AU2021105920A4 - A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used For Gas Separation And Its Preparation Method - Google Patents
A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used For Gas Separation And Its Preparation Method Download PDFInfo
- Publication number
- AU2021105920A4 AU2021105920A4 AU2021105920A AU2021105920A AU2021105920A4 AU 2021105920 A4 AU2021105920 A4 AU 2021105920A4 AU 2021105920 A AU2021105920 A AU 2021105920A AU 2021105920 A AU2021105920 A AU 2021105920A AU 2021105920 A4 AU2021105920 A4 AU 2021105920A4
- Authority
- AU
- Australia
- Prior art keywords
- solution
- parts
- preparation
- added
- imidazole polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- 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
- 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
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
Abstract
of Descriptions
The present invention relates to the field of chemical industry, in particular to a bulk
) polycondensation imidazole polymer mixed matrix membrane used for gas separation
and its preparation method; The adsorption capacity of aqueous organic matter is
small. The invention prepares the silyl amide hydrotalcite with long and short carbon
chains, the long and short carbon chains are interlaced with each other, a relatively
large specific surface area can be obtained, and the adsorption performance for
hydrophilic organics is improved. The invention aims at the problem that the
separation performance of the existing gas separation membrane is difficult to break
through the Trade-off effect. The invention utilizes the high porosity of the bulk
polycondensation imidazole polymer material, which can increase the free volume
fraction of the membrane, reduce the resistance of gas transmission in the membrane,
thereby improving the gas permeability of the membrane; In addition, this type of
structure will increase the gas selective adsorption capacity of the membrane due to
its rich N element, thereby helping to improve the selectivity of the membrane.
Description
Descriptions
A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used for Gas Separation and Its Preparation Method
Technical Field
[0001] The present invention relates to the chemical industry, in particular to a bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method.
Background Technology
[0002] China's main energy structure is dominated by coal, so the use of coal-fired power generation is a basic national policy. However, coal-fired power plants need to emit a large amount of CO 2 every year, and how to effectively reduce or use this CO 2 is a current research hotspot. Compared with other technologies, membrane technology has become a good method for separating CO2 due to its inherent advantages (for example, the membrane can act as a selective barrier, and the technology is superior in terms of low energy consumption, low capital investment, environmentally friendly operation process, and continuous operation mode).
[0003] CN104822444A provides a gas separation membrane that is soluble in organic solvents, has excellent moldability, and has excellent gas separation performance when used as a gas separation membrane. [Solution] The gas separation membrane of the present invention has a polyimide structure having the general formula (1) (in the formula, RI represents a divalent organic group and R2 represents a tetravalent organic group.) In the repeating unit shown, RI is a divalent organic group represented by the general formula (2) or a divalent organic group represented by the general formula (3).
[0004] CN103429330A A method for forming a gas separation membrane includes: depositing a first hydrophilic polymer solution; depositing a different second hydrophilic polymer solution on the first hydrophilic polymer solution, thereby forming two-layer polymer solution; The two-layer polymer solution is made to form one of a forward osmosis membrane and a pressure retarding osmosis membrane by contacting the different second hydrophilic polymer solutions with water to form a dense layer; The hydrophilic polymer solution is more resistant to a different third hydrophilic polymer thin layer of pH coating one of the forward osmosis membrane and the pressure retarding osmosis membrane to form a dense repellent layer thereon; and one of the coated forward osmosis membrane and the
Descriptions
coated pressure retarding osmosis membrane is exposed to the high pH solution. A gas separation membrane formed by the above method.
[0005] CN101432061A relates to a gas separation membrane having a polymer microporous membrane and a gas separation membrane, The polymer microporous membrane is a polymer microporous membrane with polyolefin as the main component manufactured by a wet phase separation method, with a porosity of 20%-80%, an average pore diameter of 1nm-100nm, the puncture strength of 2-50N at 100°C , the gas separation membrane is a gas separation membrane containing a fluorine-based gas separation resin as a main component on at least one surface and/or inside of a polymer microporous membrane, and its average membrane thickness is 0.01 m - less than 0.4 m , the gas separation membrane of this invention is characterized in that the oxygen-nitrogen separation coefficient is 1.4 or more.
[0006] The gas separation performance of the organic membrane of the above invention usually has a trade-off effect, which will restrict the further development of the use of organic membranes to separate gases. Although inorganic membranes have high separation performance, they are difficult to prepare into common hollow fiber membranes and are expensive, which is also an important point to prevent further applications of inorganic membranes.
Invention Summary
[0007] In order to solve the above problems, the present invention provides a bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method.
[0008] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0009] In parts by mass, 0.04-1.2 parts of the mixture solution is added to 6-10 parts of the polymer solution; 0.01-0.15 parts of organic hydrotalcite is added, and after stirring for 10-120 min , dispersed by ultrasonic for 20-50min; stirred on a stirrer for 5-10h; the resulting solution is statically defoamed for 1-5min; poured into a petri dish, placed in an oven, and placed at 55-75°C for 24-48h ; then, the solvent is removed in a vacuum oven for 24-72h, at a temperature of 50-75°C; the one-type polycondensation imidazole polymer mixed matrix film can be obtained.
