CN115350605A - Preparation method of novel carbon dioxide membrane - Google Patents

Preparation method of novel carbon dioxide membrane Download PDF

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Publication number
CN115350605A
CN115350605A CN202211082257.7A CN202211082257A CN115350605A CN 115350605 A CN115350605 A CN 115350605A CN 202211082257 A CN202211082257 A CN 202211082257A CN 115350605 A CN115350605 A CN 115350605A
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Prior art keywords
carbon dioxide
preparing
novel carbon
solution
dioxide membrane
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CN202211082257.7A
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Chinese (zh)
Inventor
张坤
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Suzhou Zero Carbon Film Technology Co ltd
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Suzhou Zero Carbon Film Technology Co ltd
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Priority to CN202211082257.7A priority Critical patent/CN115350605A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/76Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0009Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011Casting solutions therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0009Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013Casting processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a preparation method of a novel carbon dioxide membrane, which sequentially comprises the following steps: step S1, adding Cr (NO) 3 ) 3 ·9H 2 Mixing O, terephthalic acid and HF, and preparing a metal organic framework compound with nano holes by a hydrothermal method under the conditions of high temperature and high pressure; and S2, mixing the metal organic framework compound with the PVDF solution, stirring overnight, and casting the obtained solution to form a film. The invention prepares the carbon dioxide separation membrane with high permeability coefficient and selectivity, reduces the preparation cost and promotes the development of carbon dioxide separation and recycling industries.

