CN113548672A - Method for preparing foam structure zeolite molecular sieve by organic foam chemical growth method - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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Abstract
The invention discloses a method for preparing a foam structure zeolite molecular sieve by an organic foam chemical growth method, which comprises the following steps: sequentially adopting water and an alkali solution to pretreat the foamed polyurethane matrix; washing with water to remove residual alkali solution on the surface of the foamed polyurethane, and drying; h is to be2SO4Mixing the solution with concentrated sodium silicate solution, marking as mixed solution A, and adding H2SO4Mixing the solution with an aluminum sulfate solution, and marking as a mixed solution B; adding the mixed solution B into the mixed solution A, then putting the treated foamed polyurethane into the solution for soaking until the pH value of the solution reaches 8-10, gradually gelling, and aging; removing the foamed polyurethane with the growing gelAnd soaking in acid water, washing with water, drying, and sintering to obtain the final product. The foam structure of the zeolite molecular sieve is a 3D network structure, and the internal gas is communicated with each other, so that the problem of local pore blocking failure in the pore structure can be solved. And the compressive strength and the adsorption performance of the zeolite molecular sieve are superior to those of the existing honeycomb zeolite.
Description
Technical Field
The invention relates to the technical field of zeolite molecular sieve preparation, in particular to a method for preparing a foam structure zeolite molecular sieve by an organic foam chemical growth method.
Background
The porous structure ceramic has the characteristics of high strength, large specific surface area, low volume density, high temperature resistance, excellent permeability and erosion resistance and the like, and is widely applied to the fields of aerospace, nonferrous smelting, medical frameworks, filtration catalysis and the like. At present, the common preparation methods of the porous structure ceramic comprise a foaming method, a sol-gel method, a pore-forming agent adding method, an organic foam impregnation method, a gel injection molding method and the like. The organic foam impregnation method is characterized in that organic foam (polyurethane sponge) is used as a template to be impregnated in ceramic slurry prepared in advance, gas in the organic foam is removed to enable the slurry to be fully impregnated in a matrix, then excessive slurry is discharged through external acting force and is repeatedly carried out, so that the slurry is uniformly coated on a screw rod with an organic foam three-dimensional net structure, and the organic foam impregnation method is formed through processes of baking, calcining and the like. Compared with other preparation methods, the organic foam impregnation method has the following advantages: 1) the prepared porous structure ceramic has the advantages of high porosity, large specific surface area, small thermal expansion coefficient, stable size, high temperature resistance and excellent mechanical property. 2) The process is easy to control, simple and convenient to operate, low in production cost and convenient to realize industrialization. 3) The prepared porous structure ceramic has wide application field range and the like.
At present, zeolite molecular sieves mainly have a honeycomb structure and a corrugated structure, such as those disclosed in patent 201910959009.8 and patent CN201811621735.0, and molecular sieve products with a foam structure are not available. The existing honeycomb and corrugated structure zeolite is a through hole structure, and gas can not be internally mixed after entering the through hole structure and flows independently. Therefore, if the pore channels are once plugged, the whole pipeline cannot be charged with air, and the adsorption capacity is affected.
The main raw materials of the polyurethane are organic polyisocyanate and hydroxyl-terminated compound, and the polyurethane has high strength and good rebound resilience and flexibility, so that the polyurethane is widely applied to templates of foamed ceramics. But the polyurethane surface is hydrophobic, so that the surface of the polyurethane cannot be uniformly covered by the water-based ceramic slurry, and the strength of the prepared porous structure ceramic is low.
In the traditional organic foam impregnation method, polyurethane foam is mainly impregnated in ceramic slurry, and porous structure ceramic is prepared through drying and calcining. The polyurethane foam surface pretreatment and the preparation of high-performance slurry cannot promote the thickness of the ceramic rib body to be remarkably increased, and the organic template is decomposed to form a large number of hollow pore rib structures in the calcining process and generate a large number of defects on the surface of the ceramic-based pore rib; in addition, gas is introduced into the ceramic slurry during the preparation process to be doped, so that the mechanical property and the high-temperature property of the matrix are remarkably reduced during slurry hanging and later calcining. Therefore, improvements in the manufacturing process are needed to promote the performance of the ceramic foam.
Disclosure of Invention
The invention aims to provide a method for preparing a foam structure zeolite molecular sieve by an organic foam chemical growth method, which solves one or more of the problems in the prior art.
