CN113304631A - Preparation method of organic framework microporous membrane - Google Patents
Preparation method of organic framework microporous membrane Download PDFInfo
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- CN113304631A CN113304631A CN202110630001.4A CN202110630001A CN113304631A CN 113304631 A CN113304631 A CN 113304631A CN 202110630001 A CN202110630001 A CN 202110630001A CN 113304631 A CN113304631 A CN 113304631A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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Abstract
The invention belongs to the technical field of microporous membranes, and particularly relates to a preparation method of an organic framework microporous membrane, which comprises the following preparation steps: s1: under the protection of low temperature and nitrogen, 4, 4-biphenyl dimethylonitrile and trifluoromethanesulfonic acid are mixed and reacted to obtain a reaction solution; s2: defoaming the reaction solution at normal temperature; s3: scraping the solution after being defoamed by S2, and then drying for 0.5h at the temperature of 100 +/-5 ℃ to obtain an organic framework microporous membrane primary product; s5: and (3) sequentially soaking the initial product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for a certain time, and then carrying out heat treatment to obtain the organic framework microporous membrane. The preparation process is simple and easy to control; the obtained organic framework microporous membrane has stable performance, high reliability and excellent gas, liquid and ion selectivity, and can be widely used for solvent dehydration, gas separation, nanofiltration and the like.
Description
Technical Field
The invention belongs to the technical field of microporous membranes, and particularly relates to a preparation method of an organic framework microporous membrane.
Background
The organic microporous material is a group of organic high molecular materials with the pore diameter of a porous structure less than 2 nm. Due to the advantages of high porosity, high specific surface area and adjustable pore diameter of micropores, the material is an ideal adsorption and membrane separation material. Microporous polymers are easy and inexpensive to process in many practical applications, and are increasingly accepted by academia and industry, as compared to conventional inorganic microporous materials, such as porous carbon, zeolites, porous silica, etc. For example, several new microporous polymers, such as polymers with intrinsic microporosity (PIM), Thermally Rearranged (TR) polymers, Conjugated Microporous Polymers (CMP), Covalent Organic Frameworks (COF), etc., which have been emerging in recent years, have a wide application prospect in the fields of gas storage, separation, catalysis, etc. due to their controllable framework structures and sizes of free volumes; the covalent organic framework material is one of the representatives of organic porous materials, but the existing covalent organic framework material has complex preparation process, and the prepared material has poor filtering effect due to low purity.
Disclosure of Invention
In view of the problems raised by the above background art, the present invention is directed to: aiming at providing a preparation method of an organic framework microporous membrane.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an organic framework microporous membrane comprises the following preparation steps:
s1: under the protection of low temperature and nitrogen, 4, 4-biphenyl dimethylonitrile and trifluoromethanesulfonic acid are mixed and reacted to obtain a reaction solution;
s2: defoaming the reaction solution at normal temperature;
s3: scraping the solution after being defoamed by S2, and then drying for 0.5h at the temperature of 100 +/-5 ℃ to obtain an organic framework microporous membrane primary product;
s5: and (3) sequentially soaking the initial product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for a certain time, and then carrying out heat treatment to obtain the organic framework microporous membrane.
As a preferable scheme of the invention, in the S1, 4-biphenyldicarbonitrile is firstly placed in a reaction bottle, nitrogen purging protection is continuously carried out at the temperature of minus 10 ℃, then trifluoromethane sulfonic acid is dropwise added, and after the addition is finished, the stirring is kept at the temperature of minus 5 ℃ for 1-2 hours.
As a preferable scheme of the invention, the soaking time of the S5 organic framework microporous membrane in sodium hydroxide, deionized water and methanol is not less than 0.5 hour.
In a preferable embodiment of the present invention, in S5, the heat treatment of the primary organic framework microporous membrane product is to place the primary organic framework microporous membrane product in an oven for heating and drying.
In a preferred embodiment of the present invention, the heat treatment temperature in S5 is not lower than 300 ℃ to 500 ℃.
The invention has the beneficial effects that:
the preparation process is simple and easy to control; the obtained organic framework microporous membrane has stable performance, high reliability and excellent gas, liquid and ion selectivity, and can be widely used for solvent dehydration, gas separation, nanofiltration and the like.
Detailed Description
In order that those skilled in the art can better understand the present invention, the following embodiments are provided to further illustrate the present invention.
