CN111099611A - Method for synthesizing pure silicon zeolite by recycling mother liquor repeatedly - Google Patents
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Abstract
A method for synthesizing pure silicon zeolite by recycling mother liquor repeatedly comprises mixing quartz and alkali solution, heating for dissolving, filtering to remove impurities to obtain sodium silicate solution; adding hydrochloric acid into part of the sodium silicate solution to obtain silicic acid and drying; adding the obtained dry silicic acid into a diluted sodium silicate solution to obtain silica sol; adding TPABr into silica sol, adding fumed silica into the TPABr, and stirring to obtain uniform and stable gel; transferring the gel into a reaction kettle for hydrothermal crystallization, and then centrifugally separating the obtained product; washing, drying and calcining the solid product to obtain a final product, and recovering a supernatant; adding dry silicic acid, fumed silica, alkali and TPABr less than the initial dosage into the recovered mother liquor, and stirring to obtain uniform and stable gel again; transferring the sol into a reaction kettle for hydrothermal crystallization, then centrifugally separating the obtained product, washing, drying and calcining the solid product to obtain a final product; and repeating the steps after the mother liquor is recovered. Green and environment-friendly, and low cost.
Description
The technical field is as follows:
the invention relates to a method for synthesizing pure Silicalite (namely Silicalite-1, also called as all-Silicalite molecular sieve), in particular to a method for synthesizing pure Silicalite by recycling mother liquor for many times.
Background art:
pure silicalite-1 is a molecular sieve with MFI topology. The constituent elements are only silicon and oxygen. The silicalite-1 zeolite structure consists of: 5 silicon-oxygen tetrahedrons are connected through bridge oxygen to form five-membered rings, 8 five-membered rings are connected through common edges to form a cage structure, then the cage is expanded into layers, and the layers are superposed to form the silicalite-1 zeolite structure. The main channel of the silicalite-1 zeolite is of a ten-membered ring structure, the ten-membered ring channel parallel to the a axis direction is in a zigzag shape, and the aperture is 0.51 multiplied by 0.55 nm; the ten-membered ring channel parallel to the b-axis direction is linear, and the aperture is 0.53 multiplied by 0.56 nm. silicalite-1 zeolite has higher hydrophobicity and is commonly used for separating organic matters from aqueous solution; in addition, the catalyst is also used for catalyzing cyclohexanone oxime to generate Beckmann rearrangement to prepare caprolactam which is an important raw material for producing nylon-6.
The invention mainly aims at the existing synthesis process of pure silicalite-1, and the mother liquor can not be utilized and recycled like other artificially synthesized zeolites (such as NaX type zeolite, Y type zeolite and the like). The long-standing technical problem is mainly caused by Na in the sodium silicate prepared by the original method2O and SiO2The proportion of (A) is too high to meet the alkalinity requirement of synthesizing the silicalite-1 zeolite, and sulfuric acid or hydrochloric acid is required to be added to reduce the alkalinity. However, the accumulation of sodium sulfate or sodium chloride during the recycle process inhibits the formation of silicalite-1 zeolite crystals, making the recycle process impossible to continue. The method has the key points that in the process of utilizing the mother liquor, the silicon source, the alkalinity and the water are kept to be the same as those in the first synthesis process, then a proper amount of template agent is added, the synthesis process is continuously and circularly carried out, and the silicalite-1 zeolite prepared by repeated times and the silicalite-1 zeolite synthesized for the first time have no obvious difference in product purity and physical and chemical properties. The method recovers the mother liquor, simultaneously recovers the residual template agent, alkali, crystal nucleus, water and the like remained in the mother liquor, obviously improves the use efficiency of the raw materials, avoids the discharge or treatment of the mother liquor, and greatly saves the production costThe method is as follows.