[0010] The mixture solution is a bulk polycondensation imidazole polymer material mixture,the preparation method of the solution is as follows:
[0011] A cleaned reactor is prepared, and nitrogen gas is blown into it for 5-60 min;
[0012] According to the mass parts, 13.2-16.4 parts of 3,3-diaminobenzidine is charged into a nitrogen-filled reactor, and 150-400 parts of ethylene glycol phenyl
Descriptions
ether is added as a solvent and 0 .1-0.5 parts of catalyst, and heated at 600 C for -180min in an inert atmosphere, 17.1-21.4 parts of 1,3,5- trimellitic acid are added and mixed, reacted and stirred at 150-200 0C for 24-60h; then it is cooled to room temperature, then 1500-2000 parts of deionized water is added to the solution and stirred continuously, and then it is centrifuged at a centrifugal speed of 5000-10000 rpm and ished with deionized water, the supernatant is discarded, and this step is repeated 6-10 times until pH=6-7;
[0013] The obtained flocculent substance and precipitate are Soxhlet extracted with water, ethanol and acetone for 10-14 h in sequence; and then dried in a vacuum oven at 50 0 C for 20-48 h to obtain a dry bulk polycondensation imidazole polymer material;
[0014] The obtained bulk polycondensation imidazole polymer material is mixed with an ethanol solution with a mass part of 60%-100%, and is configured to obtain a bulk polycondensation imidazole polymer material mixture solution with a mass part of 0.5-1.5 wt%.
[0015] The catalyst is polyphosphoric acid.
[0016] The inert atmosphere is high-purity nitrogen or argon.
[0017] The polymer solution is a polyether block amide solution, and its preparation method is as follows:
[0018] 1-5 parts of polyether block amide polymer particles are added to 90-95 parts of a 70%-100% ethanol solution by mass, and stirred at 70-800 C for 2-4h;
[0019] @ The solution obtained in 0 is naturally cooled;
[0020] @The room temperature solution in @ is centrifuged for 5 min at a
speed of 7000 rpm;
[0021] @ The supernatant is transferred to a container to obtain a polyether
block amide solution.
[0022] The organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is as follows:
[0023] In parts by weight, 16-22 parts of hydrotalcite is dispersed in 200-500 parts of ethanol, and 2.1-4.2 parts of coupling agent are added, and the temperature is raised to 50-62 °C under the protection of nitrogen, 0.2-1.5 parts of 1-carboxymethyl-3-methylimidazole nitrate and 2-6 parts of hexanol-4 carboxylic acid are added to the reaction kettle, which is kept refluxed for 90- 180min, after filtration and ishing with ethanol, the solids obtained are dispersed in deionized water, and the solid content is controlled to 2.8%-5.4%, and is added to the dispersion with a concentration of 0.1% to 0.5% by mass percentage, and the
Descriptions
silylamide hydrotalcite can be obtained after being stirred and mixed uniformly.
[0024] Aminosiloxane reacts with the hydroxyl groups on the surface of hydrotalcite, and then 1-carboxymethyl-3-methylimidazole nitrate and 2-6 parts of hexanol-4 carboxylic acid undergo amidation reaction, which is part of the reaction mechanism The equation is shown as:
[0025]
0NO 1
[0026]
NO 00 A N H N
Hydrotalcite
[0027] The long carbon chain anionic surfactant is sodium tetradecyl sulfonate or sodium hexadecyl sulfonate or sodium dodecyl sulfonate.
[0028] The short carbon chain anionic surfactant is sodium methane sulfonate or sodium pentane sulfonate or sodium octane sulfonate.
[0029] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0030] The present invention is a bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method. The present invention aims at the fact that hydrotalcite in the prior art has a small amount of organic matter adsorption, especially for hydrophilic organic matter. The adsorption capacity is small. In the present invention, aminosiloxane reacts with the hydroxyl groups on the surface of hydrotalcite, and then 1-carboxymethyl-3-methylimidazole nitrate and 2-6 parts of hexanol-4 carboxylic acid undergo amidation reaction to prepare silanyl amide hydrotalcite with long and short carbon chains; its long and short carbon chains are intertwined, which can obtain a relatively large specific
Descriptions
surface area and improve the adsorption performance of hydrophilic organics. The invention aims at the problem that the separation performance of the existing gas separation membrane is difficult to break through the Trade-off effect. The present invention utilizes the high porosity of the bulk polycondensation imidazole polymer material, which can increase the free volume fraction of the membrane, reduce the resistance of gas transmission in the membrane, thereby improving the gas permeability of the membrane; In addition, this type of structure will increase the gas selective adsorption capacity of the membrane due to its rich N element, thereby helping to improve the selectivity of the membrane. In short, combined with the inherent separation performance of the polymer matrix, the prepared polycondensation imidazole polymer/polymer hybrid matrix membrane has both high selectivity and permeability. Therefore, the inorganic-organic hybrid membrane developed by the present invention has abundant pores and high C0 2/N 2 selective adsorption capacity, and is expected to play an important role in the field of gas separation.
