquor, comprising the following steps: adding a composite extractant to a molecular sieve crystallization product, liquid-solid separation, and obtaining a molecular sieve product and a crystallization mother liquor rich in a template; passing the crystallization mother liquor through an organic microfiltration membrane and a hollow fiber membrane in sequence, and recovering the template and the composite extractant; wherein the composite extractant is a mixture of acetate and isopropanol, and the mass ratio of acetate to isopropanol is 1:(7-10). The present invention adopts a composite extractant extraction-double membrane separation technology, which can effectively solve the enrichment problem of decomposition products and impurities in the recovered template, reduce the content of inorganic salt ions such as sodium ions in the recovered template, and make the template agent be repeatedly recycled and used for no less than 4 times, that is, the template agent recovered for the 4th time can also be used to prepare a molecular sieve material, and there will be no problem of reduced template purity caused by enrichment of ionic impurities, thereby affecting the quality of the molecular sieve.
Description
Technical Field
The invention relates to the field of molecular sieve synthesis, in particular to a method for extracting and recovering a template agent from a molecular sieve synthesis mother solution.
Background
The organic template agent is widely applied to the synthesis process of special molecular sieves such as nanometer and mesoporous molecular sieves, and the substances generally have the characteristics of strong toxicity, high unit price and large pollution, so that a large amount of waste water with strong alkalinity and high ammonia nitrogen is inevitably generated in the synthesis, washing and other processes of the special molecular sieves, and the environment is polluted. However, in the production process of the molecular sieve, only a small part of the template agent is absorbed and decomposed by the molecular sieve, and a large part of the template agent still exists in crystallized mother liquor after crystallization, so that the template agent is not utilized efficiently. At present, the template agents used in the molecular sieve synthesis process comprise Cetyl Trimethyl Ammonium Bromide (CTAB), tetraethylammonium hydroxide (TEAOH), cetyl trimethyl para-toluene ammonium sulfonate (CTATos), triethylamine (TEA), n-butylamine, ethylenediamine and the like, and the cost of the template agents accounts for about 50-70% of the cost of raw materials, so that the template agents in the crystallization mother liquor of the synthesized molecular sieve are of great significance from the aspects of environmental protection and economic cost.
The template machine is recycled and recycled for preparing the molecular sieve by a person skilled in the art, but the problem that inorganic salts accumulate in the template agent recycling process, so that the template agent recycling efficiency is low and the template agent recycling effect is poor is solved.
CN 103787370B proposes a method for recovering template agent in the process of preparing molecular sieve, said method includes mixing raw material silicon source, aluminium source, phosphorus source and template agent for preparing silicoaluminophosphate molecular sieve with solution to obtain silicoaluminophosphate molecular sieve, after reaction is carried out for 1-72 hr, gas phase substance in reaction system is led out into separation equipment, the led gas phase substance is undergone the separation operation of template agent and solvent, the separated template agent can be repeatedly used by means of pipeline. The method adopts the recycled template agent to prepare the molecular sieve, can reduce the production cost of the molecular sieve, reduce the discharge amount of chemicals, reduce environmental pollution, has simple operation and low energy consumption, and can realize large-scale use. However, in the template agent separation process, the decomposition products and impurities can be continuously enriched, so that the purity of the recovered template agent is reduced.
CN 104030499A proposes a comprehensive treatment method of special molecular sieve synthetic mother liquor, the described special molecular sieve synthetic mother liquor is mother liquor containing silicate radical and quaternary ammonium hydroxide template agent, the special molecular sieve synthetic mother liquor is first filtered by using tubular ceramic membrane whose pore diameter is 0.1-1.2 micrometers, acid is added to regulate pH value to 7-8, first filtered by using sling-type centrifugal machine, filtrate pH value is regulated to 5-6, stirring and flocculation, second filtered by using sling-type centrifugal machine, after the obtained filtrate is stood, fine filtered by using tubular ceramic membrane whose pore diameter is 10-50nm, the filtrate is treated by using bipolar membrane electrodialysis system so as to respectively obtain aqueous solution and sulfuric acid solution of quaternary ammonium hydroxide pure product correspondent to quaternary ammonium hydroxide template agent contained in mother liquor waste water. The invention adopts a ceramic membrane centrifugal filtration mode to effectively recycle the quaternary ammonium alkali template agent, but generates acidic aqueous solution in the template agent recycling process, thereby polluting the environment.
CN 112694186A proposes a method for treating organic amine wastewater, which is used for washing and treating wastewater in the production process of molecular sieves. The method firstly adopts a flocculating agent complexing method to reduce the content of suspended matters in the washing molecular sieve wastewater, then removes organic amine pollutants which are difficult to degrade and have strong toxicity in the wastewater by a membrane separation method, and the treated wastewater can reach the discharge standard.
