CN116251488B - Amino-containing functional material for separating carbon dioxide, and preparation method and application thereof - Google Patents
Amino-containing functional material for separating carbon dioxide, and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 19
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 14
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- NIDSRGCVYOEDFW-UHFFFAOYSA-N 1-bromo-4-chlorobutane Chemical compound ClCCCCBr NIDSRGCVYOEDFW-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000008204 material by function Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 33
- 238000000926 separation method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001612 separation test Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 208000032370 Secondary transmission Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- B01D71/78—Graft polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/22—Separation 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
- B01D53/228—Separation 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
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an amino-containing functional material for separating carbon dioxide, and a preparation method and application thereof, belonging to the technical field of membrane material preparation; the invention adopts amino porous polymer hyperbranched polyethyleneimine functionalized carboxymethyl shell composite material (HPFC) to graft and modify activated polybenzimidazole (CPBI) to obtain amino-containing functional material; the amino-containing functional material activates Polybenzimidazole (PBI) to take the activated polybenzimidazole (CPBI) as a membrane matrix, and HPFC is doped in the membrane matrix; the amino-containing functional material has high permeability and high selectivity, and has good application in CO 2/CH4 mixed gas under the condition of separating wet state.
Description
Technical Field
The invention belongs to the technical field of membrane material preparation, and particularly relates to an amino-containing functional material for separating carbon dioxide, and a preparation method and application thereof.
Background
Natural gas is widely mined in oil and gas fields, biogas, combustible ice, shale gas fields, etc., and thus it contains about 5% to 55% CO 2. Acid gas CO 2 can corrode plumbing during natural gas delivery and can also lead to a reduction in the combustion value of methane during natural gas use, for which efficient separation of CO 2/CH4 is desired. The membrane separation technology becomes a new direction for future decarbonization development of natural gas with the advantages of green and clean, no pollution, low energy consumption and the like, but the membrane separation technology has the technical difficulty of designing a proper membrane to simultaneously meet the requirements of high permeability and high selectivity.
The polymer membrane is an important CO 2/CH4 separation membrane material because of simple preparation, low cost, stable performance, high permeability coefficient, good solvent resistance and good mechanical property. Polymeric materials currently occupy up to ninety percent of the gas membrane separation market, and commercially available polymeric membranes cellulose acetate, perfluoropolymers, and polyimides are being used in large quantities in commercial production. Along with the wide application of the membrane separation technology in various fields, the requirements of various fields on membrane materials are continuously improved, and the membrane is required to have abundant selectivity and meet the requirements of related work in the aspects of thermal stability, chemical stability, mechanical strength and flux. But the requirements of the related work cannot be met for a single polymeric material. Therefore, a modification work of the membrane material is required to obtain a membrane material having good overall properties.
Polybenzimidazole (PBI) is an excellent polymer film material having high strength, good chemical stability, and thermal stability. In addition, the structure formed by the rigidity of the carbon chain and the strong intermolecular hydrogen bond has higher selectivity to small molecules. Thus, CO 2 is more permeable and has a higher selectivity than CH 4 molecules, but the CO 2 permeation flux is low and efficient separation of CO 2/CH4 cannot be achieved. Thus, there is a need for a polymer membrane that combines high permeability and high selectivity to achieve efficient separation of CO 2/CH4.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an amino-containing functional material for separating carbon dioxide, and a preparation method and application thereof. The invention adopts amino porous polymer hyperbranched polyethyleneimine functionalized carboxymethyl shell composite material (HPFC) to graft and modify activated polybenzimidazole (CPBI) to obtain amino-containing functional material; the amino-containing functional material takes activated polybenzimidazole (CPBI) as a membrane matrix, and HPFC is doped in the membrane matrix; the amino-containing functional material has high permeability and high selectivity, and has good application in CO 2/CH4 mixed gas under the condition of separating wet state.
