CN117700232A - Silicon-manganese slag reinforced acid and alkali resistant silicon carbide ceramic membrane support and preparation method thereof - Google Patents
Silicon-manganese slag reinforced acid and alkali resistant silicon carbide ceramic membrane support and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 49
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002893 slag Substances 0.000 title claims abstract description 41
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003513 alkali Substances 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910000720 Silicomanganese Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052661 anorthite Inorganic materials 0.000 claims abstract description 5
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 claims abstract description 5
- 238000010304 firing Methods 0.000 claims abstract description 5
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- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 5
- 239000002910 solid waste Substances 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 238000007873 sieving Methods 0.000 claims abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- 239000011148 porous material Substances 0.000 claims description 11
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- 235000011837 pasties Nutrition 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
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- 238000004898 kneading Methods 0.000 claims description 4
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
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- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
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- 239000000126 substance Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 15
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 102000007590 Calpain Human genes 0.000 description 1
- 108010032088 Calpain Proteins 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- -1 high borosilicate Chemical compound 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 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 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a silicon-manganese slag reinforced acid and alkali resistant silicon carbide ceramic membrane support and a preparation method thereof, and specifically relates to a preparation method thereof, wherein industrial solid waste silicon-manganese slag is taken as a raw material, volatile and degradable substances are removed at high temperature, grinding and sieving are carried out on the silicon carbide powder according to a proportion, and graphite powder, hydroxypropyl methylcellulose, soybean oil, glycerol and the like are added for uniform mixing; and preparing a wet blank of the membrane support body through extrusion molding, drying and then firing and molding in a muffle furnace. The preparation process is simple and short in period, the high-performance silicomanganese slag-silicon carbide ceramic membrane support is obtained through optimization by a particle grading method, and meanwhile, the solid waste-silicomanganese slag is used as a sintering aid, so that the production cost and sintering temperature of raw materials can be reduced, and the characteristics of oxides such as silicon, aluminum, calcium, manganese and the like contained in the silicomanganese slag can be utilized to form alkali-resistant mullite, anorthite and calmultifarite serving as a constituent phase for neck connection among silicon carbide particles.
Description
Technical Field
The invention relates to a silicon-manganese slag reinforced acid and alkali resistant silicon carbide ceramic membrane support, and belongs to the technical field of inorganic membrane separation materials.
Background
The emerging non-oxide silicon carbide ceramic membranes have a high anti-fouling capability in water treatment applications due to their low isoelectric points on their surfaces. In addition, the silicon carbide ceramic membrane has stronger surface hydrophilicity and more concentrated pore size distribution, so that the silicon carbide ceramic membrane shows higher water flux under low pressure conditions, and the silicon carbide ceramic membrane can be rapidly popularized and applied in the fields of food, medicine and water treatment, so that the silicon carbide ceramic membrane has become the ceramic membrane material with the most commercial prospect. However, at present, only a few enterprises realize industrialization of the silicon carbide ceramic membrane at home and abroad, and the commercialized silicon carbide ceramic membrane is mainly prepared by adopting a recrystallization sintering process, namely, high-temperature sintering at 2000 ℃ or higher under inert atmosphere, so that the problems of high energy consumption and high production cost are caused, which is contrary to the low cost required by wastewater treatment. Adding sintering aid (Al) 2 O 3 、ZrO 2 、TiO 2 Isooxides and minerals such as kaolin, potassium feldspar, etc.) are effective methods for reducing the sintering temperature (1400 ℃) of a silicon carbide ceramic membrane support body by reaction sintering, and the sintering mechanism is SiO generated by oxidation of a silicon carbide surface layer 2 React with the sintering aid to form neck bonds between the silicon carbide particles. The sintering temperature of the ceramic membrane support body prepared by the method is still higher, and the cost is high; secondly due to SiO 2 Is generally poor in alkali resistance.
The prior art discloses a SiO as patent CN 101913872A 2 As a sintering aid, a multi-element liquid phase is formed as a connecting phase between silicon carbide particles at 1400 ℃, but due to poor alkali resistance, the flux cannot be recovered or applied to an alkaline environment in practical application by washing with an alkaline solution. Also patent CN 107619281B discloses the use of zircon, high borosilicate, potash feldspar, quartz sand, sozhou earth, burnt talcum, chalk and fluorite as sintering aids at 1400 DEG CThe acid-alkali resistant porous silicon carbide ceramic membrane is prepared, but the sintering auxiliary agent composed of various minerals has relatively high raw material cost and high sintering temperature, and the prepared silicon carbide ceramic membrane has better acid and alkali resistance and lower bending strength. Therefore, there is a need to develop a low sintering temperature, low cost and high performance silicon carbide ceramic membrane support.
