CN114773090A - Method for enhancing strength of ceramic membrane support - Google Patents
Method for enhancing strength of ceramic membrane support Download PDFInfo
- Publication number
- CN114773090A CN114773090A CN202111322011.8A CN202111322011A CN114773090A CN 114773090 A CN114773090 A CN 114773090A CN 202111322011 A CN202111322011 A CN 202111322011A CN 114773090 A CN114773090 A CN 114773090A
- Authority
- CN
- China
- Prior art keywords
- ceramic membrane
- membrane support
- sol
- strength
- enhancing
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 23
- 239000013067 intermediate product Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 238000009489 vacuum treatment Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 20
- 230000004907 flux Effects 0.000 abstract description 12
- 238000005470 impregnation Methods 0.000 abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—Alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5035—Silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
- C04B41/5338—Etching
- C04B41/5353—Wet etching, e.g. with etchants dissolved in organic solvents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a strength enhancing method of a ceramic membrane support, which comprises the following steps: (1) putting the ceramic membrane support into electrochemical liquid for soaking; (2) putting the impregnated ceramic membrane support body into an enhancement solution for impregnation to obtain an intermediate product; (3) carrying out heat treatment on the intermediate product at 600-1000 ℃ for a preset time; the electrochemical solution comprises a polar solvent and a solute, wherein the solute is one or more of saturated monocarboxylic acid, sulfuric acid, nitric acid and hydrofluoric acid; the enhancing liquid is one or more of silica sol, aluminum sol, titanium sol, zirconium sol and yttrium sol. The ceramic membrane support body can effectively improve the strength of the ceramic membrane support body, and has little influence on flux.
Description
Technical Field
The invention relates to the technical field of ceramic filtering membranes, in particular to a strength enhancing method of a ceramic membrane support.
Background
The ceramic membrane is a separation membrane commonly used in the field of membrane separation. The ceramic membrane has the advantages of high temperature resistance, solvent resistance, high mechanical property and long service life. The conventional ceramic film is generally attached to a support, and the common support is generally formed by molding and firing alumina powder. The ceramic membrane module is formed by coating (soaking, spraying and the like) ceramic membrane liquid on a ceramic membrane support body and then annealing.
In the prior art, in order to reduce the preparation cost of the ceramic membrane, mineral phases such as kaolin, quartz, feldspar and the like are often introduced into the raw materials of the ceramic membrane support, the sintering temperature of the support is reduced, and the strength of the support is ensured by taking mullite, corundum, zirconia and the like as main bodies, but the strength of the ceramic membrane support is inevitably reduced. However, the ceramic membrane module has a high requirement for the strength of the support, specifically, when the ceramic membrane module is subjected to back washing, the water pressure rises to about 2bar, which requires that the ceramic support has sufficient strength without cracking.
The existing methods for improving the strength of the ceramic membrane support body comprise two types: one is to change the shape design, such as to increase the thickness or reduce the size as a whole. However, increased wall thickness causes a decrease in flux; the whole size is reduced, and then later assembly is needed, the process is complex, and the cost is high. The other is to introduce ceramic fiber into the raw materials to toughen the ceramic fiber after sintering, but the ceramic fiber has higher cost, and the ceramic fiber can block the holes of the ceramic support body to reduce the flux.
On the other hand, ceramic membrane modules are generally required to have high flux and high strength. In order to increase the flux, the porosity needs to be increased. To increase the strength, the porosity needs to be reduced. It is seen that high flux and high strength are often difficult to ensure simultaneously.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a strength enhancing method for a ceramic membrane support, which can effectively enhance the strength of the ceramic membrane support without reducing flux.