The invention firstly provides an amino-containing functional material for separating carbon dioxide, which has the structural formula:
The amino-containing functional material takes activated polybenzimidazole (CPBI) as a membrane matrix, HPFC is doped in the membrane matrix, and the doping amount of the HPFC is 3-9% wt of CPBI mass; the thickness of the amino-containing functional material is 90-110 mu m.
Wherein the structural formula of the activated polybenzimidazole (CPBI) is as follows:
The structural formula of the HPFC is as follows:
the invention also provides a preparation method of the amino-containing functional material, which comprises the following steps:
(1) Preparation of HPFC:
uniformly mixing Carboxymethyl Chitosan (CCTS) aqueous solution, polyethyleneimine (PEI) and polyvinyl alcohol (PVA) to obtain solution A; then slowly stirring the solution A, and dropwise adding Glutaraldehyde (GLA) water solution into the solution A to obtain a solution B; then, the solution B is vigorously stirred at room temperature, and after white flocculent precipitate is obtained, the solution B is filtered, washed and dried to obtain HPFC;
(2) Activation of PBI:
under the protection of nitrogen, dissolving PBI in N, N-Dimethylacetamide (DMAC), then adding NaH for stirring reaction 1, cooling after the reaction is finished, then adding 1-bromo-4-chlorobutane for stirring reaction 2, precipitating the product in ice water after the reaction is finished, washing for multiple times by using a detergent, and drying to obtain CPBI;
(3) Preparation of amino-containing functional materials:
CPBI was dissolved in an aqueous solution of N-methylpyrrolidone (NMP) to give CPBI solution; dissolving HPFC in an aqueous solution of N-methylpyrrolidone (NMP), and performing ultrasonic treatment to obtain HPFC suspension for later use;
Mixing CPBI solution with HPFC suspension to obtain mixed solution, stirring the mixed solution for reaction, drying after the reaction is finished, soaking the dried product in acid solution, and washing to neutrality after the soaking is finished to obtain the amino-containing functional material.
Preferably, in the step (1), the weight ratio of Carboxymethyl Chitosan (CCTS), polyethyleneimine (PEI) and polyvinyl alcohol (PVA) is 1:4.5:0.5.
Preferably, in the step (1), the substitution degree of the Carboxymethyl Chitosan (CCTS) is not less than 80%; the molecular weight of the Polyethylenimine (PEI) is 600; the average degree of polymerization of the polyvinyl alcohol (PVA) is 1799;
The Glutaraldehyde (GLA) is a 5wt% aqueous solution.
The time of the vigorous stirring is 6 hours, so that the Schiff base reaction is successfully completed.
The drying conditions are as follows: the temperature is 0 ℃ to minus 10 ℃ and the vacuum time is 12 to 48 hours.
Preferably, in step (2), the Polybenzimidazole (PBI), N-Dimethylacetamide (DMAC), naH and 1-bromo-4-chlorobutane are used in a ratio of 0.2g:100mL:0.4g:0.29mL;
stirring the reaction 1 for 24 hours at room temperature, and cooling to 0 ℃ after the reaction is finished;
the condition of the stirring reaction 2 is that the reaction is carried out for 12 hours at the temperature of 0 ℃;
the detergent is ice water, deionized water and ethanol.
The drying conditions are as follows: the temperature is between room temperature and 50 ℃ and the vacuum time is between 12 and 48 hours.
Preferably, in the step (3), the mass ratio of CPBI to HPFC is 1:0.03 to 0.09.
Preferably, in the step (3), the stirring time is 24-72 h;
In step (3), the drying conditions are as follows: the temperature is 50-80 ℃ and the vacuum time is 12-48 hours
Preferably, in step (3), the acid solution is 1mol/L dilute sulfuric acid.
Preferably, in the step (3), the soaking time is 12 to 48 hours. The invention also provides application of the amino-containing functional material in separating CO 2/CH4 mixed gas. Preferably, the CO 2/CH4 mixture is a CO 2/CH4 mixture under wet conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) The HPFC disclosed by the invention has the advantages of porous materials and polymer materials, and has the advantages of easy adjustment of porosity, carbon-rich framework and outstanding physicochemical characteristics. According to the invention, HPFC is introduced into CPBI for grafting modification, so that a secondary transmission mechanism such as molecular sieving, surface diffusion or Knudsen diffusion can be formed in the membrane, and a path for quick CO 2 transmission is constructed, so that the transmission resistance of CO 2 is reduced, the chain spacing of a membrane substrate is influenced, the permeability of CO 2 is improved, and the gas separation performance of a membrane material is effectively improved.
