CN1789301A - Flyash-containing composite material with high water absorption and preparation method thereof - Google Patents
Flyash-containing composite material with high water absorption and preparation method thereof Download PDFInfo
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- CN1789301A CN1789301A CN 200510020012 CN200510020012A CN1789301A CN 1789301 A CN1789301 A CN 1789301A CN 200510020012 CN200510020012 CN 200510020012 CN 200510020012 A CN200510020012 A CN 200510020012A CN 1789301 A CN1789301 A CN 1789301A
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Abstract
The invention relates to a high water adsorption composite material and its preparing method. The high water adsorption composite material containing coal ash comprises coal ash, acroleic acid, caustic soda solution, water-soluble initiating agent for the free radical polymerization and cross linker, the adding mass of the coal ash is 40-200% of that acroleic acid, the adding mass of the water-soluble initiating agent for the free radical polymerization is 0.01-1% of that acroleic acid, the adding mass of the cross linker is 0-0.5% of that acroleic acid, the adding mass of the caustic soda solution is the 60-150 mole percentage of the neutralization degree after neutralizing the acroleic acid; the employed coal ash is that of calcining under temperature of 800-1000 DEG C for 2-8 hours to remove charcoal, the calcined coal ash is grinded by oscillating grinding tool until the average grain size is 6.0-13.0mu m. The invention is characterized bt the high water-soluble, low cost and better environment-friend than that of high water-soluble resin of poly-sodium acrylate.
Description
Technical field
The present invention relates to a kind of composite material with high water absorption and preparation method thereof, especially for farmland drought-resistant water-preserving, the crop composite material with high water absorption that volume increase, wasteland, desert administer of keeping a full stand of seedings.
Background technology
High hydrophilous resin (English full name Super Absorbent Polymers, be called for short SAP) be a kind of novel functional high molecule material, because of having very strong water-absorbent and good water-retentivity has broad application prospects at aspects such as agricultural, gardening, industry and daily lifes.The throughput of High hydrophilous resin is along with the increase of demand constantly enlarges, and water-retaining capacity makes application be restricted because of cost is too high although the High hydrophilous resin that some pure chemistry medicines are made has preferably.How to reduce cost, be the problem that the water-absorbing material field needs first-class solution.
Simultaneously, also there is open defect at present in High hydrophilous resin: ionic High hydrophilous resin water-intake rate is higher, but salt tolerance is relatively poor; Non-ionic type High hydrophilous resin salt tolerance is better, but water-intake rate is lower.No matter the former, or the latter exists and reuses and prevent secondary pollution problem.Therefore the trend of developing both at home and abroad in the recent period is: (1) development salt tolerance height, and good combination property, reusable novel super absorbent resin is just being carried out the work of this respect abroad; (2) exploitation organic and inorganic composite water absorbing, oil absorption material are the effective ways that reduces cost, improves performance.As kaolin-super absorbent resin fat complexes, natural zeolite-super absorbent resin fat complexes, water-absorbent rubber, hygroscopicity fibre, oil-absorption fiber, the exploitation of nano combined High hydrophilous resin etc. draws attention.
China's powdered coal ash is abundant, and not only distribution is wide, reserves are big, cost is low, and itself just has water-absorbent, and soil is had good improved effect.So, by organic resin and flyash copolymerization, adopt simple process to prepare good combination property, the composite material with high water absorption that contains flyash that production cost is low, have crucial meaning.
Summary of the invention
The object of the present invention is to provide a kind of high-hydroscopicity, cost low contain composite material with high water absorption of flyash and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: the composite material with high water absorption that contains flyash, it is characterized in that it comprises flyash, vinylformic acid, sodium hydroxide solution, water-soluble radical polymerization initiator, linking agent raw material, the interpolation quality of flyash is acrylic acid 40%-200%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.01%-1%, the interpolation quality of linking agent is acrylic acid 0%-0.5%, the interpolation quality of sodium hydroxide solution be in and vinylformic acid after degree of neutralization be the 60-150 molar percentage; Described flyash is for adopting 800-1000 ℃ of calcined fine coal powder 2-8 hour carbon removal, and it is 6.0-13.0 μ m that calcining back flyash is milled down to median size through vibration mill.
The interpolation quality of flyash is acrylic acid 50%-100%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.05%-0.75%, the interpolation quality of linking agent is acrylic acid 0.01%-0.5%, the interpolation quality of sodium hydroxide solution be in and vinylformic acid after degree of neutralization be the 90-130 molar percentage.