The literature and patents relating to the synthesis of silicalite-1 zeolite are briefly described as follows:
flanigen et al, in the open English literature Nature (271 (1978): 512-516), first reported the synthesis of a novel hydrophobic molecular sieve silicalite. The preparation method is characterized in that a siliceous precursor consisting of alkyl ammonium cations (such as tetrapropyl ammonium cations), alkali ions and reactive silicon dioxide is put into a closed system and hydrothermally crystallized at the temperature of 100-200 ℃. And calcining the obtained crystal at 500-600 ℃ to remove organic matters to obtain a final product. This reference does not refer to quartz as a starting material and does not refer to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
The effect of a silicon source on the synthesis of nano-pure silica zeolites is described by Mintova and Valtchev in published English articles Microporous and MeOporous Materials (55 (2002): 171-. The method is characterized in that TEOS (tetraethyl orthosilicate), silica sol and fumed silica are respectively used as silicon sources for synthesizing the silicalite-1 zeolite, and the influence of the size of amorphous particles formed in precursor mixtures of different silicon sources on the particle size of the finally formed nano silicalite-1 zeolite is researched. This reference does not refer to quartz as a starting material and does not refer to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
Lu Hui Bin et al reported in published Chinese literature, Petroleum bulletin (32(2016) (461); 466) the relevant achievement of modification of the morphology and size of silicalite-1 zeolite crystals by varying the hydrothermal synthesis conditions. The method is characterized in that a certain amount of TPABr is dissolved in deionized water, NaOH is added, and fumed silica is added after uniform mixing; aging for 24h, and transferring into a reaction kettle for hydrothermal crystallization to obtain a product. In the experimental process, the influence of the change of each condition on the appearance and the particle size of the synthesized product is explored by respectively changing the dosage of alkali, water and the template agent and changing the crystallization temperature and the stirring mode during crystallization. This reference does not refer to quartz as a starting material and does not refer to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
Chinese patent (application publication No. CN105858681A, application No. CN201510036072.6) of Wangbaorong et al discloses a method for synthesizing silicalite-1 molecular sieve. The synthesis steps are as follows: (1) uniformly mixing a silicon source, a structure directing agent, water and an optional alkali source, wherein the structure directing agent is at least one of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride and triethylamine; (2) adding a mineralizer into the reaction mixture obtained in the step (1) to adjust the proportion of the mineralizer to hydroxyl, uniformly stirring, and crystallizing at the temperature of 80-200 ℃ and under the self pressure for 0.5-60 days to obtain a crystallized product; (3) recovering the product. The invention can synthesize the silicalite-1 molecular sieve with perfect and uniform crystal grains and less framework defects under the action of the novel structure directing agent. This patent does not relate to quartz as a starting material and does not relate to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
Chinese patents (application publication No. CN105289324A, application No. CN201510763842.7) such as Chenhongliang disclose a preparation method of a high-performance silicalite-1 molecular sieve membrane. The method comprises the following steps: (1) soaking and drying a porous alumina or silicon dioxide ceramic tube carrier for multiple times by using a mixed solution prepared from Arabic gum, carboxymethyl cellulose, tannic acid, soluble starch, cane sugar and glycerol; (2) weighing deionized water, NaOH, tetrapropyl ammonium bromide and silica sol, and preparing into two groups of synthetic liquids; (3) and (3) putting the carrier into a reaction kettle, and performing hydro-thermal synthesis by using the twice synthetic liquids respectively. Then washing the synthesized molecular sieve membrane to be neutral; (4) and removing the template agent from the dried silicalite-1 molecular sieve membrane at 400-600 ℃. This patent does not relate to quartz as a starting material and does not relate to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
Li jin Ping et al (application publication No. CN105645425A, application No. CN201610130032.2) discloses a method for rapidly synthesizing mesoporous silicalite-1 molecular sieve by using white carbon black as silicon source. The method is technically characterized in that a small amount of tetrapropylammonium bromide is used as a microporous template, KF with low price is used as a mesoporous template, a trace amount of seed crystal is added, white carbon black is used as a silicon source, deionized water is used as a solvent, hydrothermal crystallization is carried out in a reaction kettle, and then the mesoporous silicalite-1 molecular sieve is obtained through centrifugation, washing, drying and calcination. This patent does not relate to the use of quartz as a starting material and does not relate to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
Li jin Ping et al (application publication No. CN 105668579A, application No. CN201610130057.2) discloses a method for rapidly synthesizing a mesoporous silicalite-1 molecular sieve by using silica sol as a silicon source. The method is technically characterized in that a small amount of tetrapropylammonium bromide is used as a microporous template, KF with low price is used as a mesoporous template, a trace amount of seed crystal is added, silica sol is used as a silicon source, deionized water is used as a solvent, hydrothermal crystallization is carried out in a reaction kettle, and then the mesoporous silicalite-1 molecular sieve is obtained through centrifugation, washing, drying and calcining. This patent does not relate to quartz as a starting material and does not relate to the multiple use of recycled mother liquor for the synthesis of silicalite-1 zeolite.