(2) The amino-containing functional material combines the advantages of the amino-containing porous polymer and the polymer matrix, and the amino-containing porous polymer HPFC is grafted onto CPBI molecular frameworks through an N-substitution method, so that the molecular structure of CPBI carbon chain rigidity and strong hydrogen bonds is destroyed, the molecular chain distance is increased, an amino-containing porous transmission path is formed in the membrane, the mass transfer resistance is reduced by utilizing the porous structure, CO 2 permeation is facilitated, and CO 2 permeability is improved. In addition, HPFC is composed of PEI and CCTS, contains rich CO 2 transfer carrier (amino), can be subjected to reversible reaction with CO 2 molecules under the action of water molecules to form HCO 3 - easy to diffuse, accelerates the transfer of CO 2, is beneficial to strengthening a transfer promoting mechanism in a membrane, and is beneficial to selectively improving the permeability of CO 2. When the amino-containing functional material is used for separating CO 2/CH4 mixed gas under the wet condition, the flux of CO 2 is 16.5-52.8Barrer (the selectivity of 1 Barrer=10 -10cm3 cm/cm2 s cmHg),CO2/CH4 is 90-130. The separation performance of CO 2/CH4 of the amino-containing functional material successfully exceeds the upper limit of Robeson in 2008, wherein the amino-containing functional material CPBI/HPFC-7 with the optimal performance is close to 2019-Upper G ndara. Compared with the pure CPBI membrane performance, the CO 2 flux and CO 2/CH4 selectivity of the amino-containing functional material CPBI/HPFC-7 are respectively improved by 991.0% and 209.0%.
(3) The amino-containing functional material disclosed by the invention is simple in preparation process, controllable in reaction, low in cost and easy to obtain raw materials, mild in condition and good in industrial application value.
Drawings
FIG. 1 is a sectional view of a Scanning Electron Microscope (SEM) of an amino group-containing functional material CPBI/HPFC-3 produced in example 1.
FIG. 2 is a sectional view of a Scanning Electron Microscope (SEM) of the amino group-containing functional material CPBI/HPFC-5 produced in example 2.
FIG. 3 is a sectional view of a Scanning Electron Microscope (SEM) of the amino group-containing functional material CPBI/HPFC-7 produced in example 3.
FIG. 4 is a cross-sectional view of a Scanning Electron Microscope (SEM) of the amino group-containing functional material CPBI/HPFC-9 produced in example 4.
FIG. 5 is a cross-sectional view of a scanning electron microscope of the functional material CPBI produced in comparative example 1.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1: preparation of amino-containing functional Material CPBI/HPFC-3
(1) Preparation of HPFC:
1.0g of Carboxymethyl Chitosan (CCTS) is weighed and put into a beaker, 120mL of ultrapure water is added, and the carboxymethyl chitosan is completely dissolved by ultrasonic treatment to obtain carboxymethyl chitosan water solution; adding 4.5g of Polyethyleneimine (PEI) and 0.5g of polyvinyl alcohol (PVA) into a Carboxymethyl Chitosan (CCTS) aqueous solution to obtain a solution A; solution A was then stirred slowly and 20mL of 5wt% Glutaraldehyde (GLA) in water was added dropwise thereto over 30min to give solution B. Stirring the solution B vigorously at room temperature for 6 hours to finish Schiff base reaction to obtain white flocculent precipitate; washing the white flocculent precipitate with deionized water for several times, and vacuum drying at 0deg.C for 24h to obtain white powder to obtain HPFC.