CN 109721071B proposes a method for preparing titanium-silicon molecular sieve, which is characterized by that under the condition of hydrolysis reaction the aqueous solution containing template agent and organosilicon source are undergone the process of first contact, under the condition of hydrolysis condensation reaction the first hydrolysis mixture and aqueous solution containing titanium source are undergone the process of second contact, in the processes of first contact and second contact the produced steam is led out and condensed, and the hydrolysis condensation mixture and partial condensate are mixed, then undergone the process of hydrothermal crystallization. The method for producing the titanium-silicon molecular sieve can effectively inhibit the decomposition of the template agent in the hydrothermal crystallization process, recycle more template agent, and improve the quality of the hydrothermal crystallization, so that the prepared titanium-silicon molecular sieve has more uniform particle size and narrower particle size distribution, and can obtain improved catalytic activity and selectivity when used as a catalyst for hydroxylation reaction.
The organic template agent is widely applied to the synthesis process of special molecular sieves such as nanometer and mesoporous molecular sieves, and generally has the characteristics of strong toxicity, high unit price, large pollution, high synthesis cost of the molecular sieves, large amount of wastewater generation, environmental pollution and the like. At present, related technicians perform research on recycling of template machine and recycling of the template machine for preparing the molecular sieve, but inorganic salts are accumulated in the template agent recycling process, so that the recycling efficiency of the template agent is low, the purity of the recycled template agent is reduced due to repeated recycling, and the quality of the molecular sieve is seriously affected.
Disclosure of Invention
The invention mainly aims to provide a method for recovering an organic template agent in a molecular sieve synthesis mother solution, which aims to solve the problems of low template agent recovery efficiency and poor template agent effect of repeated recycling recovery in the prior art.
In order to achieve the above purpose, the invention provides a method for recycling an organic template agent in a molecular sieve synthesis mother solution, which comprises the following steps:
Adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent;
Sequentially passing the crystallization mother liquor through a hollow fiber membrane and an organic microfiltration membrane, and recovering to obtain a template agent and a composite extractant;
The composite extractant is a mixture of acetate and isopropanol, and the mass ratio of the acetate to the isopropanol is 1 (7-10).
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the molecular sieve crystallization product is obtained after crystallization is completed in the process of synthesizing a molecular sieve in the presence of the template agent.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the template agent is a quaternary ammonium salt cationic surfactant, and acetate is a soluble salt taking acetate ions as anions.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the template agent is at least one of cetyl trimethyl ammonium bromide, tetraethyl ammonium hydroxide and cetyl trimethyl para-toluenesulfonammonium, and the acetate is at least one of sodium acetate, potassium acetate and ammonium acetate.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the molecular sieve product is at least one of an MCM molecular sieve, a ZSM-5 molecular sieve and an SBA-15 molecular sieve, the pH value of a composite extractant is 6-8, and the adding amount is that the mass ratio of the composite extractant to the molecular sieve crystallization product is 1:1-3.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the temperature of adding a composite extractant into a molecular sieve crystallization product is 35-55 ℃.
The invention discloses a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein an organic micro-filtration membrane comprises at least one of a polyvinylidene fluoride membrane, a polytetrafluoroethylene membrane, a polyvinylidene fluoride membrane, a polyperfluoroethylene propylene membrane, a polypropylene membrane and a polyethylene membrane, and a hollow fiber membrane comprises at least one of a cellulose acetate membrane, a cellulose nitrate membrane, a mixed ester membrane regenerated cellulose membrane and a polyether sulfone membrane.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the pressure of the crystallization mother solution passing through a hollow fiber membrane is 0.1-0.3Mpa, and the aperture is 0.1-10 mu m.
The invention relates to a method for recycling an organic template agent in a molecular sieve synthesis mother solution, wherein the pressure of the crystallization mother solution passing through an organic micro-filtration membrane is 0.1-0.3Mpa, and the aperture is 0.02-10 mu m.
The method for recycling the organic template agent in the molecular sieve synthesis mother liquor comprises the steps of recycling the recycled template agent for synthesizing the molecular sieve, recycling the recycled composite extractant into a molecular sieve crystallization product for liquid-solid separation, and recycling the recycled template agent for synthesizing the molecular sieve for 1-4 times.