In order to solve the technical problem, the invention provides a strength enhancing method for a ceramic membrane support, which comprises the following steps:
(1) putting the ceramic membrane support into electrochemical solution for soaking;
(2) immersing the ceramic membrane support body immersed by the electrochemical solution into the enhancing solution to obtain an intermediate product;
(3) carrying out heat treatment on the intermediate product at 600-1000 ℃;
the electrochemical liquid comprises a polar solvent and a solute, wherein the solute is one or more of saturated monocarboxylic acid, sulfuric acid, nitric acid and hydrofluoric acid;
the enhancing solution is one or more of silica sol, aluminum sol, titanium sol, zirconia precursor solution and yttrium sol.
As an improvement of the technical scheme, the polar solvent is one or more of methanol, ethanol, acetone, propylene glycol and hexane;
the solute is one or more of formic acid, acetic acid and sulfuric acid.
As an improvement of the technical scheme, the concentration of the solute in the electrochemical liquid is 1 x 10-6～1mol/L。
As an improvement of the technical scheme, the enhancement solution also comprises a dispersing agent and a pH regulator, wherein the dispersing agent is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polyacrylamide;
the pH regulator is ammonia water and/or hydrochloric acid.
As an improvement of the technical scheme, the average grain diameter of the silica sol, the aluminum sol, the titanium sol and the yttrium sol is 20-100 nm.
As an improvement of the technical scheme, the concentration of the silica sol, the aluminum sol, the titanium sol and the yttrium sol is 1-15 wt%.
As an improvement of the technical scheme, in the step (1) and the step (2), ultrasonic treatment and/or vacuum pumping treatment are/is carried out in the dipping process.
In the step (1) and the step (2), vacuumizing treatment is performed in the dipping process, and then ultrasonic treatment is performed;
the pressure of the vacuumizing treatment is 1-3 kPa, and the treatment time is 0.1-1 h; the ultrasonic treatment frequency is 20-120 kHz, and the treatment time is 1-10 h.
As an improvement of the technical proposal, in the step (3), the heat treatment time is 30 s-2 h.
As an improvement of the technical scheme, in the step (3), the heat treatment temperature is 600-900 ℃, and the time is 0.5-1.5 h.
The implementation of the invention has the following beneficial effects:
according to the strength enhancement method of the ceramic membrane support body, the weak glass phase structure on the surface of the ceramic membrane support body is removed through the impregnation of the electrochemical liquid, and then the second phase with stronger mechanical property is repaired in the area where the weak glass phase is removed through the impregnation of the enhancement liquid, so that the strength of the ceramic membrane support body is effectively improved, and the flux of the ceramic membrane support body is not changed. The reinforcement method does not change the early-stage forming and sintering process of the ceramic membrane support body, can be integrated into the post-stage heat treatment process of the ceramic membrane component, and has the advantages of simple process, low cost and high efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to specific embodiments.
The existing ceramic membrane support (particularly the low-cost ceramic membrane support) has poor strength and short service life. For this reason, it is necessary to improve the strength thereof. In the process of studying the problem, the inventor finds that, in the use process of the ceramic membrane support, the place where cracks are easy to appear is often the place where a weak phase glass phase structure exists, although the structure partially shows crack defects immediately after sintering, initial cracks are easy to generate in the process of stress or thermal shock, and the initial cracks are easy to rapidly diffuse in the recycling process of the ceramic membrane module to form a large number of cracks, further generate the problems of fracture, breakage and the like, and reduce the service life of the ceramic membrane module. Based on the above analysis, the inventor proposes a strength enhancing method for a ceramic membrane support, which specifically comprises the following steps:
(1) putting the ceramic membrane support into electrochemical solution for soaking;
the electrochemical solution comprises a polar solvent and a solute, and the polar solvent has high polarizability and can dissociate to form protons to form electrolyte, so that electrochemical corrosion can be caused. After the second phase polar liquid (solute) is added, more protons can be dissociated from the solute, the electrochemical corrosion efficiency is higher, and the corrosivity is stronger. This proton corrosion can etch away weak glass phase structures on the support surface.