The silicomanganese slag is industrial waste slag formed in the production process of the silicomanganese alloy. At present, the yield of the silicomanganese slag in China is up to 1358.5 ten thousand tons, and the silicomanganese slag is usually treated by stacking, landfill and other modes, so that a large amount of land is occupied, and the pollution of soil and water resources caused by leaching of heavy metal ions can be caused.
At present, the traditional method for effectively utilizing the silicomanganese slag is to add the silicomanganese slag into the production of industries such as cement, mineral wool, water permeable bricks and the like. The components of the silicomanganese slag are rich in SiO 2 And Al 2 O 3 In addition, the compound contains Ca and Mn in relatively high proportion, and the main problem of the current utilization method is that functional elements such as silicon, aluminum, calcium, manganese and the like cannot be comprehensively utilized. Therefore, how to utilize the silicomanganese slag and the multifunctional elements therein, and to improve the utilization rate of the silicomanganese slag and the ecological environment are the problems to be solved.
Disclosure of Invention
(one) solving the technical problems
Based on the characteristics of oxides such as silicon, aluminum, manganese, calcium and the like in the components of the silicon-manganese slag, the invention provides the silicon carbide ceramic membrane support body with enhanced acid and alkali resistance and the preparation method thereof, so as to solve the problems of high raw material cost, high sintering temperature and general inakali resistance of the membrane support body in the membrane separation process in the prior art, and simultaneously, the invention can absorb industrial solid wastes and relieve the improvement of ecological environment. And neck connection among silicon carbide particles, bending strength, separation precision and comprehensive performance of the membrane support are improved under the low-temperature condition in a particle grading mode.
(II) technical scheme
In order to achieve the aim of the invention, the invention provides a silicon-manganese slag reinforced acid and alkali resistant silicon carbide ceramic membrane support, which takes silicon-manganese slag as a sintering aid, obtains strong neck connection through grain composition, and prepares mullite, anorthite and calpain pyroxene with high acid and alkali resistance at low temperature by adopting a reaction sintering method as a constituent phase of neck connection among silicon carbide grains.
The invention relates to a preparation method of a silicon-manganese slag reinforced acid-base resistant silicon carbide ceramic membrane support, which comprises the following steps:
(1) Placing the silicomanganese slag in a muffle furnace, and preserving heat for 2h at 500-700 ℃; cooling to room temperature, taking out, crushing by a crusher, and sieving to obtain silicon-manganese slag powder with different particle diameters;
(2) Weighing silicon-manganese slag powder with different particle sizes in the step (1) and silicon carbide powder, graphite powder and hydroxypropyl methyl cellulose according to the mass ratio of 1-3:5-7:0.5-1:1-3 respectively, and placing the powder into a kneader for uniform mixing;
(3) Weighing soybean oil, glycerol and deionized water in a certain proportion, placing the soybean oil, the glycerol and the deionized water in the step (2), continuously kneading the soybean oil, the glycerol and the deionized water to obtain pasty pug, and placing the pug in a reaction kettle for ageing for 20-30 hours;
(4) Placing the aged pasty pug in the step (3) into a vacuum pug mill for pug refining so as to eliminate bubbles in the pug and placing the vacuum pug into a reaction kettle again for ageing for 20-30 hours;
(5) Placing the pug subjected to secondary aging in the step (4) into an inner cavity of an extruder, extruding under the action of axial pressure to obtain a wet blank of the ceramic membrane support, and drying at room temperature for 48 hours to obtain a dry blank of the ceramic membrane support;
(6) Placing the dried support blank obtained in the step (5) in a muffle furnace, preserving heat at 900-1200 ℃ for 2-4h, firing to form, cooling to room temperature, taking out, placing in an ultrasonic device for ultrasonic treatment for 10-30min to remove impurities on the surface and in pores of the membrane support, and finally placing in an oven for drying at 120 ℃ for 2h;
(7) And (3) weighing the mass of the silicon carbide ceramic membrane supports obtained in the step (6), and respectively taking a certain number of membrane supports and respectively placing the membrane supports in an acid-base solution to determine the acid-base corrosiveness of the membrane supports.
Further, the particle diameters of the silicon-manganese slag powder in the step (1) are about 105, 65, 45 and 15 μm, respectively.