Example one
A preparation method of an organic framework microporous membrane comprises the following preparation steps:
s1: removing 1mol of 4, 4-biphenyldicarbonitrile, placing the 4, 4-biphenyldicarbonitrile in a reaction bottle, continuously blowing nitrogen at the temperature of minus 10 ℃ for protection, then dropwise adding 0.1mol of trifluoromethanesulfonic acid, and stirring at the temperature of minus 5 ℃ for 1-2 hours after the addition is finished, so that the 4, 4-biphenyldicarbonitrile and the trifluoromethanesulfonic acid are mixed and reacted to obtain a reaction solution;
s2: defoaming the reaction solution at normal temperature;
s3: and (3) scraping the solution after the defoaming of the S2, and then drying for 0.5h at the temperature of 100 +/-5 ℃ to obtain an organic framework microporous membrane initial product.
Example two
Preparing a framework microporous membrane primary product as in the first embodiment;
s5: and sequentially soaking the primary product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for 0.5h, and then carrying out heat treatment at the temperature of 200 ℃ to obtain the organic framework microporous membrane I.
EXAMPLE III
Preparing a framework microporous membrane primary product as in the first embodiment;
s5: and sequentially soaking the primary product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for 0.5h, and then carrying out heat treatment at the temperature of 300 ℃ to obtain an organic framework microporous membrane II.
Example four
Preparing a framework microporous membrane primary product as in the first embodiment;
s5: and sequentially soaking the primary product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for 0.5h, and then carrying out heat treatment at the temperature of 400 ℃ to obtain an organic framework microporous membrane III.
EXAMPLE five
Preparing a framework microporous membrane primary product as in the first embodiment;
s5: and sequentially soaking the primary product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for 0.5h, and then carrying out heat treatment at the temperature of 200 ℃ to obtain an organic framework microporous membrane IV.
The chemical expression for preparing the organic framework microporous membrane is as follows:
applying the organic framework microporous membrane obtained in the first to fifth embodiments to a binary system of ethanol dehydration and ethanol and water, wherein the water content is 15%, and the test temperature is 50 ℃ for detection;
the detection method comprises the following steps:
the pervaporation performance detection is carried out on pervaporation dehydration experimental equipment. The effective membrane area is 12-15cm2. On the feed side, the test temperature for the binary feed liquid components of alcohol and water was between 60 degrees celsius and the flow rate was 1 LPM. The vacuum degree of permeation measurement is 1-2 mbar; the water contents of the raw material liquid and the permeated liquid were measured by a gas chromatograph. The nanofiltration filtration performance detection is carried out on nanofiltration experimental equipment, and the effective membrane area is 12-15cm2(ii) a On the raw material side, the test temperature of the binary components of dye and water is between 25 and 28 ℃ and the flow rate is 1 LPM; the pressure was 0.5 MPa.
The membrane flux (J, kg/(m2 h)) was obtained by the following equation:
wherein Q (kg) is the permeate obtained in a fixed time interval t (h), A (m)2) Is the effective membrane area;
the retention rate (R) is obtained by the following formula:
wherein Cp is the solute content of the permeate and Cf is the solute content of the feed solution;
wherein solute refers to an alcohol or a dye molecule.
The results of the measurements are shown in Table 1,
| temperature of post-treatment | Pore diameter of micropore (nm) | Flux (kg/m2/h) | Permeate Water content (wt%) | Retention ratio R (%) |
| Is free of | 0.62 | 6.89 | 29.8 | 17.4 |
| 200 | 0.54 | 4.66 | 50.2 | 41.4 |
| 300 | 0.36 | 1.57 | 98.6 | 98.4 |
| 400 | 0.36 | 1.34 | 99.2 | 99.1 |
| 500 | 0.36 | 1.30 | 98.9 | 98.7 |
Table 1: experimental data of ethanol dehydration treatment by using organic framework microporous membrane
As can be seen from table 1, in the absence of post-treatment, the pore size of the organic framework microporous membrane is large, flux is large but permeate water content and rejection are low; in the case of the aftertreatment at 200 ℃, compared with the case of no aftertreatment, the conditions of low water content and low retention rate of the permeate can be improved, but the retention rate can not meet the requirements relatively; at 300 deg.C, 400 deg.C and 500 deg.C, the pore diameter of the organic skeleton microporous membrane is small, and the water content and retention rate of the permeating liquid are obviously high, and are highest at 400 deg.C.
In the S1, 4-biphenyldicarbonitrile is placed in a reaction bottle, nitrogen purging protection is continuously carried out at the temperature of-10 ℃, trifluoromethanesulfonic acid is added dropwise, and stirring is carried out for 1-2 hours at the temperature of-5 ℃ after the addition is finished.
The soaking time of the S5 organic framework microporous membrane in sodium hydroxide, deionized water and methanol is not less than 0.5 hour.
