CN115025629B - Ammonia-containing hydrophobic hybrid silicon film and preparation method and application thereof - Google Patents
Ammonia-containing hydrophobic hybrid silicon film and preparation method and application thereof Download PDFInfo
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- CN115025629B CN115025629B CN202210549408.9A CN202210549408A CN115025629B CN 115025629 B CN115025629 B CN 115025629B CN 202210549408 A CN202210549408 A CN 202210549408A CN 115025629 B CN115025629 B CN 115025629B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0004—Organic membrane manufacture by agglomeration of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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Abstract
The invention belongs to the technical field of membrane material separation, and particularly relates to an ammonia-containing hydrophobic hybrid silicon membrane, a preparation method and application thereof. The microstructure change and separation properties of the membrane were studied by using the amino group-introduced organosilicon membrane. Experimental results show that the organic silicon film with the amino group introduced leads the microstructure of the film to be more compact, and the organic silicon film prepared by the invention has good CO 2 Permeability, applicable to carbon dioxide gas permeation under moisture.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and relates to an ammonia-containing hydrophobic hybrid silicon membrane, and a preparation method and application thereof.
Background
Burning fossil fuels to CO 2 The emissions are increasing, causing a series of environmental problems, thus CO 2 Is critical. In industrial applications, most operations, such as removal of CO from flue gases 2 And capturing CO from natural gas 2 All in the presence of water vapor. For CO 2 The separated polymer film is susceptible to swelling under water vapor to reduce performance. The organic silicon film is a silicon dioxide base film formed by the hydrolytic polymerization of organic alkoxy silane, has high hydrothermal stability and excellent molecular sieving performance, and has a great application prospect in the aspect of separating carbon dioxide. Grafting amino groups on membranesAgglomeration to promote CO 2 A popular method of separation is disclosed in patent No. CN113385054A, which discloses the addition of amino-containing organoalkoxysilanes to silicone networks to give excellent CO 2 The separation selectivity. However, the amino group cited in the patent causes the increase of the hydrophilicity of the organosilicon, and when applied to the water vapor condition, capillary condensation phenomenon is likely to occur, so that the permeability of carbon dioxide is reduced.
Disclosure of Invention
To solve the problem of CO under the condition of water vapor caused by amino 2 The permeability is greatly reduced, an ammonia-containing hydrophobic hybrid silicon membrane, a preparation method and application thereof, wherein amino groups are grafted on benzene rings, so that the amino groups promote CO 2 At the same time of transfer, the benzene ring is utilized to repel water, thereby reducing the influence of water on the membrane and the CO 2 The competitive adsorption of water vapor in industry is solved.
A further object of the present invention is to provide an ammonia-containing hydrophobic hybrid silicon film having the structural formula:
can be applied to moisture conditions of water vapor and CO in liquid water solution 2 And (5) removing gas. The phenyl structure can enhance the water rejection, avoid capillary condensation, and reduce water and CO 2 Competitive adsorption in membranes, while amino groups may further promote CO 2 Adsorption diffusion in membranes, improving CO 2 Is a permeability of (c).
The technical aim of the invention is realized by the following technical scheme:
the invention provides a preparation method of an ammonia-containing hydrophobic hybrid silicon film, which comprises the following operation steps:
s1, adding an organosilicon source precursor into absolute ethyl alcohol, adding water and an acidic catalyst (hydrochloric acid, nitric acid or sulfuric acid and the like) under continuous water bath stirring to start a reaction to prepare organosilicon sol, wherein the organosilicon source precursor is MAPRMS or combined with BTESE, and the mass ratio of the two is 0-2:1, preferably 0.1-1:1 when the BTESE (1, 2-bis (triethoxysilyl) ethane) and the MAPRMS (para-aminophenyltrimethoxysilane) are added together;
s2 is porous alpha-Al 2 O 3 And (3) taking the material as a support, preparing an intermediate layer in advance, coating the organosilicon sol prepared in the step (1) on the intermediate layer, and calcining to form the ammonia-containing hydrophobic hybrid silicon film.