Further, an axial pressure of 5 to 15MPa is applied to the extruder in the above step (5).
Further, in the step (6), the sintering atmosphere in the muffle furnace hearth is air, and the sintering heating rate is 2-6 ℃/min.
Further, the acid-base solution in the above step (7) was 20vol% H respectively 2 SO 4 And 1wt% NaOH solution; the experimental temperature was 90℃and the etching time was 96 hours.
(III) beneficial effects
1. The preparation method has simple preparation process and short period, and simultaneously, the solid waste-silicomanganese slag is used as the sintering auxiliary agent, so that the production cost and sintering temperature of raw materials can be reduced, the alkali resistance of the ceramic membrane support can be improved, and the problem that the ceramic membrane support prepared by reaction sintering is generally not alkali-resistant is solved.
2. According to the invention, the prepared silicomanganese slag-silicon carbide ceramic membrane support has narrower pore size distribution, high porosity, high bending strength and ultra-high pure water permeability in a particle grading mode.
3. The invention not only provides great potential for preparing the silicon carbide ceramic membrane support with low cost and high performance, but also provides an effective way for the value-added utilization of solid wastes.
Drawings
FIG. 1 is a scanning electron microscope image of a silicon carbide ceramic membrane support (M1, M2, M3, M4) prepared from silicon manganese slags of the present invention 105, 65, 45, 15 μm;
FIG. 2 is a photograph of a silicon manganese slag-silicon carbide ceramic membrane support of the present invention before and after acid-base corrosion;
FIG. 3 is a scanning electron microscope image of a silicon manganese slag-silicon carbide ceramic membrane support of the invention before and after acid-base corrosion;
FIG. 4 shows pore size distribution of the silicon-manganese slag-silicon carbide ceramic membrane support of the invention before and after acid-base corrosion;
FIG. 5 is an X-ray diffraction pattern of a silicon-manganese slag-silicon carbide ceramic membrane support of the present invention before and after acid-base corrosion.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Placing 10-30wt% of silicon-manganese slag powder with the particle size of 65 mu m, 50-70wt% of silicon carbide powder, 10-30wt% of graphite powder and 10-30wt% of hydroxypropyl methyl cellulose into a kneader for uniform mixing; placing 1-5wt% of soybean oil, 1-3wt% of glycerol and 20-30wt% of deionized water into a kneader for continuous kneading for 30-60min to obtain pasty pug; placing the pasty pug into a reaction kettle for ageing for 20-30 hours; then placing the mixture in a vacuum mud refining machine for 2-4 times to eliminate bubbles in mud materials; then placing the mixture in a reaction kettle again for ageing for 20-30 hours; placing the mud after secondary aging in an inner cavity of an extruder, slowly applying axial pressure of 5-15MPa, extruding to obtain a tubular ceramic membrane support wet blank, and drying at room temperature for 48 hours to obtain a ceramic membrane support dry blank; and (3) placing the support body dry blank in a muffle furnace, preserving heat at a heating rate of 2-6 ℃/min for 2-4h, firing to form, cooling to room temperature, taking out, then placing in an ultrasonic device for ultrasonic treatment for 10-30min to remove impurities on the surface and in pores of the membrane support body, and finally drying at 120 ℃ for 2h.
The membrane support prepared in this example had an average pore diameter of 3.3. Mu.m, a porosity of 42.98%, and a pure water permeability as high as 131767.74 L.m -2 ·h -1 ·bar -1 The flexural strength was 34.17MPa.
Example 2
Placing 10-30wt% of silicon-manganese slag powder with the particle size of 15 mu m, 50-70wt% of silicon carbide powder, 10-30wt% of graphite powder and 10-30wt% of hydroxypropyl methyl cellulose into a kneader for uniform mixing; placing 1-5wt% of soybean oil, 1-3wt% of glycerol and 20-30wt% of deionized water into a kneader for continuous kneading for 30-60min to obtain pasty pug; placing the pasty pug into a reaction kettle for ageing for 20-30 hours; then placing the mixture in a vacuum mud refining machine for 2-4 times to eliminate bubbles in mud materials; then placing the mixture in a reaction kettle again for ageing for 20-30 hours; placing the mud after secondary aging in an inner cavity of an extruder, slowly applying axial pressure of 5-15MPa, extruding to obtain a tubular ceramic membrane support wet blank, and drying at room temperature for 48 hours to obtain a ceramic membrane support dry blank; and (3) placing the support body dry blank in a muffle furnace, preserving heat at a heating rate of 2-6 ℃/min for 2-4h, firing to form, cooling to room temperature, taking out, then placing in an ultrasonic device for ultrasonic treatment for 10-30min to remove impurities on the surface and in pores of the membrane support body, and finally drying at 120 ℃ for 2h.
