CN107051226B - Ceramic membrane base material - Google Patents
Ceramic membrane base material Download PDFInfo
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- CN107051226B CN107051226B CN201710373875.XA CN201710373875A CN107051226B CN 107051226 B CN107051226 B CN 107051226B CN 201710373875 A CN201710373875 A CN 201710373875A CN 107051226 B CN107051226 B CN 107051226B
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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
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/28—Pore treatments
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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
- B01D2325/24—Mechanical properties, e.g. strength
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a ceramic membrane-based material, wherein the inner layer of the ceramic membrane-based material is a pure carbon layer, the average pore diameter of the inner layer is 300-500 mu m, the outer layer is a composite layer consisting of C and SiC, and the average pore diameter of the outer layer is 10-20 mu m; the pores of the inner layer and the outer layer of the ceramic membrane base material are communicated. The ceramic membrane-based material has the advantages of uniform pore size distribution, through connection, high separation precision, good toughness, high strength, high temperature resistance, acid and alkali resistance and the like.
Description
Technical Field
The invention relates to the technical field of porous ceramic membranes, in particular to a ceramic membrane-based material.
Background
The membrane separation process is that liquid containing dissolved solute or suspended particles passes through a membrane, wherein solvent and solute small molecules permeate the membrane, and solute large molecules and suspended particles are retained by the membrane. Compared with organic membranes, the inorganic ceramic membrane is a precise ceramic material which is prepared by sintering metal oxide or mixed metal oxide powder at high temperature and has certain selective separation performance, has the advantages of good chemical stability, high mechanical strength, strong antimicrobial capability, high temperature resistance, narrow pore size distribution, high separation efficiency and the like, can be applied to gas separation, liquid separation and purification and membrane reactors, and has wide application in the fields of food industry, pharmacy and biological engineering, chemical and petrochemical industry, environmental protection and the like.
The domestic research on ceramic membranes starts from the later 90 s of the last century, mainly focuses on alumina membrane materials, and develops application in the aspect of sewage treatment, thereby obtaining good benefits. However, in the industrial wastewater aspect, the wastewater often has the characteristics of large discharge amount, high temperature, high alkalinity, high acidity, heavy metal content and the like, higher requirements are put forward on the filtering performance of the inorganic ceramic membrane, the widely used alumina membrane material at present is difficult to resist strong acid and strong alkali environments, the high-temperature thermal stability is poor, the service life of the alumina membrane material is greatly shortened under the severe environment conditions, and the sewage treatment cost is increased. In addition, the alumina membrane material has general hydrophilic property, which causes low sewage treatment efficiency and increases pollution treatment cost to a certain extent. The silicon carbide has excellent chemical stability, strong acid and alkali resistance, good high-temperature stability and good hydrophilic performance, can be used in the range of pH value 0-14, has natural advantages in the aspect of sewage treatment due to the performance characteristics, and is an important direction for the development of inorganic ceramic membranes in future.
However, most of the existing silicon carbide ceramic membranes are formed by coating coarse-particle silicon carbide and a binder on a ceramic membrane support and then sintering, pores are formed by particle stacking gaps, and the pore size distribution is uneven, so that the filtration precision is poor, and the pores of the ceramic membrane are not communicated with the pores of the support, so that the porosity and the treatment efficiency are low, and the application of the ceramic membrane in many fields with high requirements on the separation precision and the treatment efficiency is greatly limited. In addition, the membrane module is often subjected to mechanical and thermal stress generated by vibration of a pump pressure motor during installation and work, and simultaneously, the membrane module is repeatedly subjected to impact or back flushing of pulse gas, water and the like during the separation process of the membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ceramic membrane-based material which has uniform pore size distribution, is communicated, has high separation precision, good toughness, high strength, high temperature resistance and acid and alkali resistance.
In order to solve the technical problems, the invention adopts the following technical scheme:
a ceramic membrane base material, the inner layer of the ceramic membrane base material is a pure carbon layer, the average aperture of the inner layer is 300 mu m-500 mu m, the outer layer is a composite layer consisting of C and SiC, and the average aperture of the outer layer is 10 mu m-20 mu m; the pores of the inner layer and the outer layer of the ceramic membrane base material are communicated.
Preferably, the ceramic membrane-based material is prepared by the following method:
(1) preparing a ceramic membrane substrate according to a required shape by using foamed asphalt with the average pore diameter of 300-500 mu m as a raw material, immersing the ceramic membrane substrate into molten Si in a heat treatment furnace, and keeping an inert atmosphere in the furnace for 30-60 min;
(2) and taking out the ceramic membrane substrate from the molten Si, heating the ceramic membrane substrate to 150-250 ℃ in the furnace, keeping the inert atmosphere, keeping the temperature for 2-4 h, and then cooling the ceramic membrane substrate to room temperature along with the furnace to obtain the ceramic membrane substrate material.
