CN111569664A - Preparation method of organic-inorganic hybrid membrane capable of adjusting membrane aperture size - Google Patents
Preparation method of organic-inorganic hybrid membrane capable of adjusting membrane aperture size Download PDFInfo
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- CN111569664A CN111569664A CN202010319137.9A CN202010319137A CN111569664A CN 111569664 A CN111569664 A CN 111569664A CN 202010319137 A CN202010319137 A CN 202010319137A CN 111569664 A CN111569664 A CN 111569664A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/20—Plasticizers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
Abstract
The invention discloses a preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane, which comprises the steps of diluting alkoxy silane into absolute ethyl alcohol, gradually dropwise adding a proper amount of deionized water, weak acid and weak base catalyst, heating the solution to 40-65 ℃ while fully stirring, violently stirring for 2-6 hours at constant temperature, and stopping stirring; starting to carry out ultrasonic dispersion on the solution for 4-10 hours, then fully hydrolyzing the solution, and cooling to room temperature to form a particle-dispersed sol solution; adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, and coating the sol on the multilayer support body by a dip-coating method; after the multilayer support body coated by the coating is dried at the constant temperature and humidity of 20-50 ℃ and 20-50% of humidity, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen and the organic-inorganic hybrid membrane is roasted for 1-3 hours, thus preparing the organic-inorganic hybrid membrane.
Description
Technical Field
The invention relates to the technical field of preparation of organic-inorganic hybrid membranes, in particular to a preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane.
Background
Pervaporation is a novel efficient and clean membrane separation technology for liquid mixture separation. Only the component to be separated needs to be vaporized in the pervaporation process, so that the energy consumption is low; other reagents are not introduced in the separation process, the pollution is reduced or zero, and the method is suitable for application in the fields of food, medicine and environmental protection and is an energy-saving and environment-friendly 'cleaning process'. The membrane is the basis of the separation process of the pervaporation technology, the membrane is the core part of the whole system, the separation performance of the membrane is the most important factor influencing the pervaporation process, and the separation effect and the investment cost of the pervaporation system are directly influenced. The membrane material is one of the key factors determining the separation performance of the membrane, the membrane material used in the pervaporation process comprises an organic membrane and an inorganic membrane, the two membranes have advantages and disadvantages, and the organic-inorganic hybrid membrane avoids the disadvantages of the organic membrane and the inorganic membrane and combines the advantages of the organic membrane and the inorganic membrane, so that the membrane material has greater advantages and wide application prospects compared with the inorganic membrane and the organic membrane.
Chinese patent CN104159659B discloses a method for coating a layer of hybrid siloxane membrane on an organic support, wherein an inorganic silica framework includes organic bridging groups bonded to two or more silicon atoms, the obtained hybrid siloxane membrane realizes molecular level hybridization, the organic bridging groups are introduced on the molecular framework, which increases the softness of the framework and makes the material film-forming process easier, meanwhile, the organic groups can shield the hydrolysis of water molecules, and increase the hydrothermal stability of the hybrid membrane, therefore, in the pervaporation application process, the organic-inorganic hybrid membrane has better thermal stability than the organic membrane and higher hydrothermal stability than the molecular sieve membrane. However, the hybrid membrane prepared by the patent has the problems of wide pore size distribution and insufficient separation selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane so as to solve the problems in the background technology.
In order to realize the purpose, the invention provides the following technical scheme: a preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: diluting alkoxy silane into absolute ethyl alcohol, gradually dropwise adding a proper amount of deionized water, weak acid and weak base catalyst, heating the solution to 40-65 ℃ while fully stirring, and violently stirring for 2-6 hours at constant temperature, and stopping stirring;
step two: keeping the conditions unchanged, starting to perform ultrasonic dispersion on the solution for 4-10 hours, and then cooling the solution to room temperature after the solution is fully hydrolyzed to form a sol solution with relatively single particle dispersion;
step three: adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, and coating the sol on the multilayer support body by a dip-coating method;
step four: after the coated multilayer support body is dried at the constant temperature and humidity of 20-50 ℃ and 20-50% of humidity, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen and the organic-inorganic hybrid membrane is prepared after roasting for 1-3 hours.
Preferably, the method also comprises the step of carrying out pervaporation dehydration experiment on the organic-inorganic hybrid membrane prepared in the step three at 120 ℃ on water-isopropanol with the mass concentration of 20%.
Preferably, the weak acid and weak base catalyst is one of carbonic acid, H2S, HCN, HF, phosphoric acid, formic acid, acetic acid, ammonia water, calcium hydroxide, aluminum hydroxide and zinc hydroxide.
Preferably, the pore size and the roughness of the surface layer of the multilayer support in the third step are matched with the particle size of the sol.
Preferably, the film thickness of the organic-inorganic hybrid film prepared in the third step is 380 nm-430 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane, which improves the preparation process of preparing the organic-inorganic hybrid membrane by a sol-gel technology, and has the advantages of mild condition in the preparation process, easy control, simple equipment, easy operation and convenient amplification.