Specifically, the polar solvent is selected from one or more of water, methanol, ethanol, acetone, propylene glycol, and hexane, but is not limited thereto. Preferably, the polar solvent is selected from one or any two of water, methanol, ethanol and hexane. The solute is selected from one or more of formic acid, acetic acid and sulfuric acid, but is not limited thereto. Preferably, the solute is formic acid and/or acetic acid.
Specifically, the concentration of solute in the electrochemical solution is 1 × 10-6About 1mol/L, exemplary is about 1.5X 10-6mol/L、5×10-6mol/L、2×10-5mol/L、6×10-5mol/L、4×10-4mol/L, 0.003mol/L, 0.05mol/L or 0.4mol/L, but is not limited thereto.
In particular, in order to improve the removal efficiency of the weak glass phase, vacuum pumping treatment and/or ultrasonic treatment can be adopted in the impregnation process. Preferably, in the dipping process, vacuumizing treatment is firstly carried out to enable the electrochemical liquid to quickly penetrate into the cracks; sonication is then performed to accelerate the removal of the weak glassy phase. Specifically, the pressure of the vacuuming treatment is 1 to 3kPa, and is exemplarily 1.2kPa, 1.5kPa, 2.1kPa, 2.3kPa or 2.8kPa, but not limited thereto, and the time of the vacuuming treatment is 0.1 to 1h, and is exemplarily 0.2h, 0.4h, 0.6h, 0.8h or 0.9h, but not limited thereto. The frequency of the ultrasonic treatment is 20 to 120kHz, and is exemplified by 25kHz, 33kHz, 42kHz, 55kHz, 68kHz, 73kHz, or 95kHz, but is not limited thereto. The time of the ultrasonic treatment is 1 to 10 hours, and is exemplified by 1.5 hours, 2.4 hours, 3.4 hours, 4 hours, 5 hours, 7 hours or 8.5 hours, but is not limited thereto.
It should be noted that the method of the present invention can also be applied to ceramic membrane supports of different specifications by controlling the solute concentration in the electrochemical solution, the ultrasonic treatment frequency, and the ultrasonic treatment time.
Further, after the immersion is completed, the electrochemical solution is washed away. Illustratively, the washing may be repeated several times with water until the pH of the washing solution is greater than or equal to 6.8.
(2) Immersing the ceramic membrane support body immersed by the electrochemical solution into the enhancing solution to obtain an intermediate product;
wherein, the enhancing liquid is selected from one or more of silica sol, aluminum sol, titanium sol, zirconia precursor solution and yttrium sol. The sol can fill the gap formed by electrochemical impregnation, and a high-strength repair phase can be formed by post-heat treatment. Preferably, the reinforcing liquid is one or two of silica sol, aluminum sol and zirconia precursor solution. The zirconia precursor may be, but not limited to, zirconium nitrate, zirconium n-propoxide, and zirconium oxychloride. The mass fraction of the sol in the reinforcing liquid is 1 to 15 wt%, and is illustratively 1.5 wt%, 2.3 wt%, 4.8 wt%, 5.7 wt%, 6.5 wt%, 10.2 wt%, 13.5 wt%, 14.2 wt%, but is not limited thereto.
Specifically, the average particle size of the silica sol, the aluminum sol, the titanium sol, and the yttrium sol is 20 to 100nm, and is exemplified by 25nm, 35nm, 45nm, 55nm, 65nm, 75nm, 85nm, or 95nm, but not limited thereto.
Furthermore, a dispersing agent and a pH regulator are also included in the reinforcing liquid. Specifically, the dispersant may be one or more of PVP (polyvinylpyrrolidone), PEG (polyethylene glycol), PVA (polyvinyl alcohol), PAM (polyacrylamide), but is not limited thereto. Preferably, the dispersant is PVP or PEG. The mass fraction of the dispersing agent in the reinforcing liquid is 0.1-1.5 wt%. Specifically, the pH regulator is ammonia water or dilute hydrochloric acid, but is not limited thereto; the mass fraction of the reinforcing liquid is 0.01-0.5 wt%.