Brief Description of Drawings
[0031] Figure 1 is an SEM image of a bulk polycondensation imidazole polymer;
[0032] Figure 2 is a TG diagram of a bulk polycondensation imidazole polymer;
[0033] Figure 3 is a TG diagram of a mixed matrix membrane containing lwt% bulk polycondensation imidazole polymer;
[0034] Figure 4 is a FT-IR diagram of the bulk polycondensation imidazole polymer;
[0035] Figure 5 is an FT-IR diagram of a mixed matrix membrane containing lwt%
by weight of a bulk polycondensation imidazole polymer.
Detailed Description of the Presently Preferred Embodiments
[0036] The invention will be further illustrated by specific embodiments as follows:
[0037] Embodiment 1
[0038] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0039] (1) 0.04 g of the mixture solution is added to 6 g of the polymer solution;
[0040] (2) 0.Olg of organic hydrotalcite is added, stirred for 10 min and then ultrasonicated for 20 min;
[0041] (3) Then, the solution obtained in (2) is stirred on a stirrer for 5 h;
[0042] (4) The solution obtained in (3) is allowed to stand still for1 min to degas;
[0043] (5) the solution obtained in (4) is poured into a petri dish, placed in an oven,
Descriptions
and placed at 55°C for 24 h;
[0044] (6) the film obtained in step (5) is transferred to a vacuum oven for desolventizing for 24 h at a temperature of 50°C; a bulk polycondensation imidazole polymer mixed matrix membrane can be obtained.
[0045] The mixture solution is a bulk polycondensation imidazole polymer material mixture solution, and its preparation method is as follows:
[0046] (a) A cleaned reactor is prepared, and nitrogen gas is blown into it for 5 min;
[0047] (b) A reactor filled with nitrogen is charged with 13.2 g of 3,3-diaminobenzidine, 150 g of ethylene glycol phenyl ether is added as a solvent and 0.1 g of a catalyst, and the reactor is heated at 60°C for 60min under an inert atmosphere.17.lg 1,3,5-benzenetricarboxylic acid is added and mixed, and the reaction is stirred at 150°C for 24h;
[0048] (c) The solution in step (b) is allowed to stand still and wait for it to drop to room temperature, and then the solution is added to 1500 g of deionized water and continuously stirred to obtain a flocculent substance;
[0049] (d) The solution obtained in step (c) is centrifuged at a centrifugal speed of 5000 rpm, and the supernatant is discarded after ishing with deionized water, and this step is repeated 6 times until pH=6;
[0050] (e) The precipitate obtained in step (d) is sequentially added with water, ethanol and acetone for Soxhlet extraction for 10 h;
[0051] (f) Then, the precipitation in step (e) is dried in a vacuum oven at 50°C for h to obtain a dry bulk polycondensation imidazole polymer material;
[0052] (g) The bulk polycondensation imidazole polymer material obtained in (f) is mixed with an ethanol solution with a mass percentage concentration of 60%, and is configuredto obtain a mass percentage concentration of 0.5 wt% of a bulk polycondensation imidazole polymer material mixture solution.
[0053] The catalyst is polyphosphoric acid.
[0054] The inert atmosphere is high-purity nitrogen.
[0055] The polymer solution is a polyether block amide solution, and its preparation method is:
[0056] ©_xOOO_1g polyether block amide polymer particles is added to 90g of ethanol solution with a concentration of 70% by mass, and stirred at 70°C for 2 h;
[0057] @ The solution obtained in ( is naturally cooled;
[0058] @The room temperature solution in @ is centrifuged for 5 min at a speed of 7000 rpm;
[0059] @ The supernatant is transferred to a container to obtain the polyether block amide solution.
Descriptions
[0060] The organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is:
[0061] 16g of hydrotalcite is dispersed in 200g of ethanol, 2.1g of coupling agent is added, and the temperature is raised to 50°C under nitrogen protection, 0.2g of 1-carboxymethyl-3-methylimidazole nitrate, 2g of hexanol polyether-4 carboxylic acid is added to the reaction kettle, and it is reacted for 90 min at reflux temperature, after completion, it is filtered and ished with ethanol. The obtained solid is dispersed in deionized water. The solid content is controlled to 2.8%, and the dispersant sodium tripolyphosphate with a mass percentage concentration of 0.1% is added and stirred. The silyl amide hydrotalcite can be obtained after uniform mixing.