The invention content is as follows:
aiming at the defects in the prior art, the invention provides a method for synthesizing pure silicalite-1 by repeatedly recycling and recovering mother liquor, which is a method for continuously synthesizing pure-phase silicalite-1 for multiple times by using quartz as a partial silicon source, repeatedly recovering and supplementing the silicon source and a template agent in the synthesized mother liquor.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for synthesizing pure silicon zeolite by recycling mother liquor repeatedly comprises the following steps:
1) mixing quartz and a sodium hydroxide solution in proportion, heating for dissolving, filtering to remove impurities and obtain a sodium silicate solution;
2) adding hydrochloric acid into part of the sodium silicate solution in the step 1) to obtain silicic acid, washing and drying;
3) adding the dried silicic acid obtained in the step 2) into a diluted sodium silicate solution to obtain silica sol;
4) adding TPABr into the silica sol obtained in the step 3);
5) adding fumed silica into the sol obtained in the step 4), stirring to obtain uniform and stable gel, and aging;
6) transferring the gel obtained in the step 5) into a reaction kettle for hydrothermal crystallization;
7) centrifugally separating the product obtained in the step 6);
8) washing, drying and calcining the solid product obtained in the step 7) to obtain a final product;
9) recovering the supernatant obtained in the step 7) or the step 14), namely mother liquor;
10) supplementing sodium hydroxide solution and the dry silicic acid prepared in the step 2) into the mother liquor obtained in the step 9) to obtain silica sol;
11) adding TPABr into the silica sol obtained in the step 10), wherein the using amount of TPABr is less than that required in the step 4);
12) adding fumed silica into the sol obtained in the step 11), stirring to obtain uniform and stable gel, and aging;
13) transferring the gel obtained in the step 12) into a reaction kettle for hydrothermal crystallization;
14) centrifuging the product obtained in the step 13);
15) washing, drying and calcining the solid product obtained in the step 14) to obtain a final product;
16) repeating all operations of step 9) to step 15) a plurality of times.
Further, in the step 1), the concentration of the sodium hydroxide solution is 6-8 mol/L, the molar ratio of the quartz to the sodium hydroxide is 1: 2, the reaction temperature is 180-230 ℃, and the reaction time is 18-24 h.
Further, in step 2), the pH of the system after the addition of hydrochloric acid was about 1.
Further, in step 3), dry silicic acid is added to make Na in the silica sol2O and SiO2The molar ratio of (A) to (B) is 0.29 to 1.
Further, in the step 5), the molar ratio of each substance in the uniform stable sol is SiO2∶Na2O∶TPABr∶H2O＝1∶0.05～0.33∶0.04～0.5∶30～150。
Further, in the step 6), the hydrothermal crystallization temperature is 130-190 ℃, and the crystallization time is 8-24 hours.
Further, in step 11), the amount of TPABr added is equal to the SiO in the gel obtained in step 5)2The molar ratio of the amount of the component (A) is 0.02 to 0.4.
Further, in the steps 5) and 12), the aging time is 6-36 h.
Further, at step 12)Medium, uniform and stable SiO in gel2、Na2O、H2The amount of O is the same as in step 4).
Further, in step 13), the hydrothermal crystallization temperature and the crystallization time period are the same as those in step 6).
Further, in step 16), the number of operations is equal to or greater than two.
By adopting the technical scheme, the method has the key points that the amounts of a silicon source, alkalinity and water in the mother liquor utilization process are kept the same as those in the first synthesis process, and then a proper amount of template agent is added to continuously and circularly carry out the synthesis process, so that the silicalite-1 zeolite prepared by multiple cycles has no obvious difference in product purity and physicochemical properties with the silicalite-1 zeolite synthesized for the first time. The invention is characterized in that the quartz which is widely and easily obtained is used as a part of silicon source, and the cost of raw materials is reduced. Meanwhile, the method uses the recovered mother liquor in the synthesis process of the silicalite-1 zeolite, reduces the synthesis cost by improving the utilization rate of the residual raw materials and the template agent in the mother liquor, avoids the problem of environmental pollution caused by discharge of wastewater containing organic matters, and is a green and sustainable silicalite-1 zeolite synthesis method.
Description of the drawings:
the accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray powder diffraction pattern of silicalite-1 zeolite synthesized for the first time and three times using recycled mother liquor in an example of the present invention;
FIG. 2 is a scanning electron microscope image of silicalite-1 zeolite synthesized for the first time and three times by using the recycled mother liquor in the example of the present invention.