The preparation method who contains the composite material with high water absorption of flyash: it is characterized in that comprising the steps: 1). the pre-treatment of flyash: adopt 800-1000 ℃ of calcined fine coal powder 2-8 hour carbon removal, calcining back flyash is milled down to median size through vibration mill and is 6.0-13.0 μ m, and is standby;
2). choose raw material: the interpolation quality by flyash is acrylic acid 40%-200%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.01%-1%, the interpolation quality of linking agent is acrylic acid 0%-0.5%, the interpolation quality of sodium hydroxide solution be in and the degree of neutralization behind the vinylformic acid be that (illustrate: as if degree of neutralization is 100 molar percentages to the 60-150 molar percentage, then sodium hydroxide and vinylformic acid total overall reaction just; If degree of neutralization is less than 100 molar percentages, then vinylformic acid remains; If degree of neutralization is greater than 100 molar percentages, sodium hydroxide residue then), it is standby to choose flyash, vinylformic acid, sodium hydroxide solution, water-soluble radical polymerization initiator, linking agent;
3). sodium hydroxide solution slowly is added drop-wise in the Acrylic Acid Monomer solution, adjusts to degree of neutralization and be till the 60-150 molar percentage, stir simultaneously and make its thorough mixing dissolving; Add linking agent again, add pretreated flyash after the dissolving again, disperse after fully stirring, get mixing solutions;
4). water-soluble radical polymerization initiator is joined in the mixing solutions, be placed on after stirring in the 50-80 ℃ of water-bath and reacted 2-10 hour, polymerisate is dried to water content less than 10% under 80-150 ℃ of condition, promptly get product again after mechanical disintegration.
The reaction times is 3-8 hour (preferably) in the bath, and polymerisate is dry under temperature 90-130 ℃ of (preferably) condition.
Introduce the present invention below in detail.
1. flyash
Flyash is the solid, powdery waste residue that discharges in the coal-fired thermal power factory coal firing boiler waste gas, also is flying dust (fly ash).In heat power plant's coal-burning boiler coal combustion processes, ash part in the composition of coal stays because of not burning, small part is sintered state, draw off by grate, be called slag, most of because granularity is thinner, discharge with waste gas with the carbon granule of not combustion, this part grit gathers dust through flue, is called flyash.
(report number: A05065), the chemical ingredients of flyash is as shown in table 1 as can be known to the flyash analysis report according to Ministry of Land and Resources Central-South mineral products supervision detection center.
The complete chemical analysis of table 1 flyash
| SiO 2 | Al 2O 3 | Fe 2O 3 | FeO | CaO | MgO | K 2O | Na 2o | TiO 2 | P 2O 5 | MnO | SO 3 | Burn and lose | Fixed carbon |
| 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 | 10 -2 |
| 54.26 | 30.21 | 2.70 | 0.910 | 2.43 | 0.768 | 1.50 | 0.763 | 1.27 | 0.244 | 0.028 | 0.129 | 5.43 | 4.42 |
X-diffraction such as Fig. 1 of flyash.Can judge that according to diffractogram this flyash principal crystalline phase is a mullite, contain a small amount of quartz simultaneously, a large amount of amorphousness.
Flyash of the present invention according to fineness and loss on ignition classification, should belong to II level flyash.Content classification according to CaO should belong to low calcium F class flyash.According to the classification of pH value, should belong to neutrality and slightly be partial to alkaline flyash.
To successfully prepare the composite material with high water absorption that contains flyash, and improve its water absorbent rate, must carry out pre-treatment to flyash: charcoal is the lipophilic-hydrophobic property material, the present invention adopts 800-1000 ℃ of calcined fine coal powder 2-8h carbon removal, and it is 6.0-13.0 μ m that calcining back flyash is milled down to median size through vibration mill.
It is the synthetic composite material with high water absorption that contains flyash of raw material that the present invention adopts vinylformic acid and flyash, and mainly be based on following several respects and consider: the High hydrophilous resin cost that pure acrylic acid is made is too high, and biocompatibility is poor; Flyash itself has certain water-retaining capacity, it absorbs moisture except that by the capillary pore between the particle, and also retaining in the cave of grain breakage spheroid and cellular porosity is according to determination data, compare with soil moisture, flyash moisture is easier in plant utilization; China's flyash accumulative total stacking amount is about 4,000,000,000 tons, has become ash discharge state the biggest in the world, has not only taken a large amount of soils, has also aggravated the pollution to environment; Find out from the conversion process of " plant → coal → flyash ", inherited multiple nutrient element in the archaeophyte in the flyash, the physico-chemical property of can obviously improving the soil; Objectionable impurities has certain influence to farmland and crop in the flyash, but the crop of evidence flyash plantation can not be detrimental to health.