[0062] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0063] Embodiment 2
[0064] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0065] (1) 0.6 g of the mixture solution is added to 8 g of the polymer solution;
[0066] (2) 0.08 g of organic hydrotalcite is added, stirred for 90 min and then ultrasonicated for 30 min;
[0067] (3) The solution obtained in (2) is then stirred on a stirrer for 8 h;
[0068](4) The solution obtained in (3) is allowed to stand still for 3 min to degas;
[0069] (5) The solution obtained in (4) is poured into a petri dish, placed in an oven, and placed at 65°C for 36 h;
[0070] (6) The membrane obtained in (5) is transferred to a vacuum oven for desolventizing for 36 h at a temperature of 65°C; the one-type polycondensation imidazole polymer mixed matrix membrane can be obtained.
[0071] The mixture solution is a bulk polycondensation imidazole polymer material mixture solution, and its preparation method is as follows:
[0072] (a) A cleaned reactor is prepared, and nitrogen gas is blown into it for 30 min;
[0073] (b) A reactor filled with nitrogen is charged with 14.8g of 3,3-diaminobenzidine, 280 g of ethylene glycol phenyl ether is added as a solvent and 0.3 g of a catalyst, and the reactor is heated at 60°C for 120min under an inert atmosphere. 19.3g 1,3,5-benzenetricarboxylic acid is added and mixed, and the reaction is stirred at 180°C for 40 h;
[0074] (c) The solution in step (b) is allowed to stand still and wait for it to drop to room temperature, and then the solution is added to 1800 g of deionized water and continuously stirred to obtain a flocculent substance;
Descriptions
[0075] (d) The solution obtained in step (c) is centrifuged at a centrifugal speed of 8000 rpm, and the supernatant is discarded after ishing with deionized water. This step is repeated 8 times until pH=6.5;
[0076] (e) The precipitate obtained in step (d) is sequentially added with water, ethanol and acetone for Soxhlet extraction for 12 h;
[0077] (f) Then, the precipitation in step (e) is dried in a vacuum oven at 50°C for 36 h to obtain a dry bulk polycondensation imidazole polymer material;
[0078] (g) the bulk polycondensation imidazole polymer material obtained in (f) is mixed with an ethanol solution with a mass percentage concentration of 80%, and is configuredto obtain a mass percentage concentration of lwt% of a bulk polycondensation imidazole polymer material mixture solution.
[0079] The catalyst is polyphosphoric acid.
[0080] The inert atmosphere is high-purity argon.
[0081] The polymer solution is apolyether block amide solution, and its prparation method is:
[0082] ©_x0001_3g polyether block amide polymer particles is added to 93g of
ethanol solution with a concentration of 80% by mass, and stirred at 75°C for 3 h;
[0083] @ The solution obtained in 0 is naturally cooled;
[0084] @The room temperature solution in @ is centrifuged for 10 min at a speed
of 8000 rpm;
[0085] @ The supernatant is transferred to a container to obtain the polyether
block amide solution.
[0086] The organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is:
[0087] 19g of hydrotalcite is dispersed in 300g of ethanol, 3.2g of coupling agent is added, and the temperature is raised to 55°C under nitrogen protection, 0.8g of 1-carboxymethyl-3-methylimidazole nitrate, 5g of hexanol polyether-4 carboxylic acid is added to the reaction kettle, and it is reacted for 110 min at reflux temperature, after completion, it is filtered and ished with ethanol. The obtained solid is dispersed in deionized water. The solid content is controlled to 4 .3, and the dispersant sodium tripolyphosphate with a mass percentage concentration of 0.3% is added and stirred. The silyl amide hydrotalcite can be obtained after uniform mixing.
[0088] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
Descriptions
[0089] Embodiment 3
[0090] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0091] (1) 1.2 g of the mixture solution is added to 10 g of the polymer solution;
[0092] (2) 0.15 g of organic hydrotalcite is added, stirred for 120 min and then ultrasonicated for 50 min;
[0093] (3) Then, the solution obtained in (2) is stirred on a stirrer for 10 h;
[0094] (4) The solution obtained in (3) is allowed to stand still for 5 min to degas;
[0095] (5) the solution obtained in (4) is poured into a petri dish, placed in an oven, and placed at 75°C for 48 h;
[0096] (6) the film obtained in step (5) is transferred to a vacuum oven for desolventizing for 72 h at a temperature of 75°C; a bulk polycondensation imidazole polymer mixed matrix membrane can be obtained.