Further, the molar composition of the reactants is the organosilicon source precursor: h 2 O: hcl=1:10-300:0.01-0.1, the mass fraction of the organosilicon source precursor in the solution is kept at 0.5-5.0wt%.
Further, the average pore diameter of the support in step S2 is 0.2 to 1. Mu.m. And/or the support body is tubular, sheet-like or hollow fiber.
Further, the preparation method of the intermediate layer in the step S2 includes the following steps: siO is made of 2 -ZrO 2 The sol is coated on a porous ceramic support, calcined at 100-500 ℃ for 30-60 minutes, and the coating and calcining process is repeated 3-4 times to form an intermediate layer.
Further, the organosilicon sol prepared in the step S1 is coated on the intermediate layer by a rubbing sol method, calcined in an inert atmosphere at 100-500 ℃ for 30-60 minutes, and the coating and calcining processes are repeated 3-4 times to form a separation layer (an ammonia-containing hydrophobic hybrid silicon film).
On one hand, the BTESE has an adjustable network structure due to the permeability control of the organic functional group and has thermal stability at high temperature. On the other hand, the affinity of amino groups in MAPRMS to carbon dioxide can improve CO 2 The permeability in separation and benzene ring modification in the organic silicon film network structure can enhance the hydrophobicity. After MAPRMS is introduced, the microstructure of the membrane is more compact, and CO is effectively improved 2 Permeability and separation performance.
Drawings
FIG. 1 is an infrared plot of the silicone film of example 1, example 2, example 3, example 4;
FIG. 2 is an SEM image of a BTESE film prepared in comparative example 1;
FIG. 3 is a graph of the water contact angle of the film prepared in comparative example 1 (left graph in FIG. 3) and a graph of the water contact angle of the film prepared in example 1 (right graph in FIG. 3);
fig. 4 is a thermogravimetric view of the silicone film of example 1, example 2, example 3, example 4.
FIG. 5 is a schematic diagram of the gas separation of an ammonia-containing hydrophobic hybrid silicon membrane according to the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
the embodiment of the invention provides a preparation method of an ammonia-containing hydrophobic hybrid silicon film, which comprises the following steps:
(1) alpha-Al of 0.2-1 μm 2 O 3 And (3) polishing the support body, and roasting at 550 ℃ for 1h.
(2) 1.0wt% of SiO 2 -ZrO 2 The sol is coated on a support, calcined at 100-500 ℃ for 30-60 minutes, and repeated three times to form an intermediate layer.
(3) Diluting 0.5-5.0wt% organic silicon sol to 0.5-0.1% with absolute ethyl alcohol or isopropanol, coating on the surface of the intermediate layer, calcining at 100-550deg.C for 30-60 min, and repeating for three times to obtain the separation membrane.
The specific embodiment also provides an application of the ammonia-containing hydrophobic hybrid silicon membrane prepared by the method, namely the membrane is used as a gas separation membrane to mix gas CO 2 And (5) separating.
Example 1:
(1) Preparation of an organosilicon sol, 0.53g of BTESE and 0.47g of MAPRMS were dissolved in 17.7g of ethanol, then 1.2g of water and 0.1g of 35wt% HCl were added to form a uniform 5.0wt% organosilicon solution, and then the solution was stirred in a 40℃water bath for 10 hours to prepare MAPRMS/BTESE sol.
(2) Preparing a support: siO for 0.2 μm chip ceramic carrier was coated by wiping 2 -ZrO 2 The sol is calcined after being rubbed at 500 ℃ for 60min each time, and the process is repeated for 4 times.
(3) And (3) placing the support obtained in the step (2) into a baking oven at 100 ℃ for preheating for 1h, diluting the MAPRMS/BTESE sol obtained in the step (1) to 0.5% by adopting cotton, then wiping the diluted MAPRMS/BTESE sol on the support, calcining for 60min, wherein the calcining temperature is 200 ℃, and repeating for 3 times to obtain the hybrid silicon film. The measured surface contact angle was 82.2 °, as shown in the right hand graph of fig. 3.