The specific implementation mode is as follows:
in order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in FIGS. 1 and 2, FIG. 1 is an X-ray powder diffraction pattern of silicalite-1 zeolite synthesized three times by using a recovered mother liquor in an example of the present invention. In fig. 1, the abscissa is diffraction angle 2 θ/(°), and the ordinate is intensity (relative intensity). FIG. 2 is a scanning electron microscope image of silicalite-1 zeolite synthesized three times by using the recovered mother liquor in the example of the present invention. The scale in the picture is 10 μm.
The invention will be further explained by the following examples, which are given by way of illustration only and thus do not limit the invention.
Example 1
1.820g of quartz and 10.00mL of 6mol/L sodium hydroxide solution were charged into a high pressure autoclave with a Teflon liner. And (3) heating the reaction kettle at 190 ℃ for 24h, taking out and cooling. The resulting product was then filtered. The filtrate (9.00 mL) was added to 10.00mL of a 3mol/L hydrochloric acid solution to obtain silicic acid. Washing silicic acid with water for three times, and drying at 75 deg.C for 36 hr to obtain dry silicic acid. Adding water 25.00mL into 2.16mL of the filtrate, adding dried silicic acid 1.170g, stirring at room temperature for 3h, and keeping the temperature at 65 ℃ overnight to obtain transparent silica sol. 0.326g of TPABr was added to the silica sol and stirred for 15 min. 0.540g fumed silica was added and aged at room temperature for 13h to give a homogeneous stable gel, the gel composition at this time being Na2O∶TPABr∶H2O∶SiO20.2: 0.04: 50: 1. Transferring the obtained gel into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 24 hours at 150 ℃. The resulting product was centrifuged, the supernatant (mother liquor) was collected, and the solid product was washed with water three times and dried and then calcined at 550 ℃.
Weighing a certain amount of dry silicic acid, adding into the collected mother liquor, then adding 0.45mL of 6mol/L sodium hydroxide solution into the mother liquor, stirring for 3h at room temperature, and keeping the temperature at 65 ℃ overnight to obtain transparent silica sol. 0.163g of TPABr was additionally added to the above silica sol, and stirred for 15 min. 0.540g fumed silica was added and aged at room temperature for 13h to give a homogeneous stable gel. Transferring the obtained gel into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 24 hours at 150 ℃. And centrifugally separating the obtained product, collecting supernatant (mother liquor), washing the solid product with water for three times, drying, and calcining at 550 ℃ to obtain the final product.
Repeating the previous operation twice to obtain a product produced by recycling the mother liquor for three times. Phase identification of the obtained product proves that the obtained product is pure-phase silicalite-1 zeolite.
Example 2
Example 1 was repeated, but the amount of additional tetrapropylammonium bromide used in the mother liquor was changed to 0.204 g. Phase identification of the obtained product proves that the obtained product is pure-phase silicalite-1 zeolite.
Example 3
Example 1 was repeated, but the heating temperature and time after mixing the quartz with the sodium hydroxide solution were changed to 200 ℃ and 20 h. The gel crystallization temperature after aging is changed to 160 ℃ and 16 h. Phase identification of the obtained product proves that the obtained product is pure-phase silicalite-1 zeolite.
FIG. 1 is a graph comparing the powder X-ray diffraction patterns of silicalite-1 synthesized in the first synthesis (a) and in the first (b), second (c) and third (d) cycles of recovering mother liquor, showing that the silicalite-1 synthesized after the mother liquor is recycled for many times does not have any difference in product purity from that of the first synthesis. FIG. 2 is a comparison of the electron micrographs of the silicalite-1 synthesized in the first synthesis (a) and in the first (b), second (c) and third (d) cycles of the recovered mother liquor, showing that there is no difference in purity of the synthesized silicalite-1 product after the mother liquor is recycled for a plurality of times.