[00 9 7 ]The mixture solution is a bulk polycondensation imidazole polymer material mixture solution, and its preparation method is as follows:
[0098] (a) A cleaned reactor is prepared, and nitrogen gas is blown into it for 60 min;
[0099] (b) A reactor filled with nitrogen is charged with 16.4g of 3,3-diaminobenzidine, 400 g of ethylene glycol phenyl ether is added as a solvent and 0.5 g of a catalyst, and the reactor is heated at 60°C for 180 min under an inert atmosphere. 21.4g 1,3,5--benzenetricarboxylic acid is added and mixed, and the reaction is stirred at 200°C for 60 h;
[0100] (c) The solution in step (b) is allowed to stand still and wait for it to drop to room temperature, and then the solution is added to 2000 g of deionized water and continuously stirred to obtain a flocculent substance;
[0101] (d) The solution obtained in step (c) is centrifuged at a centrifugal speed of 10000rpm, and the supernatant is discarded after ishing with deionized water, and this step is repeated 10 times until pH=7;
[0102] (e) The precipitate obtained in step (d) is sequentially added with water, ethanol and acetone for Soxhlet extraction for 14h;
[0103] (f) Then, the precipitation in step (e) is dried in a vacuum oven at 50°C for 48 h to obtain a dry bulk polycondensation imidazole polymer material;
[0104](g) The bulk polycondensation imidazole polymer material obtained in (f) is mixed with an ethanol solution with a mass percentage concentration of 100%, and is configuredto obtain a mass percentage concentration of 1.5 wt% of a bulk polycondensation imidazole polymer material mixture solution.
[0105] The catalyst is polyphosphoric acid.
Descriptions
[0106] The inert atmosphere is high-purity argon.
[0107] The polymer solution is a polyether block amide solution, and its preparation method is:
[0108] ( 5g of polyether block amide polymer particles are added to 95g of ethanol solution with a concentration of 100% by mass, and stirred at 80°C for 4 h;
[0109] The solution obtained in 0 is naturally cooled;
[0110] @The room temperature solution in @ is centrifuged for 15 min at a speed of 10000 rpm;
[0111] @ The supernatant is transferred into a container to obtain the polyether block amide solution.
[0112] The organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is:
[0113] 22g of hydrotalcite is dispersed in 500g of ethanol, 4.2g of coupling agent is added, and the temperature is raised to 62°C under nitrogen protection, 1.5g of 1-carboxymethyl-3-methylimidazole nitrate, 6g of hexanol polyether-4 carboxylic acid is added to the reaction kettle, and it is reacted for 180 min at reflux temperature, after completion, it is filtered and ished with ethanol. The obtained solid is dispersed in deionized water. The solid content is controlled to 5.4%, and the dispersant sodium tripolyphosphate with a mass percentage concentration of 0.5% is added and stirred. The silyl amide hydrotalcite can be obtained after uniform mixing.
[0114] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0115] The composition of the raw material mixed gas used in the performance evaluation of the mixed matrix membrane prepared in each of the above embodiments is a mixed gas of 70% methane and 30% carbon dioxide; the mass flow of the raw gas is controlled between 40-100 ml/min. The pressure of the purge gas nitrogen is normal pressure, and the mass flow rate is controlled at 37ml/min. The content of gas components in the feed gas and the permeate gas passing through the membrane is detected by using Agilent 6820 gas chromatography. The carbon dioxide permeability coefficient and carbon dioxide/methane selectivity of the tested membrane material (the carbon dioxide/methane selectivity is the ratio of the carbon dioxide permeability coefficient to the methane permeability coefficient). The test results are shown in the following table:
[0116]
Descriptions
NO. (Barrer) C0 2/methane selectivity
CO2 permeability coefficient
Embodiment 1 428 56.2
Embodiment 2 463 61.3
Embodiment 3 472 64.8
[0117] Comparative example 1
[0118] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0119] (1) 0.04 g of the mixture solution is added to 6 g of the polymer solution;
[0120] (2) After being stirred for 10 minutes, it is ultrasonicated for 20 minutes;
[0121] (3) Then, the solution obtained in (2) is stirred on a stirrer for 5 h;
[0122] (4) The solution obtained in (3) is allowed to stand still for 1 min to degas;
[0123] (5) the solution obtained in (4) is poured into a petri dish, placed in an oven, and placed at 55°C for 24 h;
[0124] (6) the film obtained in step (5) is transferred to a vacuum oven for desolventizing for 24 h at a temperature of 50°C; a bulk polycondensation imidazole polymer mixed matrix membrane can be obtained.
[0125]The mixture solution is a bulk polycondensation imidazole polymer material mixture solution, and its preparation method is as follows:
[0126] (a) A cleaned reactor is prepared, and nitrogen gas is blown into it for 5 min;
[0127] (b) A reactor filled with nitrogen is charged with 13 2g of 3,3-diaminobenzidine, 150 g of ethylene glycol phenyl ether is added as a solvent and 0.1 g of a catalyst, and the reactor is heated at 60°C for 60 min under an inert atmosphere. 17.lg 1,3,5--benzenetricarboxylic acid is added and mixed, and the reaction is stirred at 150°C for 24 h;
[0128] (c) The solution in step (b) is allowed to stand still and wait for it to drop to room temperature, and then the solution is added to 1500 g of deionized water and continuously stirred to obtain a flocculent substance;
[0129] (d) The solution obtained in step (c) is centrifuged at a centrifugal speed of 5000rpm, and the supernatant is discarded after ishing with deionized water, and this step is repeated 6 times until pH=6;
[0130] (e) The precipitate obtained in step (d) is sequentially added with water,
Descriptions
ethanol and acetone for Soxhlet extraction for 10h;
[0131] (f) Then, the precipitation in step (e) is dried in a vacuum oven at 50°C for h to obtain a dry bulk polycondensation imidazole polymer material;
[0132] (g) The bulk polycondensation imidazole polymer material obtained in (f) is mixed with an ethanol solution with a mass percentage concentration of %, and is configuredto obtain a mass percentage concentration of 0.5 wt% of a bulk polycondensation imidazole polymer material mixture solution.