2. The preparation method of the organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane can be used for adjusting the particle size and distribution of colloidal particles, and the factors including hydrolysis conditions, ultrasonic dispersion conditions, precursor hydrocarbon group composition and the like can be used as adjusting parameters, so that the adjustment range of the colloidal particle size is wide, and the pore size of the obtained hybrid membrane can be adjusted in a wide range.
3. According to the preparation method of the organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane, the selectivity of the membrane to water is obviously improved when the prepared organic-inorganic hybrid membrane is subjected to a pervaporation dehydration experiment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The method comprises the following steps: diluting 20ml of dimethyl alkane into 150ml of absolute ethyl alcohol, gradually dropwise adding 10ml of deionized water and 15ml of ammonia water (NH3.H2O, 37%) as a catalyst, heating the solution to 40-60 ℃ while fully stirring, violently stirring for 3 hours at constant temperature, and stopping stirring;
step two: keeping the conditions unchanged, starting to perform ultrasonic dispersion on the solution for 8 hours by using a preset ultrasonic dispersion instrument, and then cooling the solution to room temperature after the solution is fully hydrolyzed to form a sol solution with relatively single particle dispersion;
step three: adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, analyzing by a particle size analyzer to obtain a colloid with the average particle size of 4.1 nanometers and the particle size distribution mainly in the range of 3.2-5.0 nanometers, and coating the sol on the multilayer support body by a dip-coating method by using a sol-gel technology;
step four: after the multilayer support body coated by the coating is dried at constant temperature and humidity under 40 ℃ and 30 percent humidity, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen, and the multilayer support body is roasted for 1-3 hours, so that the inorganic-organic hybrid membrane is prepared, and the thickness of the membrane is about 380 nanometers.
Example 2
The method comprises the following steps: diluting 20ml of dimethyl alkane into 150ml of absolute ethyl alcohol, gradually dropwise adding 10ml of deionized water and 15ml of ammonia water (NH3.H2O, 37%) as a catalyst, heating the solution to 40-60 ℃ while fully stirring, violently stirring for 8 hours at constant temperature, and stopping stirring;
step two: keeping the conditions unchanged, starting to perform ultrasonic dispersion on the solution for 4 hours by using a preset ultrasonic dispersion instrument, and then cooling the solution to room temperature after the solution is fully hydrolyzed to form a sol solution with relatively single particle dispersion;
step three: adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, analyzing by a particle size analyzer to obtain a colloid with the average particle size of 4.5 nanometers and the particle size distribution mainly in the range of 3.0-6.0 nanometers, and coating the sol on the multilayer support body by a dip-coating method by using a sol-gel technology;
step four: after the multilayer support body coated by the coating is dried at constant temperature and humidity under 50 ℃ and 40 percent of humidity, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen, and the multilayer support body is roasted for 1-3 hours to prepare the organic-inorganic hybrid membrane, wherein the thickness of the membrane is about 400 nanometers.
Example 3
The method comprises the following steps: diluting 20ml of dimethyl alkane into 150ml of absolute ethyl alcohol, gradually dropwise adding 10ml of deionized water and 15ml of ammonia water (NH3.H2O, 37%) as a catalyst, heating the solution to 40-60 ℃ while fully stirring, violently stirring for 12 hours at constant temperature, and stopping stirring without ultrasonic dispersion;
step two: adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, analyzing by a particle size analyzer to obtain a colloid with the average particle size of 5.4 nanometers and the particle size distribution mainly in the range of 2.0-10.0 nanometers, and coating the sol on the multilayer support body by a dip-coating method by using a sol-gel technology;
step three: after the multilayer support body coated by the coating is dried at constant temperature and humidity under the temperature of 30 ℃ and the humidity of 50 percent, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen, and the multilayer support body is roasted for 1 to 3 hours to prepare the inorganic-organic hybrid membrane, wherein the thickness of the membrane is about 430 nanometers.
Experimental analysis:
the organic-inorganic hybrid membrane prepared in example 1 was subjected to an osmotic vaporization dehydration experiment at 120 ℃ with respect to water-isopropyl alcohol having a mass concentration of 20%, and the hybrid membrane was obtained to have a water permeability of 15.6kg/m2.h and a selectivity to water of about 940, as shown in table 1 below.
The organic-inorganic hybrid membrane prepared in example 2 was subjected to an osmotic vaporization dehydration experiment at 120 ℃ with respect to water-isopropyl alcohol having a mass concentration of 20%, and the hybrid membrane was obtained to have a water permeability of 12.1kg/m2.h and a selectivity to water of about 420, as shown in table 1 below.