The membrane support prepared in this example had an average pore diameter of 3.15. Mu.m, a porosity of 41.03%, and a pure water permeability as high as 120074.60 L.m -2 ·h -1 ·bar -1 The flexural strength was 43.18MPa.
Weighing the mass of the dried silicon carbide ceramic membrane supports, and respectively placing a certain number of membrane supports in 20vol%H 2 SO 4 And 1wt% NaOH solution, and reacting for 96 hours at 90 ℃ to obtain the membrane support body after acid-base corrosion. Referring to fig. 2, a photograph of the inventive silicomanganese slag-silicon carbide ceramic membrane support after acid-base corrosion is shown. Meanwhile, the bending strength and the quality of the membrane support body in the embodiment are kept unchanged after acid corrosion, the quality loss rate of the membrane support body is 8% after alkali corrosion for 12 hours, the bending strength is reduced to 35.52MPa, the loss rate is 15%, and the membrane support body is stable later. This means that the membrane support has high alkali resistance, since most reaction sintering prepared silicon carbide ceramic membrane supports exhibit a high flexural strength loss rate (-35%).
Therefore, the silicon-manganese slag reinforced acid-base resistant silicon carbide ceramic membrane support prepared by the invention has the advantages of better separation precision, pure water permeability and bending strength before and after acid-base corrosion than the ceramic membrane support prepared in the prior art patent CN 107619281B by a particle grading method, and has great competitive advantage.
Referring to the scanning electron microscope images of the silicon carbide ceramic film support bodies prepared by the silicon manganese residues with different particle sizes in the figure 1, it can be seen that at the same sintering temperature, as the particle size of the silicon manganese residues is reduced, the melting degree of the silicon manganese residues is increased, so that the connection mode among the particles is changed from point contact to neck connection. Meanwhile, the silicon manganese slag with small particle size and the melting reaction have synergistic effect, so that stronger neck connection is formed among the silicon carbide particles.
Referring to the scanning electron microscope image shown in fig. 3, it can be seen that the surface of the film support hardly changes after the sample is corroded by the acid solution. Corrosion in alkali solutionNext, the film support surface becomes rough. This phenomenon is due to SiO formed on the surface of SiC particles 2 Chemical reaction with NaOH takes place.
Referring to the pore size distribution before and after alkali corrosion of fig. 4, the average pore size of the membrane support remains about 3.15 μm and the separation accuracy remains almost unchanged, although the quality and bending strength of the membrane support are reduced after alkali corrosion, as compared with the original membrane support.
Referring to the X-ray diffraction patterns of the membrane support before and after acid-base corrosion shown in FIG. 5, mullite (Al) at the neck joint of the original ceramic membrane support can be seen 6 SiO 13 ) Anorthite (CaAl) 2 Si 2 O 8 ) And calpside (CaMnSi) 2 O 6 ) The peak intensity of the characteristic peak is almost unchanged, so that the product has high acid and alkali corrosion resistance. The membrane support body has excellent comprehensive performance in the aspects of production cost, acid and alkali corrosion resistance, pure water permeability and the like, and has stronger commercial competitive advantage.
Claims (5)
1. The utility model provides a silicon manganese sediment reinforcing acid and alkali resistant carborundum ceramic membrane supporter which characterized in that: the silicon-manganese slag reinforced acid-base resistant silicon carbide ceramic membrane support comprises neck connection among silicon carbide particles, wherein alkali-resistant mullite, anorthite and caducite are used as the neck connection among the silicon carbide particles; specifically, silicomanganese slag is used as a sintering aid, and a reaction sintering method is adopted to prepare mullite, anorthite and cisco which are high in acid and alkali resistance at low temperature as constituent phases of neck connection among silicon carbide particles while strong neck connection is obtained through particle grading.