[0133] The catalyst is polyphosphoric acid.
[0134] The inert atmosphere is high-purity nitrogen.
[0135] The polymer solution is a polyether block amide solution, and its preparation method is:
[0136] ©_x0001_1g polyether block amide polymer particles are added to 90g ethanol solution with a concentration of 70% by mass, and stirred at 70°C for 2h;
[0137] The solution obtained in 0 is naturally cooled;
[0138] @The room temperature solution in @ is centrifuged for 5 min at a speed
of 7000 rpm;
[0139] @ The supernatant is transferred into a container to obtain the polyether
block amide solution.
[0140] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0141] Comparative example 2
[0142] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0143] (1) 6g polymer solution is taken;
[0144] (2) 0.01 g of organic hydrotalcite is added, stirred for 10 min and then ultrasonicated for 20 min;
[0145] (3) The solution obtained in (2) is then stirred on a stirrer for 5 h;
[0146] (4) The solution obtained in (3) is allowed to stand still for1 min to degas;
[0147] (5) The solution obtained in (4) is poured into a petri dish, placed in an oven, and placed at 55°C for 24 h;
[0148] (6) The membrane obtained in (5) is transferred to a vacuum oven for desolventizing for 24h at a temperature of 50°C; the one-type polycondensation imidazole polymer mixed matrix membrane can be obtained.
[0149] The polymer solution is a polyether block amide solution, and its
Descriptions
preparation method is:
[0150] @_x0001_1g polyether block amide polymer particles are added to 90g ethanol solution with a concentration of 70% by mass, and stirred at 70°C for 2h;
[0151] @ The solution obtained in 0 is naturally cooled;
[0152] @The room temperature solution in @ is centrifuged for 5 min at a speed
of 7000 rpm;
[0153] @ The supernatant is transferred to a container to obtain the polyether
block amide solution.
[0154] The organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is:
[0155] 19g of hydrotalcite is dispersed in 300g of ethanol, 3.2g of coupling agent is added, and the temperature is raised to 55°C under nitrogen protection, 0.8g of 1-carboxymethyl-3-methylimidazole nitrate, 5g of hexanol polyether-4 carboxylic acid is added to the reaction kettle, and it is reacted for 110 min at reflux temperature, after completion, it is filtered and ished with ethanol. The obtained solid is dispersed in deionized water. The solid content is controlled to 4 .3, and the dispersant sodium tripolyphosphate with a mass percentage concentration of 0.3% is added and stirred. The silyl amide hydrotalcite can be obtained after uniform mixing.
[0156] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0157] Comparative example 3
[0158] A bulk polycondensation imidazole polymer mixed matrix membrane is prepared according to the following method:
[0159] (1) 004g of the mixture solution is added to 6 g of the polymer solution;
[0160] (2) 0.01 g of organic hydrotalcite is added, stirred for 10 min and then ultrasonicated for 20 min;
[0161] (3) Then, the solution obtained in (2) is stirred on a stirrer for 5 h;
[0162] (4) The solution obtained in (3) is allowed to stand still for1min to degas;
[0163] (5) the solution obtained in (4) is poured into a petri dish, placed in an oven, and placed at 55°C for 24 h;
[0164] (6) the film obtained in step (5) is transferred to a vacuum oven for desolventizing for 24 h at a temperature of 50°C; a bulk polycondensation imidazole polymer mixed matrix membrane can be obtained.
Descriptions
[0165] The mixture solution is a bulk polycondensation imidazole polymer material mixture solution, and its preparation method is as follows:
[0166] (a) A cleaned reactor is prepared, and nitrogen gas is blown into it for 5 min;
[0167] (b) A reactor filled with nitrogen is charged with 13 2g of 3,3-diaminobenzidine, 150 g of ethylene glycol phenyl ether is added as a solvent and 0.1 g of a catalyst, and the reactor is heated at 60°C for 60 min under an inert atmosphere. 17.lg 1,3,5--benzenetricarboxylic acid is added and mixed, and the reaction is stirred at 150°C for 24 h;
[0168] (c) The solution in step (b) is allowed to stand still and wait for it to drop to room temperature, and then the solution is added to 1500 g of deionized water and continuously stirred to obtain a flocculent substance;
[0169] (d) The solution obtained in step (c) is centrifuged at a centrifugal speed of 5000rpm, and the supernatant is discarded after ishing with deionized water, and this step is repeated 6 times until pH=6;
[0170] (e) The precipitate obtained in step (d) is sequentially added with water, ethanol and acetone for Soxhlet extraction for 10 h;
[0171] (f) Then, the precipitation in step (e) is dried in a vacuum oven at 50°C for 20 h to obtain a dry bulk polycondensation imidazole polymer material;
[0172] (g) The bulk polycondensation imidazole polymer material obtained in (f) is mixed with an ethanol solution with a mass percentage concentration of 60%, and is configuredto obtain a mass percentage concentration of 0.5 wt% of a bulk polycondensation imidazole polymer material mixture solution.