In particular, vacuuming and/or ultrasonic treatment can be adopted in the dipping process. Preferably, in the dipping process, vacuumizing treatment is firstly carried out, so that the electrochemical liquid quickly permeates the area where the filled weak glass phase is located; then, ultrasonic treatment is performed. Specifically, the pressure of the vacuuming treatment is 1 to 3kPa, and is exemplified by 1.2kPa, 1.5kPa, 2.1kPa, 2.3kPa, or 2.8kPa, but not limited thereto, and the time of the vacuuming treatment is 0.1 to 1 hour, and is exemplified by 0.2 hour, 0.4 hour, 0.6 hour, 0.8 hour, or 0.9 hour, but is not limited thereto. The frequency of the ultrasonic treatment is 20-120 kHz, and is exemplified by 25kHz, 33kHz, 42kHz, 55kHz, 68kHz, 73kHz or 95kHz, but is not limited thereto. The time of the ultrasonic treatment is 2-10 h, and exemplary time is 3h, 4.4h, 6.4h, 7h, 8.5h, 9h or 9.5h, but is not limited thereto.
Preferably, after the impregnation is complete, the intermediate is thoroughly dried.
Preferably, in one embodiment of the present invention, the preparation process of the ceramic membrane module may be integrated with the enhancement method of the present invention, i.e. the ceramic membrane is coated (sprayed, dipped) on the surface of the intermediate body after the intermediate body is dried.
(3) Carrying out heat treatment on the intermediate product at 600-1000 ℃;
the heat treatment temperature is 600-1000 deg.C, and exemplary temperatures are 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C or 950 deg.C, but not limited thereto. Preferably, the heat treatment temperature is 600-900 ℃. The heat treatment time is 30s to 2 hours, exemplary 1min, 5min, 15min, 35min, 44min, 1h, 1.2h, 1.5h or 1.8h, but not limited thereto; preferably, the heat treatment time is 0.5-1.5 h. The heat treatment process enables the sol in the reinforcing liquid to generate chemical reaction, and high-strength repairing phases are formed in the ceramic membrane support body and the surface area, so that the strength of the ceramic membrane support body is improved, but the flux is not reduced.
Specifically, during heat treatment, the ceramic membrane support body after drying is placed on a kiln car, and the pipe orifice of the ceramic membrane support body faces the direction of a flame gun, so that the ceramic membrane support body can be rapidly heated by heat flow. Or sintering can be directly carried out by adopting a microwave sintering process.
The invention is further illustrated by the following specific examples:
example 1
The embodiment provides a strength enhancement method for a ceramic membrane support, which comprises the following steps:
(1) putting the ceramic membrane support into electrochemical liquid for soaking, and vacuumizing (1kPa) for treatment for 3 h; after the impregnation is finished, washing with water until the pH value of the washing water is 6.8;
wherein, the electrochemical solution is a sulfuric acid solution with the concentration of 0.01mol/L, and the main crystal phase of the ceramic support body is alumina and mullite.
(2) Soaking the ceramic membrane support body soaked by the electrochemical solution in the enhancing solution, and performing ultrasonic treatment in the soaking process at the frequency of 100kHz for 8 hours; obtaining an intermediate product; drying the intermediate product at 100 deg.C;
wherein the reinforcing liquid is a zirconium n-propoxide solution, the concentration of the zirconium n-propoxide is 12 wt%, and the average particle size of the zirconium n-propoxide solution is 50 nm.
(3) The intermediate product was heat treated at 1000 ℃ for 30 s.