2. vinylformic acid
Vinylformic acid is the monomer of polyreaction, needs to remove stopper through underpressure distillation.Vinylformic acid can be partly or wholly to use with sodium hydroxide solution neutral form.Degree of neutralization is 60-150% (molar percentage).
3. water-soluble radical polymerization initiator
Being fit to this type of polymeric water-soluble radical polymerization initiator is persulphate, as: any one in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate.These water soluble starters can mix use, also can fit in the redox system use with reducing substances such as ferrous ion, S-WAT etc., and each composition proportion is determined by the quantitative relation of chemical equation when being used.The interpolation quality of initiator is acrylic acid 0.01%-1%, preferred 0.05%-0.75%.
4. linking agent
The linking agent that uses among the present invention contains two polymerisable groups at least.Typical linking agent has: it is crosslinked or lightly crosslinked to improve the gel-strength of high water absorption composite material that bisacrylamide such as N,N methylene bis acrylamide, this type of linking agent make high water absorption composite material form mutually at body.The interpolation quality of linking agent is acrylic acid 0%-0.5%, preferred 0.01%-0.5%.
5. preparation method and polymeric reaction condition
Take by weighing Acrylic Acid Monomer solution in beaker, by 60-150 molar percentage degree of neutralization sodium hydroxide solution slowly is added drop-wise in the vinylformic acid to stir simultaneously and makes its thorough mixing dissolving, add linking agent again, treat to add flyash again after linking agent fully dissolves, disperse after fully stirring.Dispersion can be adopted methods such as homogenizer, colloidal mill, ultrasonic wave.If adopt ultrasonic dispersion, the power of ultrasonic generator is the 200-4000 watt, and frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute.The initiator that takes by weighing aequum joins in the mixing solutions, be placed on after stirring in the 50-80 ℃ of water-bath and reacted 2-10 hour, constantly observe, the question response transformation efficiency greater than finished product taken out and is broken into after 98% particle be placed on dry in the loft drier to water content less than 10%, after mechanical disintegration, promptly get product again.
In the present invention, adopt following method to measure and the liquid absorbency rate of technology suction distilled water, tap water, 0.9% NaCl solution:
The powder material that takes by weighing 0.5-1.0 gram thorough drying places the 500-1000 ml beaker, the powder material that adds the distilled water or the tap water of 450-900 milliliter respectively or take by weighing 0.5-1.0 gram thorough drying places 100 ml beakers to add 80 milliliters 0.9% NaCl solution, at room temperature leave standstill suction and made its abundant imbibition in 48 hours, take out then and be placed on metallic sieve, weigh up gel quality affects the gravity water elimination.Be calculated as follows liquid absorbency rate:
Liquid absorbency rate=(gel quality affects-drying material quality)/drying material quality
The present invention is a raw material by adopting vinylformic acid and flyash, by above-mentioned operational path synthetic can be fully compound, material cost is lower, strong imbibition ability is arranged, better simply manufacturing process is arranged, can improve the consistency of High hydrophilous resin and environment, the high water absorption composite material that contains flyash that the present invention makes is applicable to farmland drought-resistant water-preserving, crop keep a full stand of seedings volume increase, the improvement of wasteland, desert.
The high water absorption composite material that contains flyash that the present invention makes, material cost is than the sodium polyacrylate 20%-50% that descends.The liquid absorbency rate scope that orthogonal experiment records high water absorption composite material of the present invention is: the multiplying power of inhaling distilled water is 300-750, and the multiplying power of inhaling tap water is 150-400, and the multiplying power of the NaCl solution of suction 0.9% is 40-80.
