CN105130487A - Composition for producing filter ceramic and the filter ceramic, and preparation method and application thereof - Google Patents
Composition for producing filter ceramic and the filter ceramic, and preparation method and application thereof Download PDFInfo
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- CN105130487A CN105130487A CN201510420363.5A CN201510420363A CN105130487A CN 105130487 A CN105130487 A CN 105130487A CN 201510420363 A CN201510420363 A CN 201510420363A CN 105130487 A CN105130487 A CN 105130487A
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Abstract
The invention discloses a composition for producing filter ceramic and the filter ceramic, and a preparation method and an application thereof. The composition includes, by weight, 65-85% of fly ash, 15-35% of gasification slag and water, of which the quantity accounts for 3-25% of the total weight of the fly ash and the gasification slag. In the invention, the gasification slag is utilized, and the filter ceramic, which is excellent in performance, can be prepared without a pore-forming agent. In addition, the sintering temperature in the preparation method is lower than 1200 DEG C, so that the preparation method saves energy but not reduces product performance.
Description
Technical field
The present invention relates to a kind of composition for the production of ceramic for filtration, and prepare the method for ceramic for filtration by said composition, and the ceramic for filtration prepared by the method and the application in Coal Chemical Industry, power plant waste water process thereof.
Background technology
Flyash is mainly derived from a kind of industrial solid castoff that firepower electrical plant and various coal firing boiler are got rid of, and its quantity discharged constantly increases along with the fast development of economy.The quantity discharged of China's flyash in 2013 nearly 4.2 tons, and utilization ratio is only about 67%.Especially central/western China substantially with land-fill method for main treated coal ash, not only take a large amount of soil, but also to air, underground water produce baneful influence.Utilize the main application of flyash to have the filler of cement and concrete etc. at present, or road, agricultural construction, or aerated bricks and the building material such as non-burning brick.
The main component of flyash is based on silicon-dioxide and aluminum oxide, and the two content reaches more than 70%, close with clay component in the raw material of traditional ceramics.In addition, flyash itself also has a large amount of micropores and higher specific surface area.Therefore, reported and utilize coal ash for manufacturing for porous ceramics.
CN104211427A discloses a kind of porous ceramics utilizing coal ash for manufacturing standby, comprise material composition: flyash, pore-forming material, caking agent, additive and spent pulping liquor, the each component content of raw material is flyash 35-45%, pore-forming material 25-30%, caking agent 5-10%, additive 5-8%, spent pulping liquor 15-20%.
CN104016699A discloses a kind of high porosity porous ceramic filter material, and this filtrate comprises: fly ash float material 55-65%, clay 8-12%, caking agent 18-25%, pore-forming material 5-20%, additive 2-3%; Fly ash float material is porous silicon alumina vitreum, also includes whipping agent.
It take flyash as the Lightweight ceramic filter core of base-material that CN103382129A discloses a kind of, be prepared from by the raw material of following weight part: this property flyash 60-70, kaolin 20-30, brown sugar 3-4, carbide slag 10-15, tree ash 4-6, lignocellulose 2-3, water glass 3-4, tripoly phosphate sodium STPP 1-2, epoxy resin 1-2, polyoxylethylene abietate 1-2, borax 1-2, water-soluble nanoscale silica sol 5-8, the preparation method of modified coal ash: first flyash is dropped in the sulphuric acid soln of 15%, at 60-70 DEG C, soak 4-5 hour, leave standstill, filter, filter residue is rinsed 3-4 time with clear water, use 10%NaOH neutralising flush to pH value 7.0 again, leave standstill again and filter, dry, add the 1-2% Union carbide A-162 of solid weight, 2-3% ethylene bis stearamide, 0.5-0.6% aluminum oxide, 0.2-0.4% cupric nitrate, 0.5-0.8% dodecyl oxyethyl group sultaine, abundant stirring, dry, grind to form nanometer powder.
CN103304253A openly utilizes red mud and the standby porous ceramics of coal ash for manufacturing, comprises proportioning raw materials by weight: red mud 40-70%, flyash 5-40%, pore-forming material 10-30%, additive 1-5%, also comprises the water of the 10-20% of above-mentioned material gross weight.
But the porous ceramics of above-mentioned preparation as be applied to Coal Chemical Industry, power plant sewage disposal time, still can not meet the demands.
On the other hand, the slag that gasifies is a kind of new solid waste that coal gasification course is discharged.Along with the development of Coal Chemical Industry in China industry, the output of annual gasification slag also sharply increases.For Ning Mei group of Shenhua, the annual production of gasification slag is about 1,000,000 tons at present.Along with completing of project in construction, expect 2016, the annual emissions of gasification slag will reach about 3,500,000 tons.Can predict, gasification slag will become one of emphasis of solid waste process from now on.