The invention has the beneficial effects that:
The invention adopts a composite extractant extraction-double-membrane separation technology, can effectively solve the enrichment problem of decomposition products and impurities in the recovered template, reduces the content of inorganic salt ions such as sodium ions in the recovered template, and enables the template to be repeatedly recovered and used for at least 4 times, namely the template recovered for the 4 th time can also be used for preparing a molecular sieve material, and the problem that the purity of the template is reduced due to the enrichment of ion impurities, thereby influencing the quality of the molecular sieve is avoided.
Drawings
Figure 1 is an XRD spectrum of the molecular sieve obtained in the example of the present invention.
Detailed Description
The following describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a method for recycling an organic template agent in a molecular sieve synthesis mother solution, which comprises the following steps:
Adding a composite extractant into a molecular sieve crystallization product, and carrying out liquid-solid separation to obtain the molecular sieve product and a crystallization mother liquor rich in a template agent;
Sequentially passing the crystallization mother liquor through a hollow fiber membrane and an organic microfiltration membrane, and recovering to obtain a template agent and a composite extractant;
The composite extractant is a mixture of acetate and isopropanol, and the mass ratio of the acetate to the isopropanol is 1 (7-10).
The invention adopts a composite extractant extraction-double-membrane separation technology, can effectively solve the enrichment problem of decomposition products and impurities in the recovered template, reduces the content of inorganic salt ions such as sodium ions in the recovered template, and enables the template to be repeatedly recovered and used for at least 4 times, namely the template recovered for the 4 th time can also be used for preparing a molecular sieve material, and the problem that the purity of the template is reduced due to the enrichment of ion impurities, thereby influencing the quality of the molecular sieve is avoided.
The method can be used for recovering template agents in molecular sieves prepared by using the template agents, wherein the molecular sieves are MCM molecular sieves, ZSM-5 molecular sieves, SBA-15 molecular sieves and the like. The composite extractant is added in the preparation process of the molecular sieve, but the preparation method of the molecular sieve is not particularly limited, for example, the preparation process of the molecular sieve comprises a crystallization step, and the composite extractant is added in a crystallization product of the molecular sieve.
In one embodiment, the invention provides a method for preparing a crystallized product of a molecular sieve, comprising mixing a template agent, a silicon source and an aluminum source to form a gel solution. And adding the gel solution into a crystallization kettle for hydrothermal crystallization treatment, and obtaining a crystallization product after crystallization.
And cooling the crystallized product to room temperature, adding the composite extractant, stirring, and performing liquid-solid separation to obtain a molecular sieve product and a crystallized mother liquor rich in the template agent.
The silicon source and the aluminum source are not particularly limited, and the silicon source and the aluminum source are conventional in the art. In one embodiment, the template agent is a quaternary ammonium cationic surfactant, and in another embodiment, the template agent is at least one of cetyltrimethylammonium bromide (CTAB), tetraethylammonium hydroxide (TEAOH), and cetyltrimethyl-p-toluene-ammonium sulfonate (CTATos).
The composite extractant is a mixture of acetate and isopropanol, and the mass ratio of the acetate to the isopropanol is 1 (7-10). In one embodiment, the acetate salt of the present invention is a soluble salt having acetate ion as anion, such as sodium acetate, potassium acetate, ammonium acetate. The compound extractant is used in the mass ratio of molecular sieve crystallized product of 1 to 1-3.
The present invention is not particularly limited to the liquid-solid separation method, and examples thereof include filtration, centrifugation, and the like. The solid obtained after liquid-solid separation is a molecular sieve product, and the type of the molecular sieve depends on the preparation raw materials and the preparation method, and the added composite extractant does not influence or change the type of the prepared molecular sieve. The molecular sieve product obtained by filtration can be subjected to operation treatments such as drying, roasting and the like, and finally the expected molecular sieve is obtained.
The crystallization mother liquor sequentially passes through a hollow fiber membrane and an organic microfiltration membrane, and the template agent and the composite extractant are recovered. In one embodiment, the organic microfiltration membrane comprises at least one of a polyvinylidene fluoride membrane, a polytetrafluoroethylene membrane, a polyvinylidene fluoride propylene membrane, a polypropylene membrane and a polyethylene membrane, and the hollow fiber membrane comprises at least one of a cellulose acetate membrane, a cellulose nitrate membrane, a mixed ester membrane regenerated cellulose membrane and a polyether sulfone membrane.
After the crystallized product of the molecular sieve is treated by the composite extractant, supernatant (namely the crystallized mother liquor rich in the template agent) is taken and enters a membrane separation device, and the supernatant sequentially passes through a hollow fiber membrane and an organic microfiltration membrane under the pressure of 0.1-0.3Mpa at room temperature, wherein the flux is 600L/(m 2 h). The template agent is trapped by the hollow fiber membrane and the organic microfiltration membrane, and the template agent recovered by filtration is reused.