Description of drawings
Fig. 1 is the X-diffractogram of flyash of the present invention
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 8.89 grams slowly are added drop-wise in the vinylformic acid by degree of neutralization 100% (molar percentage) with mass percent, stir simultaneously and make its thorough mixing dissolving, add N again, N '-methylene-bisacrylamide 0.0020 gram, add flyash 2.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0100 gram then joins in the mixing solutions, be placed on after stirring in 70 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
Embodiment 2:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 8.89 grams slowly are added drop-wise to stir simultaneously in the vinylformic acid and make its thorough mixing dissolving by degree of neutralization 100% with mass percent, add N again, N '-methylene-bisacrylamide 0.0030 gram, add flyash 2.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0200 gram then joins in the mixing solutions, be placed on after stirring in 75 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
Embodiment 3:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 10.67 grams slowly are added drop-wise to stir simultaneously in the vinylformic acid and make its thorough mixing dissolving by degree of neutralization 120% with mass percent, add N again, N '-methylene-bisacrylamide 0.0030 gram, add flyash 2.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0100 gram then joins in the mixing solutions, be placed on after stirring in 80 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
Embodiment 4:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 8.89 grams slowly are added drop-wise to stir simultaneously in the vinylformic acid and make its thorough mixing dissolving by degree of neutralization 100% with mass percent, add N again, N '-methylene-bisacrylamide 0.0100 gram, add flyash 4.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0300 gram then joins in the mixing solutions, be placed on after stirring in 70 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
Embodiment 5:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 11.56 grams slowly are added drop-wise to stir simultaneously in the vinylformic acid and make its thorough mixing dissolving by degree of neutralization 130% with mass percent, add N again, N '-methylene-bisacrylamide 0.0100 gram, add flyash 4.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0300 gram then joins in the mixing solutions, be placed on after stirring in 70 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
Embodiment 6:
Take by weighing 4g Acrylic Acid Monomer solution in beaker, is that 25% sodium hydroxide solution, 8.89 grams slowly are added drop-wise to stir simultaneously in the vinylformic acid and make its thorough mixing dissolving by degree of neutralization 100% with mass percent, add N again, N '-methylene-bisacrylamide 0.0020 gram, add flyash 2.00 grams (calcining back flyash through vibration mill be milled down to median size be 6.0-13.0 μ m) of 800 ℃ of calcinings after the carbon removal in 4 hours after the dissolving again, (power of ultrasonic generator is the 200-4000 watt to carry out ultra-sonic dispersion after fully stirring, frequency of ultrasonic is 100 kilo hertzs-300 megahertzes, and ultrasonic time is 3-15 minute).Taking by weighing Potassium Persulphate 0.0100 gram then joins in the mixing solutions, be placed on after stirring in 75 ℃ of water-baths and react, constantly observe, to be placed in 110 ℃ of loft drier oven dry 8 hours to water content be 1-9% to the question response transformation efficiency greater than finished product being taken out and be broken into after 98% particle, promptly gets product again after mechanical disintegration.
The bound value and the interval value of flyash of the present invention, vinylformic acid, sodium hydroxide solution, water-soluble radical polymerization initiator, linking agent raw material can both be realized the present invention, just do not enumerate embodiment one by one at this.
Claims (4)
1. the composite material with high water absorption that contains flyash, it is characterized in that it comprises flyash, vinylformic acid, sodium hydroxide solution, water-soluble radical polymerization initiator, linking agent raw material, the interpolation quality of flyash is acrylic acid 40%-200%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.01%-1%, the interpolation quality of linking agent is acrylic acid 0%-0.5%, the interpolation quality of sodium hydroxide solution be in and vinylformic acid after degree of neutralization be the 60-150 molar percentage; Described flyash is for adopting 800-1000 ℃ of calcined fine coal powder 2-8 hour carbon removal, and it is 6.0-13.0 μ m that calcining back flyash is milled down to median size through vibration mill.
2. the composite material with high water absorption that contains flyash according to claim 1, it is characterized in that: the interpolation quality of flyash is acrylic acid 50%-100%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.05%-0.75%, the interpolation quality of linking agent is acrylic acid 0.01%-0.5%, the interpolation quality of sodium hydroxide solution be in and vinylformic acid after degree of neutralization be the 90-130 molar percentage.