The invention provides a method for preparing a foam structure zeolite molecular sieve by an organic foam chemical growth method, which comprises the following steps:
taking foamed polyurethane as a matrix, and sequentially adopting water and an alkali solution to pretreat the foamed polyurethane matrix;
washing with water to remove residual alkali solution on the surface of the foamed polyurethane, and drying for later use;
h is to be2SO4Mixing the solution with concentrated sodium silicate solution, marking as mixed solution A, and adding H2SO4Mixing the solution with an aluminum sulfate solution, and marking as a mixed solution B;
adding the mixed solution B into the mixed solution A, then putting the treated foamed polyurethane into the solution for soaking until the pH value of the solution reaches 8-10 and gradually gels, and aging for 1-3h at 35-45 ℃;
taking out the foamed polyurethane with the grown gel, soaking in acid water, washing with water, drying at 80-100 ℃, and finally sintering at high temperature of 450-600 ℃ for molding to obtain the final product.
In some embodiments, the mixed solution A is H with the concentration of 0.05mol/L2SO4The solution and a concentrated sodium silicate solution with a concentration of 60% were mixed in a ratio of 3: 11 by volume ratio; the mixed liquid B is H with the concentration of 0.07mol/L2SO4The solution and aluminum sulfate solution with the concentration of 1.5mol/L are mixed in a proportion of 1: 7 by volume ratio; the volume ratio of the mixed solution B to the mixed solution A is 1: 20.
In some embodiments, the alkali solution is a NaOH solution or a KOH solution.
In some embodiments, the concentration of the alkali solution is 0.5 to 2 mol/L.
In some embodiments, the treatment time of the alkaline solution is 12 to 36 hours.
In some embodiments, the H is2SO4The solution was mixed with concentrated sodium silicate solution with vigorous stirring.
In some embodiments, the mixed solution B is added to the mixed solution a with vigorous stirring.
In some embodiments, the foamed polyurethane acid water with the growing gel is soaked for 1-3h, and can be cut into the required size after soaking.
In some embodiments, the foamed polyurethane with the growing gel is washed 1-3 times with water.
The invention has the beneficial effects that:
through modification of a traditional organic foam impregnation method, rich hydroxyl groups are obtained after polyurethane foam surface treatment, silica alumina gel is formed on the surface of polyurethane foam by using sodium silicate as a silicon source and aluminum sulfate as an aluminum source through a chemical production method, and the zeolite molecular sieve with a foam structure is obtained after a series of treatments such as washing, drying and the like.
The foam structure of the zeolite molecular sieve is a 3D network structure, and the internal gas is communicated with each other, so that the problem of local pore blocking failure in the pore structure can be solved. And the compressive strength and the adsorption performance of the zeolite molecular sieve are superior to those of the existing honeycomb zeolite.
Drawings
FIG. 1 is a process flow diagram of a zeolite molecular sieve having a foam structure prepared in example 1;
FIG. 2 is an SEM image of the foam structure zeolite molecular sieve prepared in example 1;
FIG. 3 is an SEM image of the foam structure zeolite molecular sieve prepared in example 1;
FIG. 4 is a graph of the mechanical properties of the zeolite molecular sieve with a foam structure prepared in example 1 and the zeolite of honeycomb type in comparative example 1;
fig. 5 is a graph showing adsorption properties of the zeolite molecular sieve having a foam structure prepared in example 1 and the zeolite having a honeycomb structure of comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are only for illustrating the performance of the present invention more clearly and are not limited to the following examples.
Example 1: the preparation process is shown in figure 1
1) The foamed polyurethane is taken as a matrix, and the polyurethane is pretreated by sequentially adopting water and NaOH solution with the concentration of 1mol/L, wherein the treatment time of the NaOH solution is 24 hours.
2) And then, washing with water to remove residual NaOH on the surface of the foamed polyurethane, and drying for later use.
3) Taking 0.05mol/L of H2SO4The solution was mixed with concentrated sodium silicate solution at a concentration of 60% under vigorous stirring in a ratio of 3: 11, carrying out mixing reaction, and marking as a mixed solution A; then adding H with the concentration of 0.07mol/L2SO4The solution was mixed with an aluminum sulfate solution having a concentration of 1.5mol/L in a ratio of 1: 7, and the mixture is marked as mixed solution B.
4) Slowly adding the mixed solution B into the mixed solution A under strong stirring, wherein the volume ratio of the mixed solution B to the mixed solution A is 1:20, then putting the treated foamed polyurethane into the solution for soaking until the solution value reaches 9 and gradually gelling, and aging for 2 hours at the temperature of 40-45 ℃;
5) taking out the foamed polyurethane with the growing gel, soaking the foamed polyurethane in acid water for 2 hours, cutting the product into required sizes, washing the product for 3 times, drying the product at 100 ℃, and finally sintering and molding the product at the high temperature of 550 ℃ and 600 ℃ to obtain the final product.