10 samples are selected to be respectively reinforced by the method, and the bending strength and the flux before and after the samples are reinforced are enhanced, and the results are as follows:
example 2
The embodiment provides a strength enhancement method for a ceramic membrane support, which comprises the following steps:
(1) soaking the ceramic membrane support in an electrochemical solution, vacuumizing (1.5kPa) for 10min, and then carrying out ultrasonic treatment at 100kHz for 2 h; after the ultrasonic treatment is finished, washing with water until the pH value of the washing water is 7;
wherein the solvent of the electrochemical solution is methanol, the solute is formic acid, and the concentration is 1 × 10-3mol/L, the main crystal phase of the ceramic support body is alumina, mullite and kaolin.
(2) Soaking the ceramic membrane support body soaked by the electrochemical solution into the enhancement solution, vacuumizing (1kPa) for 30min, and then carrying out ultrasonic treatment at 100kHz for 2 h; obtaining an intermediate product after dipping; airing the intermediate product for 24 hours at room temperature in a ventilating way;
wherein the concentration of the silica sol in the reinforcing liquid is 10 wt%, the average grain diameter is 80nm, the concentration of the aluminum sol is 5 wt%, and the average grain diameter is 30 nm; the PVP content was 0.5 wt% and adjusted to pH 9 with ammonia.
(3) The intermediate product is heat treated at 900 ℃ for 1 h.
10 samples are selected to be reinforced by the method respectively, and the bending strength and the flux before and after the samples are reinforced are enhanced, and the results are as follows:
example 3
The embodiment provides a strength enhancing method for a ceramic membrane support, which comprises the following steps:
(1) soaking the ceramic membrane support body in an electrochemical solution, firstly vacuumizing (1.5kPa) for 10min, and then carrying out ultrasonic treatment for 6h at 120 kHz; after the ultrasonic treatment is finished, washing with water until the pH value of the washing water is 7;
wherein the electrochemical solution comprises ethanol and hexane (volume ratio of 1:1) as solvent, acetic acid as solute, and concentration of 1 × 10- 5And the main crystal phase of the ceramic support body is alumina and mullite.
(2) Soaking the ceramic membrane support body soaked by the electrochemical solution into the enhancement solution, vacuumizing (1kPa) for 30min, and then performing ultrasonic treatment at 120kHz for 3 h; obtaining an intermediate product after dipping; drying the intermediate product at 110 ℃ for 10 h;
wherein the concentration of zirconium nitrate in the enhancing solution is 10 wt%, the average grain diameter is 50nm, the concentration of silica sol is 5 wt%, and the average grain diameter is 60 nm; the PEG200 content was 0.3 wt%, adjusted to pH 5 with ammonia.
(3) The intermediate product was heat treated at 600 ℃ for 1 h.
10 samples are selected to be respectively reinforced by the method, and the bending strength and the flux before and after the samples are reinforced are enhanced, and the results are as follows:
while the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The strength enhancement method of the ceramic membrane support is characterized by comprising the following steps of:
(1) putting the ceramic membrane support into electrochemical solution for soaking;
(2) soaking the ceramic membrane support body soaked by the electrochemical solution into the enhancement solution to obtain an intermediate product;
(3) carrying out heat treatment on the intermediate product at 600-1000 ℃;
the electrochemical solution comprises a polar solvent and a solute, wherein the solute is one or more of saturated monocarboxylic acid, sulfuric acid, nitric acid and hydrofluoric acid;
the enhancement solution is selected from one or more of silica sol, aluminum sol, titanium sol, zirconia precursor solution and yttrium sol.
2. The method for enhancing strength of a ceramic membrane support according to claim 1, wherein the polar solvent is one or more selected from methanol, ethanol, acetone, propylene glycol, and hexane;
the solute is one or more of formic acid, acetic acid and sulfuric acid.
3. A method for increasing strength of a ceramic membrane support according to claim 1 or 2, wherein the concentration of said solute in said electrochemical solution is 1 x 10-6～1mol/L。
4. The method for enhancing the strength of a ceramic membrane support according to claim 1, wherein the enhancing solution further comprises a dispersing agent and a pH regulator, wherein the dispersing agent is one or more selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polyacrylamide;
the pH regulator is ammonia water and/or hydrochloric acid.