3. the preparation method who contains the composite material with high water absorption of flyash as claimed in claim 1: it is characterized in that comprising the steps: 1). the pre-treatment of flyash: adopt 800-1000 ℃ of calcined fine coal powder 2-8 hour carbon removal, calcining back flyash is milled down to median size through vibration mill and is 6.0-13.0 μ m, and is standby;
2). choose raw material: the interpolation quality by flyash is acrylic acid 40%-200%, the interpolation quality of water-soluble radical polymerization initiator is acrylic acid 0.01%-1%, the interpolation quality of linking agent is acrylic acid 0%-0.5%, the interpolation quality of sodium hydroxide solution be in and the degree of neutralization behind the vinylformic acid be the 60-150 molar percentage, it is standby to choose flyash, vinylformic acid, sodium hydroxide solution, water-soluble radical polymerization initiator, linking agent;
3). sodium hydroxide solution slowly is added drop-wise in the Acrylic Acid Monomer solution, adjusts to degree of neutralization and be till the 60-150 molar percentage, stir simultaneously and make its thorough mixing dissolving; Add linking agent again, add pretreated flyash after the dissolving again, disperse after fully stirring, get mixing solutions;
4). water-soluble radical polymerization initiator is joined in the mixing solutions, be placed on after stirring in the 50-80 ℃ of water-bath and reacted 2-10 hour, polymerisate is dried to water content less than 10% under 80-150 ℃ of condition, promptly get product again after mechanical disintegration.
4. the preparation method who contains the composite material with high water absorption of flyash according to claim 3: it is characterized in that in the described step 4) that the reaction times is 3-8 hour in the bath, polymerisate is dry under 90-130 ℃ of condition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100392014C (en) * | 2006-08-17 | 2008-06-04 | 中国地质大学（武汉） | Polyacrylic acid super absorbent resin containing illite and fly ash and preparation method |
| CN103342775A (en) * | 2013-07-24 | 2013-10-09 | 天津市环亚建筑工程环境质量检测有限公司 | Dual-functional environment-friendly wall material capable of regulating temperature and humidity, and preparation method of environment-friendly wall material |
| CN103554390A (en) * | 2013-11-19 | 2014-02-05 | 宜兴丹森科技有限公司 | Method for preparing super absorbent resin from coal ash |
| CN104845630A (en) * | 2014-02-19 | 2015-08-19 | 亿利资源集团有限公司 | Ecological water storage and moisture retention composite material and preparation method thereof |
| CN109126723A (en) * | 2018-09-13 | 2019-01-04 | 太原理工大学 | A kind of preparation method and applications of the fly ash base adsorbent material of hydroxyl are administered in nickel contamination |
| CN111205871A (en) * | 2020-03-09 | 2020-05-29 | 宁夏大学 | Multi-source coal-based solid waste soil water-retaining conditioner and processing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1239535C (en) * | 2003-11-19 | 2006-02-01 | 中国林业科学研究院林产化学工业研究所 | Method for making water-absorbent acrylate resin |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392014C (en) * | 2006-08-17 | 2008-06-04 | 中国地质大学（武汉） | Polyacrylic acid super absorbent resin containing illite and fly ash and preparation method |
| CN103342775A (en) * | 2013-07-24 | 2013-10-09 | 天津市环亚建筑工程环境质量检测有限公司 | Dual-functional environment-friendly wall material capable of regulating temperature and humidity, and preparation method of environment-friendly wall material |
| CN103342775B (en) * | 2013-07-24 | 2016-02-24 | 天津市环亚建筑工程环境质量检测有限公司 | Difunctional green wall material of a kind of conditioning and preparation method thereof |
| CN103554390A (en) * | 2013-11-19 | 2014-02-05 | 宜兴丹森科技有限公司 | Method for preparing super absorbent resin from coal ash |
| CN104845630A (en) * | 2014-02-19 | 2015-08-19 | 亿利资源集团有限公司 | Ecological water storage and moisture retention composite material and preparation method thereof |
| CN109126723A (en) * | 2018-09-13 | 2019-01-04 | 太原理工大学 | A kind of preparation method and applications of the fly ash base adsorbent material of hydroxyl are administered in nickel contamination |
| CN109126723B (en) * | 2018-09-13 | 2021-04-16 | 太原理工大学 | Preparation method of fly ash-based adsorption material containing hydroxyl and application of fly ash-based adsorption material in nickel pollution treatment |
| CN111205871A (en) * | 2020-03-09 | 2020-05-29 | 宁夏大学 | Multi-source coal-based solid waste soil water-retaining conditioner and processing method thereof |
| CN111205871B (en) * | 2020-03-09 | 2021-02-19 | 宁夏大学 | Multi-source coal-based solid waste soil water-retaining conditioner and processing method thereof |
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