The appearance of the product obtained by the embodiment of the invention is shown in fig. 2 and 3, and fig. 2 and 3 are scanning electron micrographs of the product. The foam structure of the product is a 3D network structure, and the internal gas is communicated with each other, so that the problem of local pore blocking failure in the pore structure can be solved.
Comparative example 1: commercially available honeycomb-like zeolite
The product foam zeolite of example 1 and the honeycomb-like zeolite of comparative example 1 were tested for compressive strength according to the HG/T2783-2020 molecular sieve crush resistance test method.
The results of compressive strength are shown in table 1 and fig. 4:
| sample (I) | Foamed zeolite/Mpa | Honeycomb zeolite/Mpa |
| Sample 1 | 1.9 | 1.7 |
| Sample 2 | 1.9 | 1.7 |
| Sample 3 | 1.9 | 1.7 |
| Sample 4 | 1.9 | 1.6 |
| Sample 5 | 1.9 | 1.7 |
| Sample 6 | 2 | 1.7 |
| Sample 7 | 1.9 | 1.7 |
| Sample 8 | 1.9 | 1.6 |
| Sample 9 | 1.9 | 1.6 |
| Sample 10 | 1.9 | 1.7 |
TABLE 1
As can be seen from table 1 and fig. 4, the compressive strength of the product foam zeolite of example 1 is significantly higher than that of the honeycomb-type zeolite of comparative example 1.
The product foam zeolite of example 1 and the honeycomb-like zeolite of comparative example 1 were subjected to ethyl acetate: xylene (1:1) adsorption performance was measured as follows:
loading a sample into a sample loading tube; and then blowing the material to be detected for 30min at 300 ℃ by using hot air to remove water vapor and impurities on the material to be detected, and cooling to normal temperature for later use. And stabilizing the concentration of the VOCs in the test gas circuit to a required value, and accurately weighing and recording the weight 'a' of the VOCs liquid bottle. Then stable VOCs gas is introduced into the material to be detected,the outlet of the material to be detected is connected with a handheld measuring instrument to detect the outlet concentration of VOCs in real time, and the experiment is stopped after the outlet reaches 90 percent of adsorption concentration (for example, the inlet concentration is 1000mg/m3When the concentration at the outlet exceeds 100mg/m3Then stopped), and the VOCs liquid bottle weight 'b' is accurately weighed and recorded again.
Calculating the formula: 1000(b-a)/v
In the formula:
s-zeolite adsorption capacity in kg/m3；
a. b, weighing the VOCs liquid bottle weight twice in unit g;
v-volume of zeolite adsorbent, unit cm3。
Wherein, the adsorption efficiency is the ratio of the zeolite adsorption capacity in a certain time period to the zeolite adsorption capacity before adsorption, and as can be seen from fig. 5, the adsorption of the product foam zeolite of example 1 is saturated at 90min, and the adsorption efficiency is linearly reduced; the honeycomb zeolite of comparative example 1 was saturated in adsorption at 61.8min, and the adsorption efficiency decreased linearly; therefore, the adsorption capacity of the zeolite foam of the product of example 1 was greater than that of the honeycomb-type zeolite.
According to the embodiment of the invention, through modification of a traditional organic foam impregnation method, rich hydroxyl groups are obtained after polyurethane foam surface treatment, silica alumina gel is formed on the surface of the polyurethane foam by using a chemical production method and using sodium silicate as a silicon source and aluminum sulfate as an aluminum source, and the zeolite molecular sieve with a foam structure is obtained after a series of treatments such as washing, drying and the like.
The foam structure of the zeolite molecular sieve is a 3D network structure, and the internal gas is communicated with each other, so that the problem of local pore blocking failure in the pore structure can be solved. And the compressive strength and the adsorption performance of the zeolite molecular sieve are superior to those of the existing honeycomb zeolite.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these should also be construed as being within the scope of the present invention.