5. A method for enhancing strength of a ceramic membrane support according to claim 1 or 4, wherein the silica sol, the aluminum sol, the titanium sol, and the yttrium sol have an average particle size of 20 to 100 nm.
6. A method for enhancing the strength of a ceramic membrane support according to claim 1 or 4, wherein the concentration of the silica sol, the aluminum sol, the titanium sol, or the yttrium sol is 1 to 15 wt%.
7. A method for enhancing strength of a ceramic membrane support according to claim 1, wherein in step (1) and step (2), the dipping process is performed by ultrasonic treatment and/or vacuum treatment.
8. A ceramic membrane support strength enhancement method according to claim 1 or 7, wherein in the step (1) and the step (2), the dipping process is performed with vacuum pumping treatment and then ultrasonic treatment;
the pressure of the vacuumizing treatment is 1-3 kPa, and the treatment time is 0.1-1 h; the ultrasonic treatment frequency is 20-120 kHz, and the treatment time is 1-10 h.
9. A method for enhancing strength of a ceramic membrane support according to claim 1, wherein in step (3), the heat treatment time is 30 s-2 h.
10. The method for enhancing strength of a ceramic membrane support according to claim 1 or 9, wherein in step (3), the heat treatment temperature is 600 to 900 ℃ and the time is 0.5 to 1.5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111322011.8A CN114773090A (en) | 2021-11-09 | 2021-11-09 | Method for enhancing strength of ceramic membrane support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111322011.8A CN114773090A (en) | 2021-11-09 | 2021-11-09 | Method for enhancing strength of ceramic membrane support |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114773090A true CN114773090A (en) | 2022-07-22 |
Family
ID=82423177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111322011.8A Pending CN114773090A (en) | 2021-11-09 | 2021-11-09 | Method for enhancing strength of ceramic membrane support |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773090A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003165A (en) * | 2022-11-16 | 2023-04-25 | 西安聚能高温合金材料科技有限公司 | Surface strengthening method of shaped refractory material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0199618A (en) * | 1987-10-13 | 1989-04-18 | Mitsubishi Heavy Ind Ltd | Production of ceramics porous film |
| US20050172811A1 (en) * | 2004-02-10 | 2005-08-11 | Conocophillips Company | Hydrogen-selective silica-based membrane |
| CN110002893A (en) * | 2019-02-20 | 2019-07-12 | 谭九香 | A kind of preparation method of ceramic super-filtering film |
| CN112047711A (en) * | 2020-07-23 | 2020-12-08 | 北京卫星制造厂有限公司 | Method for improving high-temperature heat-insulating property of nano porous heat-insulating material |
| CN112679231A (en) * | 2021-01-12 | 2021-04-20 | 广东金刚新材料有限公司 | Enhancement treatment method for ceramic roller |
| CN112939580A (en) * | 2021-01-29 | 2021-06-11 | 广西碧清源环保投资有限公司 | Preparation method of ceramic filtering membrane |
-
2021
- 2021-11-09 CN CN202111322011.8A patent/CN114773090A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0199618A (en) * | 1987-10-13 | 1989-04-18 | Mitsubishi Heavy Ind Ltd | Production of ceramics porous film |
| US20050172811A1 (en) * | 2004-02-10 | 2005-08-11 | Conocophillips Company | Hydrogen-selective silica-based membrane |
| CN110002893A (en) * | 2019-02-20 | 2019-07-12 | 谭九香 | A kind of preparation method of ceramic super-filtering film |
| CN112047711A (en) * | 2020-07-23 | 2020-12-08 | 北京卫星制造厂有限公司 | Method for improving high-temperature heat-insulating property of nano porous heat-insulating material |
| CN112679231A (en) * | 2021-01-12 | 2021-04-20 | 广东金刚新材料有限公司 | Enhancement treatment method for ceramic roller |
| CN112939580A (en) * | 2021-01-29 | 2021-06-11 | 广西碧清源环保投资有限公司 | Preparation method of ceramic filtering membrane |