Preferably, in step (1), the ceramic membrane pre-matrix is a multi-channel tube, a single-channel tube or a flat plate.
Preferably, in the step (1), the temperature of the heat treatment furnace is raised to 1450-1550 ℃ at a temperature raising rate of 15-20 ℃/min, so that the crystalline silicon is melted to form molten Si.
Preferably, the inert atmosphere in step (1) is argon.
Compared with the prior art, the invention has the advantages that:
according to the ceramic membrane base material, the foamed asphalt is selected as the ceramic membrane base body, the molten silicon is subjected to in-situ reaction with carbon on the surface and near the surface of the foamed asphalt through high-temperature infiltration of the molten silicon, and a silicon carbide ceramic layer is generated on the surface and near the surface of the foamed asphalt in situ. The obtained pores are uniform in size and distribution, the structural defects are fewer, and the separation precision is greatly improved. And the pore size of the final silicon carbide ceramic layer can be regulated and controlled through the pore size of the foamed asphalt and the reaction conditions, the unreacted C layer in the central part of the foamed asphalt plays the roles of toughening and preventing the brittle failure of the material, the impact resistance is greatly improved, and the industrial application range of the foamed asphalt is greatly expanded, such as the foamed asphalt can be used in various membrane reactors or in severe mechanical application environments.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1:
a ceramic membrane base material, the inner layer of the ceramic membrane base material is a pure carbon layer, the average aperture of the inner layer is 300 mu m, the outer layer is a composite layer consisting of C and SiC, and the average aperture of the outer layer is 15 mu m; the pores of the inner layer and the outer layer of the ceramic membrane base material are communicated.
The preparation method of the ceramic membrane-based material comprises the following steps:
(1.1) preparing a flat ceramic membrane substrate according to a required shape by using foamed asphalt with the average pore diameter of 300 mu m as a raw material. Putting the monocrystalline silicon into a heat treatment furnace, heating to 1500 ℃ at the heating rate of 15 ℃/min under the argon atmosphere to melt the crystalline silicon to form molten Si, then immersing the flat ceramic membrane substrate into the molten Si, keeping the argon atmosphere in the furnace, and keeping the temperature for 60 min.
(1.2) taking out the flat ceramic membrane substrate from the molten Si, heating the furnace to 1700 ℃, keeping the argon atmosphere, keeping the temperature for 4 hours, cooling the furnace to room temperature to obtain the ceramic membrane substrate material, and testing the aperture of a composite layer consisting of C and SiC on the surface of the ceramic membrane substrate material by adopting a gas bubble method, wherein the average aperture on the surface is 15 microns.
Example 2:
a ceramic membrane base material, the inner layer of the ceramic membrane base material is a pure carbon layer, the average aperture of the inner layer is 300 mu m, the outer layer is a composite layer consisting of C and SiC, and the average aperture of the outer layer is 16 mu m; the pores of the inner layer and the outer layer of the ceramic membrane base material are communicated.
The preparation method of the ceramic membrane-based material comprises the following steps:
and (1.1) preparing the multi-channel tube ceramic membrane substrate according to the required shape by using foamed asphalt with the average pore diameter of 300 mu m as a raw material. Putting the monocrystalline silicon into a heat treatment furnace, heating to 1500 ℃ at the heating rate of 15 ℃/min under the argon atmosphere to melt the crystalline silicon to form molten Si, then immersing the multichannel tube ceramic membrane substrate into the molten Si, keeping the argon atmosphere in the furnace, and keeping the temperature for 60 min.
(1.2) taking out the multi-channel tube ceramic membrane substrate from the molten Si, heating the inside of the furnace to 1750 ℃, keeping the argon atmosphere, keeping the temperature for 4 hours, cooling the furnace to room temperature to obtain a ceramic membrane base material, and testing the aperture of a composite layer consisting of C and SiC on the surface of the ceramic membrane base material by adopting a gas bubble method, wherein the average aperture on the surface is 16 microns.
Example 3:
a ceramic membrane base material, the inner layer of the ceramic membrane base material is a pure carbon layer, the average aperture of the inner layer is 300 mu m, the outer layer is a composite layer consisting of C and SiC, and the average aperture of the outer layer is 20 mu m; the pores of the inner layer and the outer layer of the ceramic membrane base material are communicated.