Claims (8)
1. A method for preparing a foam structure zeolite molecular sieve by an organic foam chemical growth method is characterized by comprising the following steps:
taking foamed polyurethane as a matrix, and sequentially adopting water and an alkali solution to pretreat the foamed polyurethane matrix;
washing with water to remove residual alkali solution on the surface of the foamed polyurethane, and drying for later use;
h is to be2SO4Mixing the solution with concentrated sodium silicate solution, marking as mixed solution A, and adding H2SO4Mixing the solution with an aluminum sulfate solution, and marking as a mixed solution B;
adding the mixed solution B into the mixed solution A, then putting the treated foamed polyurethane into the solution for soaking until the pH value of the solution reaches 8-10 and gradually gels, and aging for 1-3h at 35-45 ℃;
taking out the foamed polyurethane with the grown gel, soaking in acid water, washing with water, drying at 80-100 ℃, and finally sintering at high temperature of 450-600 ℃ for molding to obtain the final product.
2. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the mixed solution A is prepared by H with the concentration of 0.05mol/L2SO4The solution and a concentrated sodium silicate solution with a concentration of 60% were mixed in a ratio of 3: 11 by volume ratio; the mixed liquid B is prepared from H with the concentration of 0.07mol/L2SO4The solution and aluminum sulfate solution with the concentration of 1.5mol/L are mixed in a proportion of 1: 7 by volume ratio; the volume ratio of the mixed solution B to the mixed solution A is 1: 20.
3. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the alkali solution is a NaOH solution or a KOH solution, and the concentration of the alkali solution is 0.5-2 mol/L.
4. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the treatment time of the alkali solution is 12-36 h.
5. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the H is2SO4The solution was mixed with concentrated sodium silicate solution with vigorous stirring.
6. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the mixed solution B is added into the mixed solution A with strong stirring.
7. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method as claimed in claim 1, wherein the foamed polyurethane acid water with the growing gel is soaked for 1-3h and can be cut into the required size after being soaked.
8. The method for preparing the zeolite molecular sieve with the foam structure by the organic foam chemical growth method according to claim 1, wherein the foamed polyurethane with the grown gel is washed by water for 1-3 times.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183407A1 (en) * | 2000-10-05 | 2002-12-05 | Kyung-Byung Yoon | Macroporous foams comprising microporous zeolite or zeotype material and preparation thereof by using polymeric templates having sponge structure |
| CN102432031A (en) * | 2011-09-30 | 2012-05-02 | 常熟市星源金属涂层厂 | Preparation method of zeolite molecular sieve and carbon foam integrated composite material |
| CN107266113A (en) * | 2017-06-30 | 2017-10-20 | 常州市瑞泰物资有限公司 | A kind of gradient pore pipe silicon carbide ceramic filter plate and preparation method thereof |
| CN108620121A (en) * | 2018-05-23 | 2018-10-09 | 广东工业大学 | A kind of monoblock type molecular sieve catalyst and its preparation method and application |
| CN111087199A (en) * | 2019-12-20 | 2020-05-01 | 南通斐腾新材料科技有限公司 | Preparation method of porous hollow zeolite particles for adsorbing VOCs (volatile organic compounds) |
| CN111203176A (en) * | 2020-02-26 | 2020-05-29 | 北京泷涛环境科技有限公司 | Hydrophobic molecular sieve based porous foam adsorbent and preparation method and application thereof |
-
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- 2021-07-22 CN CN202110829390.3A patent/CN113548672A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183407A1 (en) * | 2000-10-05 | 2002-12-05 | Kyung-Byung Yoon | Macroporous foams comprising microporous zeolite or zeotype material and preparation thereof by using polymeric templates having sponge structure |
| CN102432031A (en) * | 2011-09-30 | 2012-05-02 | 常熟市星源金属涂层厂 | Preparation method of zeolite molecular sieve and carbon foam integrated composite material |
| CN107266113A (en) * | 2017-06-30 | 2017-10-20 | 常州市瑞泰物资有限公司 | A kind of gradient pore pipe silicon carbide ceramic filter plate and preparation method thereof |
| CN108620121A (en) * | 2018-05-23 | 2018-10-09 | 广东工业大学 | A kind of monoblock type molecular sieve catalyst and its preparation method and application |
| CN111087199A (en) * | 2019-12-20 | 2020-05-01 | 南通斐腾新材料科技有限公司 | Preparation method of porous hollow zeolite particles for adsorbing VOCs (volatile organic compounds) |
| CN111203176A (en) * | 2020-02-26 | 2020-05-29 | 北京泷涛环境科技有限公司 | Hydrophobic molecular sieve based porous foam adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周颖等: "模板预处理对泡沫炭结构的影响", 《化工学报》 * |
| 马广伟等: "ZSM-5/MOR共生分子筛的合成机理Ⅰ——合成工艺对共生物相的影响", 《硅酸盐学报》 * |
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