Therefore, need to provide the method for rationally process gasification slag, improve the performance of the porous ceramics of preparation, the environmental problem that the sewage disposal that can solve current Coal Chemical Industry and enterprise of power plant brings.
Summary of the invention
The object of the invention is the utilization in order to solve gasification slag and how to improve porous ceramics to be applicable to the problem of the sewage disposal of Coal Chemical Industry and power plant, providing composition and ceramic for filtration and its preparation method and application for the production of ceramic for filtration.
To achieve these goals, the invention provides a kind of composition for the production of ceramic for filtration, said composition comprises flyash, gasification slag and water, with the gross weight of flyash and gasification slag for benchmark, the content of flyash is 65-85 % by weight, and the content of gasification slag is 15-35 % by weight; The consumption of water is the 3-25 % by weight of flyash and gasification slag gross weight.
Present invention also offers a kind of method preparing ceramic for filtration, the method comprises:
1) composition provided by the invention is carried out wet grinding, form mixed slurry;
2) mixed slurry that step (1) obtains is carried out ageing, then carry out extrusion forming;
3) mold compound that step (2) obtains is sintered, then cooling obtains ceramic for filtration.
Present invention also offers the ceramic for filtration that a kind of composition provided by the invention and/or method prepare, the density of this ceramic for filtration is 1600-1700kg/m
3, water-intake rate is more than 30%, and folding strength is the water flux under more than 15MPa, 0.2MPa is 40000L/hm
2above.
Present invention also offers the application of ceramic for filtration provided by the invention in process Coal Chemical Industry and power plant waste water.
Composition for the production of ceramic for filtration provided by the invention can using gasification slag as composition, and the pore-forming material not having prior art to use can prepare ceramic for filtration, realize the utilization of gasification slag, and the ceramic for filtration performance obtained is applicable to process Coal Chemical Industry and power plant waste water.When adopting composition provided by the invention to prepare ceramic for filtration in addition, sintering temperature, lower than 1200 DEG C, is saved energy consumption but does not affect product performance.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of composition for the production of ceramic for filtration, said composition comprises flyash, gasification slag and water, and with the gross weight of flyash and gasification slag for benchmark, the content of flyash is 65-85 % by weight, and the content of gasification slag is 15-35 % by weight; The consumption of water is the 3-25 % by weight of flyash and gasification slag gross weight.
Composition in the present invention can without the need to separately adding pore-forming material, the such as conventional pore-forming material such as carbon black, starch based powder, calcium carbonate, granules of polystyrene.
According to the present invention, under preferable case, described flyash is first level flour coal ash and/or the second class powered coal ash of thermal power plant's generation, and described gasification slag is the waste residue that coal gasification course produces.
Preferably, described flyash contains the SiO of 30-65 % by weight
2, 14-41 % by weight Al
2o
3, loss on ignition is 1-5 % by weight.
, preferably, described gasification slag contains the SiO of 30-50 % by weight
2, 10-20 % by weight Al
2o
3, loss on ignition is more than 15 % by weight; More preferably, loss on ignition is 20-25 % by weight.
According to the present invention, under preferable case, described composition also comprises binding agent, and the content of described binding agent is not more than 10 % by weight of flyash and gasification slag gross weight, more preferably, can be the 3-8 % by weight of flyash and gasification slag gross weight.
Further preferably, described binding agent can be at least one in Walocel MT 20.000PV, hydroxypropylcellulose, polyvinyl alcohol, pregelatinized Starch and dextrin.
According to the present invention, under preferable case, described composition also comprises fusing assistant, and the content of described fusing assistant is not more than 8 % by weight of flyash and gasification slag gross weight.。
Preferably, described fusing assistant main component is the SiO of 60-70 % by weight
2, the Al of 10-20 % by weight
2o
3, its loss on ignition is 1-5 % by weight.More preferably, described fusing assistant is at least one in albite, potassium felspar sand and kaolin.
Present invention also offers a kind of method preparing ceramic for filtration, the method comprises:
1) composition provided by the invention is carried out wet grinding, form mixed slurry;
2) mixed slurry that step (1) obtains is carried out ageing, then carry out extrusion forming;
3) mold compound that step (2) obtains is sintered, then cooling obtains ceramic for filtration.
According to the present invention, the wet grinding of step (1) can be carry out in ball mill, and alumina balls can be utilized for grinding medium, and be the ratio mixed grinding of 2-3:1 according to the weight ratio of alumina balls and composition, milling time is 1-2h.