The organic-inorganic hybrid membrane prepared in example 3 was subjected to an osmotic vaporization dehydration test on 20% water-isopropanol at 120 ℃ to obtain a hybrid membrane having a water permeability of 13.5kg/m2.h and a selectivity to water of about 130, as shown in table 1 below.
| Serial number | Average particle diameter/nm | Thickness of functional layer/nm | Dehydration rate kg/hm2 | Selectivity is |
| 1 | 4.1 | 380 | 15.6 | 940 |
| 2 | 4.5 | 400 | 12.1 | 420 |
| 3 | 5.4 | 430 | 13.5 | 130 |
TABLE 1
The experimental results are as follows: the organic-inorganic hybrid membranes prepared in examples 1 and 2 have significantly higher selectivity for water than the organic-inorganic hybrid membrane prepared in example 3.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (5)
1. A preparation method of an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: diluting alkoxy silane into absolute ethyl alcohol, gradually dropwise adding a proper amount of deionized water, weak acid and weak base catalyst, heating the solution to 40-65 ℃ while fully stirring, and violently stirring for 2-6 hours at constant temperature, and stopping stirring;
step two: keeping the conditions unchanged, starting to perform ultrasonic dispersion on the solution for 4-10 hours, and then cooling the solution to room temperature after the solution is fully hydrolyzed to form a sol solution with relatively single particle dispersion;
step three: adding a small amount of organic high molecular polymer into the sol solution to change the viscosity of the sol, adding a proper amount of plasticizer to adjust the plasticity of the sol, and coating the sol on the multilayer support body by a dip-coating method;
step four: after the multilayer support body coated by the coating is dried at the constant temperature and humidity of 20-50 ℃ and 20-50% of humidity, the temperature is slowly raised to 200-400 ℃ under the protection of nitrogen and the organic-inorganic hybrid membrane is roasted for 1-3 hours, thus preparing the organic-inorganic hybrid membrane.
2. The method for preparing an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane as claimed in claim 1, wherein: and the method also comprises a pervaporation dehydration experiment of the organic-inorganic hybrid membrane prepared in the third step on water-isopropanol with the mass concentration of 20% at 120 ℃.
3. The method for preparing an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane as claimed in claim 1, wherein: the weak acid and weak base catalyst is one of carbonic acid, H2S, HCN, HF, phosphoric acid, formic acid, acetic acid, ammonia water, calcium hydroxide, aluminum hydroxide and zinc hydroxide.
4. The method for preparing an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane as claimed in claim 1, wherein: and step three, the surface aperture size and the roughness of the multilayer support body are matched with the particle size of the sol.
5. The method for preparing an organic-inorganic hybrid membrane capable of adjusting the pore size of the membrane as claimed in claim 1, wherein: the film thickness of the organic-inorganic hybrid film prepared in the third step is 380 nm-430 nm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150124A (en) * | 1995-11-14 | 1997-05-21 | 中国科学院大连化学物理研究所 | Method for in-situ dressing surface of sol particles |
| KR20020005777A (en) * | 2000-05-22 | 2002-01-18 | 이영무 | Method for manufacturing microporous chlorinated poly(vinyl-chloride) membrane and microporous chlorinated poly(vinyl-chloride) manufactured thereby |
| CN104524988A (en) * | 2015-01-22 | 2015-04-22 | 联合环境技术（厦门）有限公司 | Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane |
| CN109650935A (en) * | 2019-02-15 | 2019-04-19 | 中国计量大学 | A kind of preparation method of the adjustable alumina porous ceramic film of hole shape |
| CN109847601A (en) * | 2019-03-06 | 2019-06-07 | 常州大学 | A kind of preparation method and application of fluosilicic hydridization copolymer membrane |
| CN109847592A (en) * | 2019-01-04 | 2019-06-07 | 广州汉至蓝能源与环境技术有限公司 | A kind of organic-inorganic hybrid films preparation method |
-
2020
- 2020-04-21 CN CN202010319137.9A patent/CN111569664A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150124A (en) * | 1995-11-14 | 1997-05-21 | 中国科学院大连化学物理研究所 | Method for in-situ dressing surface of sol particles |
| KR20020005777A (en) * | 2000-05-22 | 2002-01-18 | 이영무 | Method for manufacturing microporous chlorinated poly(vinyl-chloride) membrane and microporous chlorinated poly(vinyl-chloride) manufactured thereby |
| CN104524988A (en) * | 2015-01-22 | 2015-04-22 | 联合环境技术（厦门）有限公司 | Polyvinylidene fluoride hollow fiber membrane of in-situ pore-forming agent and preparation method of polyvinylidene fluoride hollow fiber membrane |
| CN109847592A (en) * | 2019-01-04 | 2019-06-07 | 广州汉至蓝能源与环境技术有限公司 | A kind of organic-inorganic hybrid films preparation method |
| CN109650935A (en) * | 2019-02-15 | 2019-04-19 | 中国计量大学 | A kind of preparation method of the adjustable alumina porous ceramic film of hole shape |
| CN109847601A (en) * | 2019-03-06 | 2019-06-07 | 常州大学 | A kind of preparation method and application of fluosilicic hydridization copolymer membrane |
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Application publication date: 20200825 |