In one embodiment, the recovered template agent is recycled for synthesizing the molecular sieve, and the recovered composite extractant is recycled for adding the molecular sieve crystallization product for liquid-solid separation.
The template agent recovered by the method has fewer impurities, can be circularly used for preparing the molecular sieve, can still synthesize the molecular sieve material with high specific surface area and large pore volume, the specific surface area of the prepared material can be kept at about 800m 2/g, the pore volume is 1.39-1.91 mL/g, the template agent can be repeatedly used for 1-4 times, and the recovery rate of the template agent is 89.6%.
The technical scheme of the invention is further described in detail through specific examples.
Evaluation analysis method:
Specific surface area and pore volume test the specific surface area and pore structure of the silica alumina material and the catalyst were measured on ASAP2020M specific surface area and porosity analyzer manufactured by Micromeritics company, and the specific surface area was calculated according to BET method, and the pore volume was calculated according to BJH method.
Example 1
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a 60 ℃ constant-temperature water bath, 29G of deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G of water glass solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:7 into the cooled crystallized product, wherein the adding amount of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product. The separated mother liquor rich in the template agent passes through a membrane separation device under the conditions of room temperature and 0.3Mpa of operation pressure, the double-membrane combination is arranged in the membrane separation device, the mother liquor sequentially passes through a cellulose acetate membrane and a polytetrafluoroethylene membrane, the flux is 600L/(m 2 h), the mother liquor passes through the membrane separation device to be a composite extraction solvent, and the recovered template agent is filtered, recovered and reused. Template agent M1=17.16 g is recovered, template agent recovery rate is 76.3%, and texture properties of the synthesized MCM molecular sieve material are shown in table 1.
Example 2
Template M1 recovered in example 1 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g2=5.24G (22.5G-M1), the procedure was the same as in example 1, and template m2=15.41G was recovered to give the resultant MCM molecular sieve material with texture properties as shown in table 1.
Example 3
Template M2 recovered in example 2 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g3=6.99G (22.5G-M2), the procedure was the same as in example 1, and template m3=13.21G was recovered to give the resultant MCM molecular sieve material with texture properties as shown in table 1.
Example 4
Template M3 recovered in example 3 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g4=9.19G (22.5G-M3), the procedure was the same as in example 1, and template m4=10.5G was recovered to give the synthesized MCM molecular sieve material with texture properties as shown in table 1.
Example 5
Template M4 recovered in example 4 was used in duplicate to prepare MCM molecular sieve material along with additional fresh template g5=11.9G (22.5G-M4), the procedure was the same as in example 1, and template m5=7.31G was recovered to give the resultant MCM molecular sieve material with texture properties as shown in table 1.
Example 6
Template M5 recovered in example 5 was used in duplicate with additional fresh template g6=15.09G (22.5G-M5) to prepare MCM molecular sieve material, the procedure was the same as in example 1, and the texture properties of the synthesized MCM molecular sieve material are shown in table 1.
FIG. 1 is an XRD spectrum of a molecular sieve obtained in examples 1-6 of the invention, and the molecular sieve is shown in FIG. 1, and four crystal face diffraction characteristic peaks (100), (110), (200) and (210) appear at about 2 theta of 2.1 degrees, 3.7 degrees, 4.3 degrees and 5.6 degrees, wherein the (100) crystal face peak with high peak intensity is MCM-41 characteristic peak, and can prove that recovered template CTAB spontaneously aggregates to form hexagonal liquid crystal phase to control the molecular sieve to synthesize crystals, so as to form the MCM-41 molecular sieve.
Example 7
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a 60 ℃ constant-temperature water bath, 29G of deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G of water glass solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:8 into the cooled crystallized product, wherein the adding amount of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product. The separated mother liquor rich in the template agent passes through a membrane separation device under the conditions of room temperature and 0.3Mpa of operation pressure, the double-membrane combination is arranged in the membrane separation device, the mother liquor sequentially passes through a cellulose acetate membrane and a polytetrafluoroethylene membrane, the flux is 600L/(m 2 h), the mother liquor passes through the membrane separation device to be a composite extraction solvent, and the recovered template agent is filtered, recovered and reused. Template agent M1=17.57 g is recovered, template agent recovery rate is 78.08%, and texture properties of the synthesized MCM molecular sieve material are shown in table 2.