According to the present invention, described in step (2), there is no particular limitation in ageing, and can be the ageing that this area routine adopts, can be left standstill by the mixed slurry that step (1) obtains, preferably, described digestion time be 24-48h.
According to the present invention, the extrusion forming of step (2) can be conventional forming method, can be compression moulding or extrusion moulding.Preferably, the slurry after ageing can be put into steel die to be pressed.Preferably, the pressure of described compression moulding is 10-40MPa.
According to the present invention, after above-mentioned compression moulding, the demoulding obtains product, and this product, after 100-150 DEG C of drying in 10-24 hour, carries out the sintering of step (3).Described sintering can complete at the temperature lower than prior art.Preferably, the condition of described sintering comprises: after room temperature rises to 900-1150 DEG C, be incubated 1-3h with the rate of heating of 5-15 DEG C/min.
Present invention also offers the ceramic for filtration that a kind of composition provided by the invention and/or method prepare, the density of this ceramic for filtration is 1600-1700kg/m
3, water-intake rate is more than 30%, and folding strength is the water flux under more than 15MPa, 0.2MPa is 40000L/hm
2above.
Preferably, the water-intake rate of the ceramic for filtration prepared is more than 35%, and folding strength is the water flux under more than 20MPa, 0.2MPa is 45000L/hm
2above.
Present invention also offers the application of ceramic for filtration provided by the invention in process Coal Chemical Industry and power plant waste water.
Below will be described the present invention by embodiment.
In following examples and comparative example,
The test of the density of ceramic for filtration: get test specimen one group 3 pieces, be of a size of 62.5mm × 12.5mm × 5mm, answers block-by-block to measure the axial dimension in length and width, thick three directions, and should be accurate to 1mm, the volume V of calculation testing piece.Three pieces of test specimens being placed on temperature is dry to permanent quality in 105 DEG C ± 2 DEG C loft drier.After test specimen is cooled to room temperature, test specimen dries quantity M should be taken
0, be accurate to 0.01g; Be calculated as follows density:
in formula: r
0-density (kg/m
3), M
0-dries quantity (g), the volume (mm of V-test specimen
3); The density value of this group test specimen should be the mean value of 3 pieces of Sample density, is accurate to 1kg/m
3.
The test of the ultimate compression strength of ceramic for filtration: condition of molding is room temperature and relative humidity is (50 ± 10) %.After shaping, sample is transferred in cement standard maintaining box, places 24 hours under normal curing condition (20 ± 2 DEG C, relative humidity 100%).Then the sample demoulding is continued maintenance at constant-temp. and-moisture maintenance.Adopt the three-point bending method that specifies of GB1965-1996 in the model of Wuxi Jianyi Instrument Machinery Co., Ltd. be TYE-300D compressive strength tester on measure the folding strength of sample, span is 10mm, loading rate is 0.1mm/min, and often organize sample and take 3 samples, calculation formula is as follows:
in formula: K-folding strength, MPa; P: maximal destruction loading, N; L: span (length of support), mm; B: specimen width, mm; H: sample thickness, mm.
The test of the water-intake rate of ceramic for filtration: get test specimen one group 3 pieces, is of a size of (R) 30mm × (H) 5mm.Three pieces of test specimens being placed on temperature is dry to permanent quality in 105 DEG C ± 2 DEG C loft drier.After test specimen is cooled to room temperature, takes test specimen dries quantity M0, be accurate to 0.01g.Being placed by sample pours in the vessel of distilled water, and sample is dipped into 24h completely.Take out sample and use saturated sponge adsorption surface excessive moisture, claim the weight M1 of its saturated sample in atmosphere, be accurate to 0.01g.Water-intake rate Wa is calculated as follows: Wa=[(M1-M0)/M0] × 100%
The test of the water flux of ceramic for filtration: get test specimen one group 3 pieces, is of a size of (R) 10mm × (H) 5mm, and being placed on temperature is dry to permanent quality in 105 DEG C ± 2 DEG C loft drier.Be to test in 1min water under 0.2MPa by the water yield of sample film at hydraulic pressure.
In following examples and comparative example, binding agent and fusing assistant are Beijing Pharmaceutical Group company limited product be purchased; Flyash is thermal power plant's first level flour coal ash, and it mainly contains the SiO of 45.46 % by weight
2with 32.76 % by weight Al
2o
3, loss on ignition is 1.75 % by weight; Gasification slag is the SiO of 31.83 % by weight
2, 15.83 % by weight Al
2o
3, loss on ignition is 39.27 % by weight.