(2) Activation of PBI:
0.1g of PBI was completely dissolved in a three-necked flask containing 50mL of N, N-Dimethylacetamide (DMAC) solvent under nitrogen atmosphere, and then 0.2g of NaH was added thereto at room temperature, and the reaction was continuously stirred for 24 hours to form a dark red viscous mixture. Then placing the obtained dark red viscous mixture in a low-temperature constant-temperature reactor, cooling to 0 ℃, adding 0.145mL of 1-bromo-4-chlorobutane into the low-temperature constant-temperature reactor, and continuously stirring for 12 hours; after the completion of stirring, the obtained reaction mixture was precipitated in ice water, which was centrifugally washed 3 times with ice water, deionized water and ethanol, respectively, and the product CPBI was collected and dried at 40 ℃ for 12 hours to obtain CPBI powder.
(3) Preparation of amino-containing functional materials:
0.3g CPBI g of the powder was dissolved in 9mL of an aqueous solution of N-methylpyrrolidone (NMP) to completely dissolve CPBI, yielding a CPBI solution; 0.00928g of HPFC was weighed and dissolved in an aqueous solution of N-methylpyrrolidone (NMP), and sonicated for 2 hours to disperse it into a homogeneous HPFC suspension for further use.
Mixing CPBI solution with HPFC suspension, wherein the mass ratio of CPBI to HPFC is 1:0.03, magnetically stirring for 48 hours to uniformly mix the two; and finally pouring the mixture into a clean culture dish, putting the culture dish into a vacuum drying oven, drying the culture dish at 60 ℃ in vacuum for 12 hours until the solvent is removed, soaking the membrane in 1mol/L dilute sulfuric acid solution for 24 hours, soaking the membrane in deionized water, and washing the membrane to be neutral to obtain the amino-containing functional material. Because of the mass ratio of CPBI to HPFC of 1:0.03, and the amino group-containing functional material was designated CPBI/HPFC-3. The thickness of the amino group-containing functional material CPBI/HPFC-3 was measured to be 98. Mu.m.
FIG. 1 is a cross-sectional view of a scanning electron microscope of an amino group-containing functional material CPBI/HPFC-3, from which it can be seen that the amino group-containing functional material has a uniform cross-section without defects.
In this example, a separation test of a CO 2/CH4 mixed gas (CO 2 volume fraction 20%) under wet conditions of CPBI/HPFC-3 at 25℃and 2bar was also examined. The test results show that the CO 2 flux of the amino-containing functional material CPBI/HPFC-3 is 16.5Barrer and the CO 2/CH4 selectivity is 96.
Example 2:
The amino-functional material CPBI/HPFC-5 was prepared in this example using the method described in example 1, with the following differences: in the step (1), the vacuum drying at 0 ℃ is changed into the vacuum drying at-10 ℃ for 12 hours; in the step (2), drying at 40 ℃ for 12 hours is changed into drying at room temperature for 48 hours; CPBI to HPFC mass ratio 1:0.05, namely, in the step (3), the weighing of 0.00928g of HPFC is changed into the weighing of 0.0158g of HPFC; in the step (3), the magnetic stirring is changed to 24 hours for 48 hours; in the step (3), the vacuum drying is carried out for 12 hours at 60 ℃ until the solvent is removed, and the vacuum drying is carried out for 36 hours at 50 ℃ until the solvent is removed; in the step (3), the membrane is soaked in 1mol/L dilute sulfuric acid solution for 24 hours, and the membrane is soaked in 1mol/L dilute sulfuric acid solution for 12 hours.
The thickness of the amino group-containing functional material CPBI/HPFC-5 was measured to be 101. Mu.m.
The cross section of the scanning electron microscope of the amino-containing functional material CPBI/HPFC-5 is shown as figure 2, and the cross section of the amino-containing functional material is uniform and has no defects as can be seen from figure 2.
In this example, a separation test of a CO 2/CH4 mixed gas (CO 2 volume fraction 20%) under wet conditions was also examined at 25℃and 2bar for the amino group-containing functional material CPBI/HPFC-5. The test results show that the CO 2 flux of the amino-containing functional material CPBI/HPFC-5 is 26.4Barrer and the CO 2/CH4 selectivity is 117.