Gas testing was performed on the MAPRMS/BTESE organosilicon film prepared, CO 2 Introducing water-containing bubbling tank after gas is led out of the steel cylinder, continuously introducing into a membrane module heated to 200 ℃, controlling the gauge pressure of the raw material side to be 200kPa, and measuring CO 2 Has a permeability of 1.25x10 -7 mol/m 2 s Pa。
Example 2
(1) Preparation of an organosilicon sol, 0.3g of BTESE and 0.7g of MAPRMS were dissolved in 17.55g of ethanol, then 1.35g of water and 0.1g of 35wt% HCl were added to form a uniform 5.0wt% organosilicon solution, and then the solution was stirred in a 40℃water bath for 10 hours to prepare MAPRMS/BTESE sol.
The other steps are the same as in example 1.
Gas testing was performed on the MAPRMS/BTESE organosilicon film prepared, CO 2 Introducing water-containing bubbling tank after gas is led out of the steel cylinder, continuously introducing into a membrane module heated to 200 ℃, controlling the gauge pressure of the raw material side to be 200kPa, and measuring CO 2 Has a permeability of 1.81x10 -7 mol/m 2 s Pa。
Example 3
(1) Preparation of an organosilicon sol, 0.45g of BTESE and 0.55g of MAPRMS were dissolved in 16.83g of ethanol, then 2.07g of water and 0.1g of 35wt% HCl were added to form a uniform 5.0wt% organosilicon solution, and then the solution was stirred in a 40℃water bath for 10 hours to prepare MAPRMS/BTESE sol.
The other steps are the same as in example 1.
Gas testing was performed on the MAPRMS/BTESE organosilicon film prepared, CO 2 Introducing water-containing bubbling tank after gas is led out of the steel cylinder, continuously introducing into a membrane module heated to 200 ℃, controlling the gauge pressure of the raw material side to be 200kPa, and measuring CO 2 Has a permeability of 1.96×10 -7 mol/m 2 s Pa。
Example 4
(1) Preparation of an organosilicon sol, 1.0g of MAPRMS was dissolved in 15.90g of ethanol, then 3.0g of water and 0.1g of 35wt% HCl were added to form a uniform 5.0wt% organosilicon solution, and then the solution was stirred in a 40℃water bath for 10 hours to prepare MAPRMS sol.
The other steps are the same as in example 1.
Gas testing is carried out on the MAPRMS organic silicon film, and CO is carried out 2 Introducing water-containing bubbling tank after gas is led out of the steel cylinder, continuously introducing into a membrane module heated to 200 ℃, controlling the gauge pressure of the raw material side to be 200kPa, and measuring CO 2 Has a permeability of 1.57x10 -7 mol/m 2 s Pa。
Comparative example 1
(1) Prepare an organosilicon sol, dissolve 1g of BTESE in 15.90g of ethanol, then add 3g of water and 0.1g of 35wt% HCl to form a homogeneous 5.0wt% organosilicon solution, then stir in a 40℃water bath for 2h to prepare a BTESE sol.
The other steps are the same as in example 1.
Gas testing of the prepared BTESE organosilicon film, CO 2 Introducing water-containing bubbling tank after gas is led out of the steel cylinder, continuously introducing into a membrane module heated to 200 ℃, controlling the gauge pressure of the raw material side to be 200kPa, and measuring CO 2 Has a permeability of 6.99X10 -8 mol/m 2 sPa, the measured surface contact angle was 53.5℃as shown in the left-hand graph of FIG. 3. Whereas the water contact angle of the first embodiment shown in the right-hand graph of fig. 3 is improved compared to the hydrophilicity of BTESE.
TABLE 1
Table 1 shows the CO of MAPRMS/BTESE silicone films prepared in examples 1 to 4 and pure silicone film prepared in comparative example 1 2 The permeability and the result show that the permeability of BTESE to carbon dioxide is obviously increased after MAPRMS doping, which shows that the hydrophobic hybridization silicon membrane containing amino has higher CO 2 Permeability.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (8)
1. An ammonia-containing hydrophobic hybrid silicon film, characterized in that: the structural formula is as follows:
，
the preparation of the ammonia-containing hydrophobic hybrid silicon film comprises the following operation steps:
s1, adding an organosilicon source precursor into absolute ethyl alcohol, and adding water and an acid catalyst under continuous water bath stirring to start reaction to prepare organosilicon sol, wherein the organosilicon source precursor is prepared by combining MAPRMS and BTESE, and the mass ratio of the BTESE to the MAPRMS is 0.43-1:1;
s2 is porous alpha-Al 2 O 3 And (3) taking the material as a support, coating an intermediate layer in advance, coating the organosilicon sol prepared in the step (1) on the intermediate layer, and calcining to form the ammonia-containing hydrophobic hybrid silicon film.