Embodiment 1
The present embodiment prepares the method for ceramic for filtration for illustration of the present invention.
The composition of the composition for the production of ceramic for filtration listed according to table 1 and consumption, various material is put into ball mill (Changsha meter Qi plant and instrument company limited model YXQM-2L) grinding 1.5h, wherein the weight ratio of the material of alumina balls and composition is 2:1, obtains mixed slurry.Binding agent is Walocel MT 20.000PV, and addition is 5 % by weight of flyash and gasification slag gross weight.
By still aging for mixed slurry 30h, then put into the steel die 10MPa that pressurizes and be pressed; Dry 24h by the mold compound demoulding and at 100 DEG C, then puts into sintering oven, is incubated 1h, obtains ceramic for filtration after cooling with the rate of heating of 5 DEG C/min after room temperature rises to 1150 DEG C.
Testing method according to the density of ceramic for filtration, water-intake rate, folding strength and water flux prepares each test sample, and test result is in table 2.
Embodiment 2
The present embodiment prepares the method for ceramic for filtration for illustration of the present invention.
The composition of the composition for the production of ceramic for filtration listed according to table 1 and consumption, put into grinding in ball grinder 2h by various material, and wherein the weight ratio of the material of alumina balls and composition is 3:1, obtains mixed slurry.
By still aging for mixed slurry 24h, then put into the steel die 30MPa that pressurizes and be pressed; Dry 10h by the mold compound demoulding and at 150 DEG C, then puts into sintering oven, is incubated 3h, obtains ceramic for filtration after cooling with the rate of heating of 15 DEG C/min after room temperature rises to 900 DEG C.
Testing method according to the density of ceramic for filtration, water-intake rate, folding strength and water flux prepares each test sample, and test result is in table 2.
Embodiment 3
The present embodiment prepares the method for ceramic for filtration for illustration of the present invention.
The composition of the composition for the production of ceramic for filtration listed according to table 1 and consumption, put into grinding in ball grinder 1h by various material, and wherein the weight ratio of the material of alumina balls and composition is 2:1, obtains mixed slurry.Binding agent is pregelatinized Starch, and addition is 4 % by weight of flyash and gasification slag gross weight.
By still aging for mixed slurry 20h, then put into the steel die 20MPa that pressurizes and be pressed; Dry 18h by the mold compound demoulding and at 120 DEG C, then puts into sintering oven, is incubated 2h, obtains ceramic for filtration after cooling with the rate of heating of 10 DEG C/min after room temperature rises to 1050 DEG C.
Testing method according to the density of ceramic for filtration, water-intake rate, folding strength and water flux prepares each test sample, and test result is in table 2.
Embodiment 4
According to the method for embodiment 3, unlike, there is no fusing assistant in composition.Result is as shown in table 2.
Comparative example 1
According to the method for embodiment 3, the composition of composition in table 1, unlike, do not gasify in composition slag.Result is as shown in table 2.
Comparative example 2
According to the method for embodiment 3, the composition of composition in table 1, unlike, do not gasify in composition slag and fusing assistant.Result is as shown in table 2.
Comparative example 3
According to the method for embodiment 3, the composition of composition in table 1, unlike, also containing as the carbon black (the F900A trade mark, Tianjin Yi Bo Chemical Co., Ltd.) of pore-forming material in composition.Result is as shown in table 2.
Table 1
Table 2
As can be seen from embodiment above and comparative example result, the composition for the production of ceramic for filtration provided by the invention to contain gasification slag for component, and does not contain pore-forming material, and can sinter preparation at lower than 1200 DEG C, and obtaining density is 1600-1700kg/m
3, water-intake rate is more than 30%, and folding strength is the water flux under more than 15MPa, 0.2MPa is 40000L/hm
2above ceramic for filtration.
Claims (10)
1. for the production of a composition for ceramic for filtration, said composition comprises flyash, gasification slag and water, and with the gross weight of flyash and gasification slag for benchmark, the content of flyash is 65-85 % by weight, and the content of gasification slag is 15-35 % by weight; The consumption of water is the 3-25 % by weight of flyash and gasification slag gross weight.
2. composition according to claim 1, wherein, described composition also comprises binding agent, and the content of described binding agent is not more than 10 % by weight of flyash and gasification slag gross weight.
3. composition according to claim 2, wherein, described binding agent is be selected from least one in Walocel MT 20.000PV, hydroxypropylcellulose, polyvinyl alcohol, pregelatinized Starch and dextrin.