[0173] The catalyst is polyphosphoric acid.
[0174] The inert atmosphere is high-purity nitrogen.
[0175] The polymer solution is a polyether block amide solution, and its preparation method is:
[0176] @_x0001_1g polyether block amide polymer particles are added to 90g
ethanol solution with a concentration of 70% by mass, and stirred at 70°C for 2h;
[0177] The solution obtained in @ is naturally cooled;
[0178] @The room temperature solution in @ is centrifuged for 5 min at a speed
of 7000 rpm;
[0179] @) The supernatant is transferred into a container to obtain the polyether
block amide solution.
Descriptions
[0180] The bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
[0181] The performance test of the sample of the above comparative example, the statistical results of the results are as follows:
NO. (Barrer) C0 2/methane selectivity
CO 2 permeability coefficient
(Barrer)
Comparative example 1 371 41.8
Comparative example 2 284 29.3
Comparative example 3 396 43.2
Claims (9)
1. A bulk polycondensation imidazole polymer mixed matrix membrane, prepared according to the following method: In parts by mass, 0.04-1.2 parts of the mixture solution is added to 6-10 parts of the polymer solution; 0.01-0.15 parts of organic hydrotalcite is added, and after stirring for 10-120 min , dispersed by ultrasonic for 20-50min; stirred on a stirrer for -10h; the resulting solution is statically defoamed for 1-5min; poured into a petri dish, placed in an oven, and placed at 55-75°C for 24-48h ; then, the solvent is removed in a vacuum oven for 24-72h, at a temperature of 50-75°C; the one-type polycondensation imidazole polymer mixed matrix film can be obtained.
2. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 1, characterized in that the mixture solution is a bulk polycondensation imidazole polymer material mixture,the preparation method of the solution is as follows: A cleaned reactor is prepared, and nitrogen gas is blown into it for 5-60 min; According to the mass parts, 13.2-16.4 parts of 3,3-diaminobenzidine is charged into a nitrogen-filled reactor, and 150-400 parts of ethylene glycol phenyl ether is added as a solvent and 0 .1-0.5 parts of catalyst, and heated at 60°C for -180min in an inert atmosphere, 17.1-21.4 parts of 1,3,5- trimellitic acid are added and mixed, reacted and stirred at 150-200°C for 24-60h; then it is cooled to room temperature, then 1500-2000 parts of deionized water is added to the solution and stirred continuously, and then it is centrifuged at a centrifugal speed of 5000-10000 rpm and ished with deionized water, the supernatant is discarded, and this step is repeated 6-10 times until pH=6-7; The obtained flocculent substance and precipitate are Soxhlet extracted with water, ethanol and acetone for 10-14 h in sequence; and then dried in a vacuum oven at 50°C for 20-48 h to obtain a dry bulk polycondensation imidazole polymer material; The obtained bulk polycondensation imidazole polymer material is mixed with an ethanol solution with a mass part of 60%-100%, and is configured to obtain a bulk polycondensation imidazole polymer material mixture solution with a mass part of 0.5-1.5 wt%.
3. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 2, characterized in that the catalyst is polyphosphoric acid.
4. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 2, characterized in that the inert atmosphere is high-purity nitrogen or argon.
Claims
5. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 1, characterized in that the polymer solution is a polyether block amide solution, and its preparation method is as follows: 1-5 parts of polyether block amide polymer particles are added to 90-95 parts of a 70%-100% ethanol solution by mass, and stirred at 70-80°C for 2-4h; naturally cooled to room temperature; it is centrifuged for 5-15 min at a speed of 7000-10000 rpm; the supernatant is transferred to a container to obtain a polyether block amide solution.
6. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 1, characterized in that the organic hydrotalcite is a silyl amide hydrotalcite, and its preparation method is as follows: In parts by weight, 16-22 parts of hydrotalcite is dispersed in 200-500 parts of ethanol, and 2.1-4.2 parts of coupling agent are added, and the temperature is raised to 50-62°C under the protection of nitrogen, 0.2-1.5 parts of 1-carboxymethyl-3-methylimidazole nitrate and 2-6 parts of hexanol-4 carboxylic acid are added to the reaction kettle, which is kept refluxed for 90- 180min, after filtration and ishing with ethanol, the solids obtained are dispersed in deionized water, and the solid content is controlled to 2.8%-5.4%, and is added to the dispersion with a concentration of 0.1% to 0.5% by mass percentage, and the silylamide hydrotalcite can be obtained after being stirred and mixed uniformly.
7. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 6, characterized in that the coupling agent is N-aminoethyl-3-aminopropyltriethoxysilane or N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxy Silane.
8. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 6, characterized in that the said hydrotalcite has a particle size of 40-200 mesh.
9. A bulk polycondensation imidazole polymer mixed matrix membrane used for gas separation and its preparation method according to claim 1, characterized in that the bulk polycondensation imidazole polymer mixed matrix membrane is used for the separation of gaseous carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2021105920A AU2021105920A4 (en) | 2021-08-19 | 2021-08-19 | A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used For Gas Separation And Its Preparation Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2021105920A AU2021105920A4 (en) | 2021-08-19 | 2021-08-19 | A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used For Gas Separation And Its Preparation Method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2021105920A4 true AU2021105920A4 (en) | 2021-10-21 |
Family
ID=78177106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2021105920A Active AU2021105920A4 (en) | 2021-08-19 | 2021-08-19 | A Bulk Polycondensation Imidazole Polymer Mixed Matrix Membrane Used For Gas Separation And Its Preparation Method |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2021105920A4 (en) |
-
2021
- 2021-08-19 AU AU2021105920A patent/AU2021105920A4/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | The enhanced hydrogen separation performance of mixed matrix membranes by incorporation of two-dimensional ZIF-L into polyimide containing hydroxyl group | |
| Wu et al. | Nanoporous ZIF-67 embedded polymers of intrinsic microporosity membranes with enhanced gas separation performance | |
| He et al. | Recent progress in PIM-1 based membranes for sustainable CO2 separations: Polymer structure manipulation and mixed matrix membrane design | |
| Gao et al. | Functionalized ZIF-7/Pebax® 2533 mixed matrix membranes for CO2/N2 separation | |
| Hua et al. | ZIF-90/P84 mixed matrix membranes for pervaporation dehydration of isopropanol | |
| Cao et al. | Penetrated COF channels: amino environment and suitable size for CO2 preferential adsorption and transport in mixed matrix membranes | |
| Tian et al. | Enhanced gas separation performance of mixed matrix membranes from graphitic carbon nitride nanosheets and polymers of intrinsic microporosity | |
| Liu et al. | Highly permeable and aging resistant 3D architecture from polymers of intrinsic microporosity incorporated with beta-cyclodextrin | |
| Khan et al. | SPEEK and functionalized mesoporous MCM-41 mixed matrix membranes for CO 2 separations | |
| Ahmadijokani et al. | Amino-silane-grafted NH 2-MIL-53 (Al)/polyethersulfone mixed matrix membranes for CO 2/CH 4 separation | |
| Wang et al. | Enhancing the CO2 separation performance of SPEEK membranes by incorporation of polyaniline-decorated halloysite nanotubes | |
| Saqib et al. | Perylene based novel mixed matrix membranes with enhanced selective pure and mixed gases (CO2, CH4, and N2) separation | |
| Wang et al. | Sealing Tröger base/ZIF-8 mixed matrix membranes defects for improved gas separation performance | |
| Sarfraz et al. | A novel zeolitic imidazolate framework based mixed-matrix membrane for efficient CO2 separation under wet conditions | |
| Jiang et al. | Solvent-processable 0D covalent organic framework quantum dot engineered composite membranes for biogas upgrading | |
| Lee et al. | Improved performance of nanocomposite polyimide membranes for pervaporation fabricated by embedding spirobisindane structure-functionalized graphene oxide | |
| CN111617645A (en) | Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material | |
| Gao et al. | Surface functionalization of Polymers of Intrinsic Microporosity (PIMs) membrane by polyphenol for efficient CO2 separation | |
| Mao et al. | Zeolitic imidazolate frameworks in mixed matrix membranes for boosting phenol/water separation: Crystal evolution and preferential orientation | |
| Wang et al. | A mechanically enhanced metal-organic framework/PDMS membrane for CO2/N2 separation | |
| Yang et al. | Water-selective hybrid membranes with improved interfacial compatibility from mussel-inspired dopamine-modified alginate and covalent organic frameworks | |
| Chen et al. | Veiled metal organic frameworks nanofillers for mixed matrix membranes with enhanced CO2/CH4 separation performance | |
| Li et al. | A defects-free ZIF-90/6FDA-Durene membrane based on the hydrogen bonding/covalent bonding interaction for gas separation | |
| CN108744991B (en) | Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material | |
| Chen et al. | Phenolic resin regulated interface of ZIF-8 based mixed matrix membrane for enhanced gas separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGI | Letters patent sealed or granted (innovation patent) |