2. The method for preparing the silicon-manganese slag reinforced acid-base-resistant silicon carbide ceramic membrane support body according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
(1) Placing the silicomanganese slag in a muffle furnace, and preserving heat for 2h at 500-700 ℃; cooling to room temperature, taking out, crushing by a crusher, and sieving to obtain silicon-manganese slag powder with different particle diameters;
(2) Weighing silicon-manganese slag powder with different particle sizes in the step (1) and silicon carbide powder, graphite powder and hydroxypropyl methyl cellulose according to the mass ratio of 1-3:5-7:0.5-1:1-3 respectively, and placing the powder into a kneader for uniform mixing;
(3) Weighing soybean oil, glycerol and deionized water in a certain proportion, placing the soybean oil, the glycerol and the deionized water in the step (2), continuously kneading the soybean oil, the glycerol and the deionized water to obtain pasty pug, and placing the pug in a reaction kettle for ageing for 20-30 hours;
(4) Placing the aged pasty pug in the step (3) into a vacuum pug mill for pug refining so as to eliminate bubbles in the pug and placing the vacuum pug into a reaction kettle again for ageing for 20-30 hours;
(5) Placing the pug subjected to secondary aging in the step (4) into an inner cavity of an extruder, extruding under the action of axial pressure to obtain a wet blank of the ceramic membrane support, and drying at room temperature for 48 hours to obtain a dry blank of the ceramic membrane support;
(6) Placing the dried support blank obtained in the step (5) in a muffle furnace, preserving heat at 900-1200 ℃ for 2-4h, firing to form, cooling to room temperature, taking out, placing in an ultrasonic device for ultrasonic treatment for 10-30min to remove impurities on the surface and in pores of the membrane support, and finally placing in an oven for drying at 120 ℃ for 2h;
(7) And (3) weighing the mass of the silicon carbide ceramic membrane supports obtained in the step (6), and respectively taking a certain number of membrane supports and respectively placing the membrane supports in an acid-base solution to determine the acid-base corrosiveness of the membrane supports.
3. The method for preparing the silicon-manganese slag reinforced acid-base-resistant silicon carbide ceramic membrane support body according to claim 2, which is characterized by comprising the following steps: the silicomanganese slag in the step (1) is industrial solid waste; the grain sizes of the silicon-manganese slag powder with different grain sizes are respectively about 105, 65, 45 and 15 mu m.
4. The method for preparing the silicon-manganese slag reinforced acid-base-resistant silicon carbide ceramic membrane support body according to claim 2, which is characterized by comprising the following steps: and (3) the sintering atmosphere in the muffle furnace hearth in the step (6) is air, and the sintering heating rate is 2-5 ℃/min.
5. The silicon-manganese slag reinforced acid-base-resistant silicon carbide ceramic membrane support according to claim 2The preparation method is characterized in that: the acid-base solution in the step (7) is 20vol% H respectively 2 SO 4 And 1wt% NaOH solution; the experimental temperature was 90℃and the etching time was 96 hours.
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| KR20140127622A (en) * | 2013-04-25 | 2014-11-04 | 주식회사 에코마이스터 | Geopolymer using silicon manganese slag powder and the method of manufacturing the same |
| CN108395252A (en) * | 2018-01-26 | 2018-08-14 | 山东理工大学 | Liquid-phase sintering multichannel silicon carbide ceramic support body and preparation method thereof |
| CN110627512A (en) * | 2019-10-14 | 2019-12-31 | 青岛青力环保设备有限公司 | Method for preparing foamed ceramic by using water-quenched silicomanganese slag |
| CN113480324A (en) * | 2021-07-27 | 2021-10-08 | 辽宁工业大学 | Foamed ceramic prepared from fly ash and metallurgical waste residues and preparation method thereof |
| CN117142860A (en) * | 2022-05-23 | 2023-12-01 | 宁夏大学 | Gangue-silicon carbide tubular ceramic membrane support and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140127622A (en) * | 2013-04-25 | 2014-11-04 | 주식회사 에코마이스터 | Geopolymer using silicon manganese slag powder and the method of manufacturing the same |
| CN108395252A (en) * | 2018-01-26 | 2018-08-14 | 山东理工大学 | Liquid-phase sintering multichannel silicon carbide ceramic support body and preparation method thereof |
| CN110627512A (en) * | 2019-10-14 | 2019-12-31 | 青岛青力环保设备有限公司 | Method for preparing foamed ceramic by using water-quenched silicomanganese slag |
| CN113480324A (en) * | 2021-07-27 | 2021-10-08 | 辽宁工业大学 | Foamed ceramic prepared from fly ash and metallurgical waste residues and preparation method thereof |
| CN117142860A (en) * | 2022-05-23 | 2023-12-01 | 宁夏大学 | Gangue-silicon carbide tubular ceramic membrane support and preparation method thereof |
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