Description

Preparation method of novel carbon dioxide membrane
Technical Field
The invention relates to the technical field related to preparation of carbon dioxide membranes, in particular to a preparation method of a novel carbon dioxide membrane.
Background
In the aspect of carbon emission reduction, carbon Capture Utilization and Sequestration (CCUS) is an important technical means. The method aims to capture and purify carbon dioxide discharged in the production process, and then put the carbon dioxide into a new production process for recycling or sealing, so that the carbon dioxide is prevented from being discharged into the atmosphere. 59% of the total amount of carbon dioxide emission in China comes from fossil power, cement and steel (statistics in 2018), the carbon dioxide centralized treatment in large-scale industrial production is imperative, and the CCUS technology is favorable for realizing large-scale greenhouse gas emission reduction and is an important method for dealing with climate change in the future. The best method for realizing the CCUS is a membrane separation method, which has the advantages of energy conservation, high efficiency, simple operation, convenient use, no secondary pollution and the like. Particularly, the cost of each ton of carbon dioxide is reduced to about 80 yuan/ton by the membrane separation technology, and compared with other methods, the method has huge cost advantages.
The Chinese membrane technology level has great progress, and a batch of novel separation membranes are prepared. For example, zhou Jincheng and the like are used for preparing the asymmetric nanofiltration membrane of the CA/CTA blend, monovalent and multivalent anions can be effectively separated, small molecular organic matters can be effectively removed, the NaCl desalination rate is 15-60%, the Na2S04 rejection rate is 85-98070, and the relative molecular weight rejection is 200-600. However, the existing commercial membranes (such as acetate fiber membranes, polysulfone membranes and polyimide membranes) still have certain technical problems in the field of carbon dioxide separation, and the permeability coefficient and separation performance of carbon dioxide are not high, so that the parameter requirements of industrial separation are difficult to meet.
In summary, the disadvantages of the prior art are:
1. the carbon dioxide permeability coefficient and selectivity of the acetate fiber membrane are not high.
2. The cost of the Polaris separation membrane from MTR is high.
In view of the above-mentioned drawbacks, the present inventors have made active research and innovation to create a novel method for preparing a carbon dioxide membrane, which is more valuable in industrial applications.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a novel carbon dioxide membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a novel carbon dioxide membrane sequentially comprises the following steps:
step S1, adding Cr (NO) 3 ) 3 ·9H 2 Mixing O, terephthalic acid and HF, and preparing a metal organic framework compound with nano holes by a hydrothermal method under the conditions of high temperature and high pressure;
and S2, mixing the metal organic framework compound with the PVDF solution, stirring overnight, and casting the obtained solution to form a film.
As a further improvement of the present invention, step S1 comprises the following steps in sequence:
step S11, adding 1.2g Cr (NO) 3 ) 3 ·9H 2 O and 500mg terephthalic acid were mixed with 15ml deionized water and 1ml HF;
s12, heating the reactant to a reaction kettle, heating to 220 ℃, keeping for 6 hours, cooling, and filtering a crude product;
step S13, heating the crude product in a DMF solution at 343K for 3 hours, and then heating the crude product in an ethanol solution at 70 ℃ for 3 hours;
s14, after the two steps, placing the sample in a DMF solution at 120 ℃ for one week, and then filtering;
and S15, drying the product at 80 ℃ to obtain MIL-101-Cr.
As a further development of the invention, the concentration of HF in step S11 is 3mol/L.
As a further improvement of the present invention, step S2 comprises the following steps in sequence:
step S21, dissolving the dried PVDF in chloroform, mixing with the MIL-101-Cr in the step S15, and stirring the obtained filler solution overnight;
step S22, after the ultrasonic treatment to remove bubbles, casting the resulting solution onto a clean glass substrate, and forming a film by solvent evaporation at ambient temperature for two days;
and S23, preparing the nano composite film with the MIL-101-Cr particle loading of 30% by weight.
As a further development of the invention, in step S21 the PVDF is dissolved in 8% by weight of chloroform.
As a further improvement of the invention, the thickness of the nano composite film is 85-95 μm.
As a further improvement of the invention, the thickness of the nanocomposite film is 90 μm.
By means of the scheme, the invention at least has the following advantages:
1. the invention prepares the carbon dioxide separation membrane with high permeability coefficient and selectivity, reduces the preparation cost and promotes the development of carbon dioxide separation and recycling industries.
2. The invention takes the MIL-101-Cr with the nano-pores as the inorganic filling material to adjust the pore diameter of the composite material and the chemical interaction between the composite material and the carbon dioxide, thereby improving the separation efficiency of the carbon dioxide.
3. The PVDF substrate for simultaneous film formation belongs to widely used and cheap engineering materials, and the combination of the PVDF substrate and the engineering materials can exert a synergistic effect to obtain a low-price and high-efficiency membrane separation product.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution 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 of the embodiments. The components of embodiments of the present invention generally shown herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Examples
A preparation method of a novel carbon dioxide membrane sequentially comprises the following steps:
step S1, adding Cr (NO) 3 ) 3 ·9H 2 Mixing O, terephthalic acid and HF, and preparing a metal organic framework compound with nano holes by a hydrothermal method under the conditions of high temperature and high pressure;
and S2, mixing the metal organic framework compound with the PVDF solution, stirring overnight, and casting the obtained solution to form a film.
According to the invention, a carbon dioxide separation membrane is prepared by mixing a metal organic framework compound MIL-101-Cr and a PVDF material, wherein the mass percentage of the MIL-101-Cr is 30%.
The step S1 comprises the following steps in sequence:
step S11, adding 1.2g of Cr (NO) 3 ) 3 ·9H 2 O and 500mg terephthalic acid were mixed with 15ml deionized water and 1ml HF (3 mol/L);
s12, heating the reactant to a reaction kettle, heating to 220 ℃, keeping for 6 hours, cooling, and filtering a crude product;
step S13, heating the crude product in a DMF solution at 343K for 3 hours, and then heating the crude product in an ethanol solution at 70 ℃ for 3 hours;
s14, after the two steps, placing the sample in a DMF solution at 120 ℃ for one week, and then filtering;
and S15, drying the product at 80 ℃ to obtain MIL-101-Cr.
The step S2 comprises the following steps in sequence:
step S21, dissolving the dried PVDF in 8% chloroform, mixing with the MIL-101-Cr in the step S15, and stirring the obtained filler solution overnight;
step S22, after the ultrasonic treatment to remove bubbles, casting the resulting solution onto a clean glass substrate, and forming a film by solvent evaporation at ambient temperature for two days;
and S23, preparing the nano composite film according to the loading of 30 weight percent of MIL-101-Cr particles, and finally obtaining the composite film with the thickness of about 90 mu m.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (7)