Non-Patent Citations (1)
| Title |
|---|
| 陈纲领等: "多孔陶瓷膜支撑体在HNO_3溶液中的腐蚀性能研究", 《化学工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003165A (en) * | 2022-11-16 | 2023-04-25 | 西安聚能高温合金材料科技有限公司 | Surface strengthening method of shaped refractory material |
| CN116003165B (en) * | 2022-11-16 | 2023-11-24 | 西安聚能高温合金材料科技有限公司 | Surface strengthening method of shaped refractory material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102345127B (en) | Surface treatment method of superhydrophobic aluminum foil | |
| CN105113213B (en) | A kind of method for preparing anti-oxidation composite coating in carbon fiber surface | |
| CA2071942C (en) | Sol-gel process for glass and ceramic articles | |
| CN106653373B (en) | A kind of aluminium electrolutic capacitor Waste Acid From Hua Cheng Foil and its production technology | |
| CN114773090A (en) | Method for enhancing strength of ceramic membrane support | |
| CN109133891B (en) | In-situ preparation method of high-density and non-complex-phase high-purity quartz ceramic | |
| CN112047711A (en) | Method for improving high-temperature heat-insulating property of nano porous heat-insulating material | |
| CN111005226A (en) | Method for modifying interface of three-dimensional fabric of alumina fiber and modified three-dimensional fabric of alumina fiber prepared by method | |
| Packham et al. | Mechanical factors in the adhesion of polyethylene to aluminium | |
| CN109928780A (en) | A kind of manufacturing method of ceramic core surface inertness coat | |
| CN104478475A (en) | High-temperature-resistant high-strength SiC clad carbon foam composite thermal insulating material and preparation method thereof | |
| CN110318253A (en) | A kind of preparation method of carbon fiber surface modification anti-oxidation composite coating | |
| CN110904404B (en) | Technological method and device based on titanium alloy surface laser nitriding and shot blasting synchronous compounding technology | |
| CN102418098A (en) | Low-damage preparation method of super-hydrophobic surface of industrial aluminum foil | |
| CN109309142B (en) | Liquid source diffusion process before silicon wafer glass passivation | |
| CN113941370A (en) | Method for preparing monolithic catalyst cordierite carrier by adopting plasma | |
| CN108947498B (en) | Preparation method of alumina-silicon carbide porous composite ceramic | |
| CN112679231B (en) | Enhancement treatment method for ceramic roller | |
| CN115093209A (en) | Preparation method of high-strength high-stability multilayer composite structure fused quartz material | |
| CN116496069A (en) | Preparation method of fiber porous ceramic and fiber porous ceramic | |
| CN106148962A (en) | The treatment fluid of a kind of stainless steel surface nano hole and application process thereof | |
| CN104774027A (en) | Preparation method of tubular ceramic membranes | |
| CN112390658B (en) | Mechanical processing and forming method for oxide foamed ceramic material | |
| CN104774025A (en) | Supporting body preparation method of membrane for water treatment | |
| CN113816754A (en) | Preparation method of novel SiC/SiC micro composite material containing multilayer zirconium silicate interface phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220901 Address after: Original Changjiang carton factory, Guanyao Dalan Industrial Zone, Shishan town, Nanhai District, Foshan City, Guangdong Province Applicant after: GUANGDONG JINGANG NEW MATERIAL CO.,LTD. Applicant after: Guangdong Foshan Ceramic Research Institute Holding Group Co.,Ltd. Address before: 528000 No. 18, Huiyuan Road, Chancheng District, Foshan City, Guangdong Province Applicant before: Guangdong Foshan Ceramic Research Institute Holding Group Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220722 |
|
| RJ01 | Rejection of invention patent application after publication |