Example 3:
The amino-functional material CPBI/HPFC-7 was prepared in this example using the method described in example 1, with the following differences: in the step (1), the vacuum drying at 0 ℃ for 24 hours is changed into the vacuum drying at 0 ℃ for 48 hours; in the step (2), drying at 40 ℃ for 12 hours is changed into drying at 50 ℃ for 36 hours; CPBI to HPFC mass ratio 1:0.07, namely, in the step (3), the weighing 0.00928g of HPFC is changed into the weighing 0.0226g of HPFC; in the step (3), the magnetic stirring is changed to 36 hours for 48 hours; in the step (3), the vacuum drying is carried out for 12 hours at 60 ℃ until the solvent is removed, and the vacuum drying is carried out for 48 hours at 80 ℃ until the solvent is removed; in the step (3), the membrane is soaked in 1mol/L dilute sulfuric acid solution for 24 hours, and the membrane is soaked in 1mol/L dilute sulfuric acid solution for 48 hours.
The thickness of the amino group-containing functional material CPBI/HPFC-5 was measured to be 105. Mu.m.
The cross section of the scanning electron microscope of the amino-containing functional material CPBI/HPFC-7 is shown in figure 3, and the cross section of the amino-containing functional material is uniform and has no defects as can be seen from figure 3.
In this example, a separation test of a CO 2/CH4 mixed gas (CO 2 volume fraction 20%) under wet conditions was also examined at 25℃and 2bar for an amino group-containing functional material CPBI/HPFC-7. The test results show that the CO 2 flux of the amino-containing functional material CPBI/HPFC-7 is 52.8Barrer and the CO 2/CH4 selectivity is 130.
Example 4:
The amino-functional material CPBI/HPFC-9 prepared in this example was prepared by the method described in example 1, with the following differences: in the step (1), the vacuum drying at 0 ℃ is changed into the vacuum drying at-5 ℃ for 24 hours; in the step (2), drying at 40 ℃ for 12 hours is changed into drying at 35 ℃ for 12 hours; CPBI to HPFC mass ratio 1:0.09, namely, in the step (3), the weighing 0.00928g of HPFC is changed into the weighing 0.0226g of HPFC; in the step (3), the magnetic stirring is changed to 72 hours; in the step (3), the vacuum drying is carried out for 12 hours at 60 ℃ until the solvent is removed, and the vacuum drying is carried out for 12 hours at 70 ℃ until the solvent is removed.
The thickness of the amino group-containing functional material CPBI/HPFC-5 was measured to be 110. Mu.m. The cross section of the scanning electron microscope of the amino-containing functional material CPBI/HPFC-9 is shown as figure 4, and as can be seen from figure 4, a small amount of protruding particles appear on the cross section of the amino-containing functional material, and the particle agglomeration phenomenon is obvious.
In this example, a separation test of a CO 2/CH4 mixed gas (CO 2 volume fraction 20%) under wet conditions was also examined at 25℃and 2bar for the amino group-containing functional material CPBI/HPFC-9. The test results show that the CO 2 flux of the amino-containing functional material CPBI/HPFC-9 is 37.4Barrer and the CO 2/CH4 selectivity is 90.
Comparative example 1:
In this comparative example, a functional material CPBI was prepared, and the preparation method of the functional material CPBI is as follows:
0.3g CPBI g of powder was weighed, dissolved in 9mL of an aqueous solution of N-methylpyrrolidone (NMP), magnetically stirred for 48h, poured into a clean petri dish, and placed in a vacuum drying oven, and dried in vacuum at 60℃for 12h until the solvent was removed, to obtain CPBI film.
FIG. 5 is a cross-sectional view of a scanning electron microscope of the functional material CPBI obtained in the comparative example, and it can be seen from the figure that the functional material has a uniform cross-section and is smooth and defect-free. In addition, the thickness of the functional material CPBI was 102 μm by measurement.