1. The preparation method of the novel carbon dioxide membrane is characterized by sequentially comprising the following steps of:
step S1, adding Cr (NO) 3 ) 3 ·9H 2 Mixing O, terephthalic acid and HF, and preparing a metal organic framework compound with nano holes by a hydrothermal method under the conditions of high temperature and high pressure;
and S2, mixing the metal organic framework compound with the PVDF solution, stirring overnight, and casting the obtained solution to form a film.
2. The method for preparing a novel carbon dioxide membrane according to claim 1, wherein the step S1 comprises the following steps in sequence:
step S11, adding 1.2g of Cr (NO) 3 ) 3 ·9H 2 O and 500mg terephthalic acid were mixed with 15ml deionized water and 1ml HF;
s12, heating the reactant to a reaction kettle, heating to 220 ℃, keeping for 6 hours, cooling, and filtering a crude product;
step S13, heating the crude product in a DMF solution at 343K for 3 hours, and then heating the crude product in an ethanol solution at 70 ℃ for 3 hours;
step S14, after the two steps, putting the sample in a DMF solution at 120 ℃ for one week, and then filtering;
and S15, drying the product at 80 ℃ to obtain MIL-101-Cr.
3. The method for producing a novel carbon dioxide membrane according to claim 2, wherein the concentration of HF in the step S11 is 3mol/L.
4. The method for preparing a novel carbon dioxide membrane according to claim 1, wherein the step S2 comprises the following steps in sequence:
step S21, dissolving the dried PVDF in chloroform, mixing with the MIL-101-Cr in the step S15, and stirring the obtained filler solution overnight;
step S22, after the ultrasonic treatment to remove bubbles, casting the resulting solution onto a clean glass substrate, and forming a film by solvent evaporation at ambient temperature for two days;
and S23, preparing the nano composite film with the MIL-101-Cr particle loading of 30% by weight.
5. The method for preparing a novel carbon dioxide membrane according to claim 4, wherein the PVDF is dissolved in 8% by weight of chloroform in step S21.
6. The method for preparing a novel carbon dioxide membrane as claimed in claim 4, wherein the thickness of the nano composite membrane is 85 to 95 μm.
7. The method of claim 6, wherein the nanocomposite film has a thickness of 90 μm.
CN202211082257.7A 2022-09-06 2022-09-06 Preparation method of novel carbon dioxide membrane Pending CN115350605A (en)

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Application Number Priority Date Filing Date Title
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110559884A (en) * 2019-08-29 2019-12-13 浙江工业大学 MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof
CN110639374A (en) * 2019-09-03 2020-01-03 大连理工大学 Preparation method of gas separation membrane with high MOF (Metal organic framework) filler content
US20200055005A1 (en) * 2018-08-20 2020-02-20 Nanjing University Method of preparing hybrid membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200055005A1 (en) * 2018-08-20 2020-02-20 Nanjing University Method of preparing hybrid membrane
CN110559884A (en) * 2019-08-29 2019-12-13 浙江工业大学 MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof
CN110639374A (en) * 2019-09-03 2020-01-03 大连理工大学 Preparation method of gas separation membrane with high MOF (Metal organic framework) filler content

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAJAR RAJATI ET AL.,: "Preparation and characterization of mixed matrix membranes based on Matrimid/PVDF blend and MIL-101(Cr) as filler for CO2/CH4 separation", 《CHEMICAL ENGINEERING SCIENCE》, vol. 185, pages 92 - 104 *

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