In the step S5, the heat treatment of the primary organic framework microporous membrane product is to put the primary organic framework microporous membrane product into an oven for heating and drying.
Applying the organic framework microporous membrane obtained in the second to fifth embodiments to gas separation, and detecting at the test temperature of 50 ℃; the results of the measurements are shown in Table 2,
table 2: experimental data of applying organic framework microporous membrane to gas separation
As can be seen from table 2, the higher the post-treatment temperature, the better the gas permeability coefficient, but the relatively poorer the gas selectivity.
Applying the organic framework microporous membrane obtained in the first to third embodiments to nanofiltration to simulate a dye solution of printing and dyeing wastewater, wherein the dye is in a water content range of 0-100% and the test temperature is 35-28 ℃; the pure water flux is 60LMH/bar, and the detection results are shown in Table 3;
| temperature of post-treatment | Flux (LMH/bar) | MgSO4 rejection% | Retention rate of NaCl% | Indigocamine Retention% |
| Is free of | 18.9 | 99.5 | 89.5 | 99.9 |
| 200 | 13.3 | 99.7 | 92.7 | 99.9 |
| 300 | 12.6 | 99.8 | 93.8 | 99.9 |
Table 2: experimental data of nanofiltration for applying organic framework microporous membrane
As can be seen from table 3, the organic framework microporous membrane prepared by the present invention has a high rejection rate in nanofiltration.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (5)
1. A preparation method of an organic framework microporous membrane is characterized by comprising the following steps: the preparation method comprises the following steps:
s1: under the protection of low temperature and nitrogen, 4, 4-biphenyl dimethylonitrile and trifluoromethanesulfonic acid are mixed and reacted to obtain a reaction solution;
s2: defoaming the reaction solution at normal temperature;
s3: scraping the solution after being defoamed by S2, and then drying for 0.5h at the temperature of 100 +/-5 ℃ to obtain an organic framework microporous membrane primary product;
s5: and (3) sequentially soaking the initial product of the organic framework microporous membrane in sodium hydroxide, deionized water and methanol for a certain time, and then carrying out heat treatment to obtain the organic framework microporous membrane.
2. The method of claim 1, wherein the microporous membrane comprises: in the S1, 4-biphenyldicarbonitrile is placed in a reaction bottle, nitrogen purging protection is continuously carried out at the temperature of-10 ℃, trifluoromethanesulfonic acid is added dropwise, and stirring is carried out for 1-2 hours at the temperature of-5 ℃ after the addition is finished.
3. The method of claim 2, wherein the microporous membrane with organic framework is prepared by the following steps: the soaking time of the S5 organic framework microporous membrane in sodium hydroxide, deionized water and methanol is not less than 0.5 hour.
4. The method of claim 3, wherein the microporous membrane with organic skeleton is prepared by the following steps: in the step S5, the heat treatment of the primary organic framework microporous membrane product is to put the primary organic framework microporous membrane product into an oven for heating and drying.
5. The method of claim 1, wherein the microporous membrane comprises: the heat treatment temperature in the S5 is 300-500 ℃.
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Citations (5)
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| CN104722212A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Covalent triazine skeleton doped hybrid membrane preparation method |
| CN105017529A (en) * | 2014-04-24 | 2015-11-04 | 中国科学院大连化学物理研究所 | Preparing method of multi-stage hole structure covalent triazine framework microporous polymers |
| CN106861446A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of microporous polymer membranes, its preparation method and application |
| CN111701458A (en) * | 2020-06-16 | 2020-09-25 | 北京工业大学 | Preparation method of covalent triazine framework organic solvent nanofiltration membrane |
| KR20210044160A (en) * | 2019-10-11 | 2021-04-22 | 고려대학교 산학협력단 | Pervaporation composite membranes using covalent triazine framework for alcohol recovery |
-
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- 2021-06-07 CN CN202110630001.4A patent/CN113304631A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104722212A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Covalent triazine skeleton doped hybrid membrane preparation method |
| CN105017529A (en) * | 2014-04-24 | 2015-11-04 | 中国科学院大连化学物理研究所 | Preparing method of multi-stage hole structure covalent triazine framework microporous polymers |
| CN106861446A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of microporous polymer membranes, its preparation method and application |
| KR20210044160A (en) * | 2019-10-11 | 2021-04-22 | 고려대학교 산학협력단 | Pervaporation composite membranes using covalent triazine framework for alcohol recovery |
| CN111701458A (en) * | 2020-06-16 | 2020-09-25 | 北京工业大学 | Preparation method of covalent triazine framework organic solvent nanofiltration membrane |
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