4. the composition according to any one of claim 1-3, wherein, described composition also comprises fusing assistant, and the content of described fusing assistant is not more than 8 % by weight of flyash and gasification slag gross weight.
5. composition according to claim 4, wherein, described fusing assistant is at least one in albite, potassium felspar sand and kaolin.
6. composition according to claim 1, wherein, described flyash contains the SiO of 30-65 % by weight
2, 14-41 % by weight Al
2o
3, loss on ignition is 1-5 % by weight; Described gasification slag contains the SiO of 30-50 % by weight
2, 10-20 % by weight Al
2o
3, loss on ignition is more than 15 % by weight.
7. prepare a method for ceramic for filtration, the method comprises:
1) composition according to any one of claim 1-6 is carried out wet grinding, form mixed slurry;
2) mixed slurry that step (1) obtains is carried out ageing, then carry out extrusion forming;
3) mold compound that step (2) obtains is sintered, then cooling obtains ceramic for filtration.
8. method according to claim 7, wherein, described digestion time is 24-48h; The pressure of described extrusion forming is 10-40MPa; The condition of described sintering comprises: after room temperature rises to 900-1150 DEG C, be incubated 1-3h with the rate of heating of 5-15 DEG C/min.
9. the ceramic for filtration that the method described in the composition according to any one of claim 1-6 or 7 prepares, the density of this ceramic for filtration is 1600-1700kg/m
3, water-intake rate is more than 30%, and folding strength is the water flux under more than 15MPa, 0.2MPa is 40000L/hm
2above.
10. the application of ceramic for filtration according to claim 9 in process Coal Chemical Industry and power plant waste water.
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| CN108585779A (en) * | 2018-05-04 | 2018-09-28 | 中国科学院过程工程研究所 | A method of preparing Al-Si composites using gasification slag |
| CN109200831A (en) * | 2017-06-30 | 2019-01-15 | 上海清粼环保科技有限公司 | A kind of preparation method of single side film flat ceramic filtration membrane |
| CN109516775A (en) * | 2018-12-29 | 2019-03-26 | 陕西尧柏新型墙材有限公司 | A kind of coal chemical industry gasification slag fired brick and preparation method thereof |
| CN110759713A (en) * | 2018-07-27 | 2020-02-07 | 广东清大同科环保技术有限公司 | Gasification slag porous sintered brick and preparation method thereof |
| CN114478059A (en) * | 2021-12-31 | 2022-05-13 | 西安理工大学 | Preparation method of ceramic filter material |
| CN115159957A (en) * | 2021-04-01 | 2022-10-11 | 国家能源投资集团有限责任公司 | Composition for producing coal-based solid waste porous ceramic, coal-based solid waste porous ceramic and preparation method and application thereof |
| CN116023120A (en) * | 2023-02-28 | 2023-04-28 | 西安工程大学 | Coal gasification fine slag-based inorganic ceramic membrane and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109200831A (en) * | 2017-06-30 | 2019-01-15 | 上海清粼环保科技有限公司 | A kind of preparation method of single side film flat ceramic filtration membrane |
| CN108585779A (en) * | 2018-05-04 | 2018-09-28 | 中国科学院过程工程研究所 | A method of preparing Al-Si composites using gasification slag |
| CN108585779B (en) * | 2018-05-04 | 2021-10-15 | 中国科学院过程工程研究所 | Method for preparing aluminum-silicon composite material by using gasified slag |
| CN110759713A (en) * | 2018-07-27 | 2020-02-07 | 广东清大同科环保技术有限公司 | Gasification slag porous sintered brick and preparation method thereof |
| CN109516775A (en) * | 2018-12-29 | 2019-03-26 | 陕西尧柏新型墙材有限公司 | A kind of coal chemical industry gasification slag fired brick and preparation method thereof |
| CN115159957A (en) * | 2021-04-01 | 2022-10-11 | 国家能源投资集团有限责任公司 | Composition for producing coal-based solid waste porous ceramic, coal-based solid waste porous ceramic and preparation method and application thereof |
| CN115159957B (en) * | 2021-04-01 | 2023-09-01 | 国家能源投资集团有限责任公司 | Composition for producing coal-based solid waste porous ceramic, preparation method and application thereof |
| CN114478059A (en) * | 2021-12-31 | 2022-05-13 | 西安理工大学 | Preparation method of ceramic filter material |
| CN116023120A (en) * | 2023-02-28 | 2023-04-28 | 西安工程大学 | Coal gasification fine slag-based inorganic ceramic membrane and preparation method thereof |
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Application publication date: 20151209 |
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| RJ01 | Rejection of invention patent application after publication |