The invention relates to a method for synthesizing silicalite-1 zeolite (pure silicalite) by taking quartz and gas-phase silica as silicon sources and TPABr (tetrapropylammonium bromide) as a template agent, recycling the mother liquor after hydrothermal synthesis for many times, and supplementing raw materials and a small amount of template agent. Relates to a zeolite. Mixing quartz and an alkali solution, heating for dissolving, and filtering to remove impurities to obtain a sodium silicate solution; adding hydrochloric acid into part of the sodium silicate solution to obtain silicic acid and drying; adding the obtained dry silicic acid into a diluted sodium silicate solution to obtain silica sol; adding TPABr into silica sol, adding fumed silica into the TPABr, and stirring to obtain uniform and stable gel; transferring the gel into a reaction kettle for hydrothermal crystallization, and then centrifugally separating the obtained product; washing, drying and calcining the solid product to obtain a final product, and recovering a supernatant (mother liquor); adding dry silicic acid, fumed silica, alkali and TPABr less than the initial dosage into the recovered mother liquor, and stirring to obtain uniform and stable gel again; transferring the sol into a reaction kettle for hydrothermal crystallization, then centrifugally separating the obtained product, washing, drying and calcining the solid product to obtain the final product. Repeating the steps after the mother liquor is recovered to obtain the silicalite-1 zeolite for many times. According to the method, the residual raw materials and the template agent in the mother liquor are recycled, so that the silicalite-1 zeolite prepared repeatedly in a circulating mode and the silicalite-1 zeolite synthesized for the first time have no obvious difference in product purity and physical and chemical properties, the problem that the pure silicalite cannot be recycled to prepare a high-purity phase from the recycled mother liquor is solved, the utilization rate of the raw materials and the template agent is greatly improved, the cost for synthesizing the silicalite-1 zeolite is reduced, the problem of environmental pollution possibly caused by discharge of the mother liquor containing organic matters is also avoided, and the method has the advantages of environmental friendliness and low cost.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for synthesizing pure silicon zeolite by recycling mother liquor for multiple times is characterized in that: the method comprises the following steps:
1) mixing quartz and a sodium hydroxide solution in proportion, heating for dissolving, filtering to remove impurities and obtain a sodium silicate solution;
2) adding hydrochloric acid into part of the sodium silicate solution in the step 1) to obtain silicic acid, washing and drying;
3) adding the dried silicic acid obtained in the step 2) into a diluted sodium silicate solution to obtain silica sol;
4) adding TPABr into the silica sol obtained in the step 3);
5) adding fumed silica into the sol obtained in the step 4), stirring to obtain uniform and stable gel, and aging;
6) transferring the gel obtained in the step 5) into a reaction kettle for hydrothermal crystallization;
7) centrifugally separating the product obtained in the step 6);
8) washing, drying and calcining the solid product obtained in the step 7) to obtain a final product;
9) recovering the supernatant obtained in the step 7) or the step 14), namely mother liquor;
10) supplementing sodium hydroxide solution and the dry silicic acid prepared in the step 2) into the mother liquor obtained in the step 9) to obtain silica sol;
11) adding TPABr into the silica sol obtained in the step 10), wherein the using amount of TPABr is less than that required in the step 4);
12) adding fumed silica into the sol obtained in the step 11), stirring to obtain uniform and stable gel, and aging;
13) transferring the gel obtained in the step 12) into a reaction kettle for hydrothermal crystallization;
14) centrifuging the product obtained in the step 13);
15) washing, drying and calcining the solid product obtained in the step 14) to obtain a final product;
16) repeating all operations of step 9) to step 15) a plurality of times.
2. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the step 1), the concentration of the sodium hydroxide solution is 6-8 mol/L, the mass molar ratio of quartz to sodium hydroxide is 1: 2, the reaction temperature is 180-230 ℃, and the reaction time is 18-24 h.
3. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the step 2), the pH value of the system is about 1 after the hydrochloric acid is added; in step 3), dry silicic acid is added to make Na in the silica sol2O and SiO2The molar ratio of (A) to (B) is 0.29 to 1.
4. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the step 5), the molar ratio of each substance in the uniform stable sol is SiO2∶Na2O∶TPABr∶H2O＝1∶0.05～0.33∶0.04～0.5∶30～150。
5. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the step 6), the hydrothermal crystallization temperature is 130-190 ℃, and the crystallization time is 8-24 h.
6. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in step 11), the amount of TPABr added is equal to the SiO in the gel obtained in step 5)2The molar ratio of the amount of the component (A) is 0.02 to 0.4.
7. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the steps 5) and 12), the aging time is 6-36 h.
8. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in step 12), SiO in the homogeneously stabilized gel2、Na2O、H2The amount of O is the same as in step 4).
9. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in the step 13), the hydrothermal crystallization temperature and the crystallization time are the same as those in the step 6).
10. A method as claimed in claim 1 for synthesizing pure silicalite by recycling the mother liquor a plurality of times, characterized in that: in step 16), the number of operations is equal to or greater than two.
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