The preparation method of the ceramic membrane-based material comprises the following steps:
and (1.1) preparing the multi-channel tube ceramic membrane substrate according to the required shape by using foamed asphalt with the average pore diameter of 300 mu m as a raw material. Putting the monocrystalline silicon into a heat treatment furnace, heating to 1500 ℃ at the heating rate of 15 ℃/min under the argon atmosphere to melt the crystalline silicon to form molten Si, then immersing the multichannel tube ceramic membrane substrate into the molten Si, keeping the argon atmosphere in the furnace, and keeping the temperature for 60 min.
(1.2) taking out the multi-channel tube ceramic membrane substrate from the molten Si, heating the inside of the furnace to 1650 ℃, keeping the argon atmosphere, keeping the temperature for 2 hours, cooling the furnace to room temperature to obtain a ceramic membrane base material, and testing the aperture of a composite layer consisting of C and SiC on the surface of the ceramic membrane base material by adopting a gas bubble method, wherein the average aperture on the surface is 20 microns.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention. Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (3)
1. A ceramic membrane based material is characterized in that the inner layer of the ceramic membrane based material is a pure carbon layer, the average pore diameter of the inner layer is 300-500 mu m, the outer layer is a composite layer consisting of C and SiC, and the average pore diameter of the outer layer is 10-20 mu m; the pores of the inner layer and the outer layer of the ceramic membrane-based material are communicated;
the ceramic membrane base material is prepared by the following method:
(1) preparing a ceramic membrane substrate according to a required shape by using foamed asphalt with the average pore diameter of 300-500 mu m as a raw material, immersing the ceramic membrane substrate into molten Si in a heat treatment furnace, and keeping an inert atmosphere in the furnace for 30-60 min; in the step (1), the temperature of a heat treatment furnace is raised to 1450-1550 ℃ at the temperature rise rate of 15-20 ℃/min, so that crystalline silicon is melted to form molten Si;
(2) and taking out the ceramic membrane substrate from the molten Si, heating the ceramic membrane substrate to 150-250 ℃ in the furnace, keeping the inert atmosphere, keeping the temperature for 2-4 h, and then cooling the ceramic membrane substrate to room temperature along with the furnace to obtain the ceramic membrane substrate material.
2. Ceramic membrane based material according to claim 1, wherein in step (1) the ceramic membrane substrate is a multi-channel tube, a single-channel tube or a flat plate.
3. Ceramic membrane based material according to claim 1, wherein the inert atmosphere in step (1) is argon.
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| CN201710373875.XA CN107051226B (en) | 2017-05-24 | 2017-05-24 | Ceramic membrane base material |
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| CN201710373875.XA CN107051226B (en) | 2017-05-24 | 2017-05-24 | Ceramic membrane base material |
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| CN107051226A CN107051226A (en) | 2017-08-18 |
| CN107051226B true CN107051226B (en) | 2020-12-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4024946B2 (en) * | 1998-09-11 | 2007-12-19 | 東洋炭素株式会社 | Mechanical seal member |
| CN100457682C (en) * | 2003-09-22 | 2009-02-04 | 中国科学院金属研究所 | Compact foamy thyrite in high intensity and preparation method |
| US20100234481A1 (en) * | 2009-03-13 | 2010-09-16 | Japan Atomic Energy Agency | Porous ceramics manufacturing method |
| CN102173853A (en) * | 2011-02-16 | 2011-09-07 | 北京科技大学 | Method for preparing highly-oriented perforated porous SiC ceramic material |
| CN103721578B (en) * | 2013-12-17 | 2016-05-04 | 杭州创享环境技术有限公司 | The preparation method of the pure matter silicon carbide film of a kind of multichannel unsymmetric structure |
| CN105688684B (en) * | 2014-11-27 | 2018-01-16 | 中国科学院金属研究所 | With three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and preparation method |
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Effective date of registration: 20210129 Address after: 543000 room 330, 3 / F, Yuegui building, the junction of the two provinces at the east exit of Wuzhou City, Guangxi Zhuang Autonomous Region Patentee after: GUANGXI BIQINGYUAN ENVIRONMENTAL PROTECTION INVESTMENT Co.,Ltd. Address before: 543000 Zhaoping Town, Zhaoping County, Hezhou, the Guangxi Zhuang Autonomous Region (Lingjiao Village) Patentee before: GUANGXI BRIWATER ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
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Denomination of invention: A ceramic membrane based material Effective date of registration: 20221227 Granted publication date: 20201201 Pledgee: Nanning Branch of China Everbright Bank Co.,Ltd. Pledgor: GUANGXI BIQINGYUAN ENVIRONMENTAL PROTECTION INVESTMENT Co.,Ltd. Registration number: Y2022450000238 |
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