Example 8
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a 60 ℃ constant-temperature water bath, 29G of deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G of water glass solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:10 into the cooled crystallized product, wherein the adding amount of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product. The separated mother liquor rich in the template agent passes through a membrane separation device under the conditions of room temperature and 0.3Mpa of operation pressure, the double-membrane combination is arranged in the membrane separation device, the mother liquor sequentially passes through a cellulose acetate membrane and a polytetrafluoroethylene membrane, the flux is 600L/(m 2 h), the mother liquor passes through the membrane separation device to be a composite extraction solvent, and the recovered template agent is filtered, recovered and reused. Template agent M1=18.01 g is recovered, template agent recovery rate is 80.04%, and texture properties of the synthesized MCM molecular sieve material are shown in table 2.
Example 9
A solution A is prepared by mixing 23.26g of tetrapropylammonium hydroxide (TPAOH), 24.22g of Tetraethoxysilane (TEOS) and 70g of deionized water, a solution B is prepared by mixing 1.09g of Al (NO 3)39H2 O, 0.47g of NaOH and 27.75g of g H 2 O), then the solution A is hydrolyzed for 3 hours at 35 ℃, the solution B is added into the solution A, the molar ratio of each component in the raw materials is n(Na2O)∶n(Al2O3)∶n(SiO2)∶n(TPAOH)∶n(H2O)＝0.05∶0.0125∶1∶0.25∶55; continuously at 35 ℃, the mixture is stirred for 90 minutes, then the mixture is transferred into a stainless steel crystallization kettle, and is placed in a 170 ℃ oven for standing and crystallization for 24 hours, after the crystallization is finished, a solid product is separated, the deionized water is washed for 3 times, and a sample obtained after the solution A is baked for 4 hours at 120 ℃ and 12 hours at 540 ℃ is the ZSM-5 molecular sieve.
Comparative example 1
25Wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were added in sequence, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:3 into the cooled crystallized product, wherein the total mass of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product, and the template agent recovery rate is 48.2%.
Comparative example 2
25Wt% CTAB solution (CTAB mass G1=22.5G) was placed in a 60 ℃ constant temperature water bath, 29G of deionized water was added, and after stirring until CTAB was dissolved uniformly, 91.6G of 25wt% sodium silicate solution and 72.5G of 20wt% aluminum sulfate solution were added in sequence, and the solution was dynamically treated at 30 ℃ for 4 hours to form an A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And adding a sodium acetate/isopropanol composite extractant with the mass ratio of 1:14 into the cooled crystallized product, wherein the total mass of the composite extractant is 145g, stirring, filtering and separating to obtain mother liquor rich in template agent and a molecular sieve product, and the template agent recovery rate is 58%.
Comparative example 3
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a 60 ℃ constant-temperature water bath, 29G of deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G of water glass solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B. And then 145g of extractant ethanol is added into the cooled crystallized product, and the mixture is stirred, filtered and separated to obtain mother liquor rich in template agent and molecular sieve product. The separated mother liquor rich in the template agent passes through a membrane separation device under the conditions of room temperature and 0.3Mpa of operation pressure, the double-membrane combination is arranged in the membrane separation device, the mother liquor sequentially passes through a cellulose acetate membrane and a polytetrafluoroethylene membrane, the flux is 600L/(m 2 h), the mother liquor passes through the membrane separation device and is a composite extraction solvent, the recovered template agent is filtered and recycled, and the recovery rate of the template agent is 65.7%.
Comparative example 4
CTAB solution with the concentration of 25wt% (CTAB mass G1=22.5G) is placed in a 60 ℃ constant-temperature water bath, 29G of deionized water is added, after the CTAB solution is stirred until the CTAB solution is uniformly dissolved, 91.6G of water glass solution with the concentration of 25wt% and 72.5G of aluminum sulfate solution with the concentration of 20wt% are sequentially added, and the solution is dynamically treated for 4 hours at the temperature of 30 ℃ to form A gel solution. And (3) transferring the mixture gel into a crystallization kettle, and performing hydrothermal crystallization for 48 hours at the temperature of 100 ℃ to obtain a crystallized product B. And cooling the synthesized crystallized product B, and filtering and separating to obtain mother liquor rich in template agent and molecular sieve product. The separated mother liquor rich in the template agent passes through a membrane separation device under the condition of the operating pressure of 0.3Mpa, the double-membrane combination is arranged in the membrane separation device, the mother liquor sequentially passes through a cellulose acetate membrane and a polytetrafluoroethylene membrane, the flux is 600L/(m 2 h), the mother liquor passes through the membrane separation device and is a composite extraction solvent, the recovered template agent is filtered and recycled, and the recovery rate of the template agent is 57.7%.
Table 1 example synthetic molecular sieve properties
Note that: template total recovery = (m1+m2+m3) +m4)/(g1+g2 +G3+G4+G5)
Table 2 example synthetic molecular sieve properties
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
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