The separation test of the functional material CPBI on CO 2/CH4 mixed gas (CO 2 volume fraction 20%) in wet condition at 25 ℃ and 2bar was also examined in this comparative example. The test results found that the functional material CPBI had a CO 2 flux of 4.84barrer and a CO 2/CH4 selectivity of 42.
In conclusion, the amino-containing functional material combines the advantages of the amino porous polymer and the polymer matrix, forms an amino porous transfer path in the membrane, reduces mass transfer resistance by utilizing a porous structure, is beneficial to CO 2 permeation and improves CO 2 permeability. In addition, HPFC is rich in amino groups, is beneficial to strengthening a transmission promoting mechanism in the membrane and is beneficial to selectively improving the permeability of CO 2. The CO 2/CH4 containing amino functional material has good separation performance, simple preparation process, controllable reaction, low-cost and easily obtained raw materials, mild conditions and good industrial application value. The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (10)
1. An amino-containing functional material for separating carbon dioxide, characterized in that the amino-containing functional material has the structural formula:
2. The amino-functional material of claim 1, wherein the amino-functional material comprises an activated polybenzimidazole (CPBI) as a membrane matrix, wherein an amino-porous polymer hyperbranched polyethyleneimine functionalized carboxymethyl shell composite (HPFC) is doped in the membrane matrix; the doping amount of the HPFC is 3-9%wt of CPBI mass percent; the thickness of the amino-containing functional material is 90-110 mu m.
3. The method for producing an amino-functional material according to claim 1, comprising the steps of:
(1) Preparation of HPFC:
uniformly mixing Carboxymethyl Chitosan (CCTS) aqueous solution, polyethyleneimine (PEI) and polyvinyl alcohol (PVA) to obtain solution A; then slowly stirring the solution A, and dropwise adding Glutaraldehyde (GLA) water solution into the solution A to obtain a solution B; then, the solution B is vigorously stirred at room temperature, and after white flocculent precipitate is obtained, the solution B is filtered, washed and dried to obtain HPFC;
(2) Activation of PBI:
under the protection of nitrogen, dissolving PBI in N, N-Dimethylacetamide (DMAC), then adding NaH for stirring reaction 1, cooling after the reaction is finished, then adding 1-bromo-4-chlorobutane for stirring reaction 2, precipitating the product in ice water after the reaction is finished, washing for multiple times by using a detergent, and drying to obtain CPBI;
(3) Preparation of amino-containing functional materials:
CPBI was dissolved in an aqueous solution of N-methylpyrrolidone (NMP) to give CPBI solution; dissolving HPFC in an aqueous solution of N-methylpyrrolidone (NMP), and performing ultrasonic treatment to obtain HPFC suspension for later use;
Mixing CPBI solution with HPFC suspension to obtain mixed solution, stirring the mixed solution for reaction, drying after the reaction is finished, soaking the dried product in acid solution, and washing to neutrality after the soaking is finished to obtain the amino-containing functional material.
4. A method for producing an amino-functional material according to claim 3, wherein in the step (1), the drying condition is: vacuum drying is carried out for 12-48 h at 0-minus 10 ℃.
5. A method for producing an amino-functional material according to claim 3, wherein in the step (2), the drying condition is as follows: vacuum drying at room temperature-50 deg.c for 12-48 hr.
6. The method for producing an amino-functional material according to claim 3, wherein in the step (3), the mass ratio of CPBI to HPFC is 1:0.03 to 0.09.
7. The method for producing an amino group-containing functional material according to claim 3, wherein in the step (3), the stirring reaction is carried out for 24 to 72 hours;
the acid solution is 1mol/L dilute sulfuric acid;
The soaking time is 12-48 hours.
8. The method for producing an amino-functional material according to claim 3, wherein in the step (3), the drying condition is as follows: vacuum drying at 50-80 deg.c for 12-48 hr.
9. The use of the amino-functional material according to claim 1 for separating CO 2/CH4 gas mixtures.
10. The use according to claim 9, wherein the CO 2/CH4 mixture is a CO 2/CH4 mixture in wet conditions.
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