2. A method for preparing an ammonia-containing hydrophobic hybrid silicon film as claimed in claim 1, comprising the following steps:
s1, adding an organosilicon source precursor into absolute ethyl alcohol, and adding water and an acid catalyst under continuous water bath stirring to start reaction to prepare organosilicon sol, wherein the organosilicon source precursor is prepared by combining MAPRMS and BTESE, and the mass ratio of the BTESE to the MAPRMS is 0.43-1:1;
s2 is porous alpha-Al 2 O 3 And (3) taking the material as a support, coating an intermediate layer in advance, coating the organosilicon sol prepared in the step (1) on the intermediate layer, and calcining to form the ammonia-containing hydrophobic hybrid silicon film.
3. The method for preparing the ammonia-containing hydrophobic hybrid silicon film according to claim 2, wherein: the molar composition of the reactants is that of the organosilicon source precursor: h 2 O: hcl=1:10-300:0.01-0.1, the mass fraction of the organosilicon source precursor in the solution is kept at 0.5-5.0wt%.
4. The method for preparing the ammonia-containing hydrophobic hybrid silicon film according to claim 2, wherein: the organic silicon sol prepared in the step S1 is coated on the intermediate layer in a rubbing sol mode, the intermediate layer is calcined for 30-60 minutes in an inert atmosphere at 100-500 ℃, and the coating and calcining processes are repeated for 3-4 times.
5. The method for preparing the ammonia-containing hydrophobic hybrid silicon film according to claim 2, wherein: the acid catalyst in the step S1 is any one of hydrochloric acid, nitric acid or sulfuric acid.
6. A method for preparing an ammonia-containing hydrophobic hybrid silicon film as defined in claim 2, wherein: the porous support selected in step S2 has an average pore size of 0.2-1 μm and is tubular, sheet-like or hollow fiber-like in shape.
7. An ammonia-containing hydrophobic hybrid silicon film as defined in claim 2The preparation method is characterized in that: the preparation method of the intermediate layer in the step S2 comprises the following steps: siO is made of 2 -ZrO 2 The sol is coated on a porous ceramic support, calcined at 100-500 ℃ for 30-60 minutes, and the coating and calcining process is repeated 3-4 times to form an intermediate layer.
8. Use of an ammonia-containing hydrophobic hybrid silicon film according to claim 1, characterized in that: for separating water vapor or carbon dioxide from water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218270A (en) * | 2011-04-07 | 2011-10-19 | 北京工业大学 | Phenyl decorated organic-inorganic hybridization millipore silicon dioxide film preparation method |
| CN113385054A (en) * | 2021-07-07 | 2021-09-14 | 常州大学 | Preparation method and application of amino-modified organic silicon film |
| CN113648855A (en) * | 2021-08-27 | 2021-11-16 | 常州大学 | For separating CO2/N2Method for preparing organic silicon film |
| CN113856489A (en) * | 2021-09-26 | 2021-12-31 | 常州大学 | MoS2Organic silicon blending matrix membrane, preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218270A (en) * | 2011-04-07 | 2011-10-19 | 北京工业大学 | Phenyl decorated organic-inorganic hybridization millipore silicon dioxide film preparation method |
| CN113385054A (en) * | 2021-07-07 | 2021-09-14 | 常州大学 | Preparation method and application of amino-modified organic silicon film |
| CN113648855A (en) * | 2021-08-27 | 2021-11-16 | 常州大学 | For separating CO2/N2Method for preparing organic silicon film |
| CN113856489A (en) * | 2021-09-26 | 2021-12-31 | 常州大学 | MoS2Organic silicon blending matrix membrane, preparation method and application |
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