CN102964015A - Method for removing heavy metals Zn and Cu in dredged river sediment - Google Patents
Method for removing heavy metals Zn and Cu in dredged river sediment Download PDFInfo
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- CN102964015A CN102964015A CN2012105307784A CN201210530778A CN102964015A CN 102964015 A CN102964015 A CN 102964015A CN 2012105307784 A CN2012105307784 A CN 2012105307784A CN 201210530778 A CN201210530778 A CN 201210530778A CN 102964015 A CN102964015 A CN 102964015A
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Abstract
The invention discloses a method for removing heavy metals Zn and Cu in dredged river sediment, which comprises the following steps: mixing dredged river sediment and water according to a mass ratio of 1:(2-10) to obtain sediment slurry; acidizing and oxidizing the sediment slurry, performing microwave heating on the obtained reaction product to 60-120 DEG C, and keeping the temperature for 5-10 minutes; after the heating reaction is finished, filtering to obtain sediment slag and a filtrate containing Zn and Cu; and chemically depositing the filtrate, and regulating the pH value to 7.5-8.5, thus obtaining a clear solution and heavy metal slag containing Zn and Cu. The method disclosed by the invention is simple in process, convenient to operate, low in investment and cost, short in treatment period and good in treatment effect, and can realize the reutilization of sediment, thereby having certain economic and social benefits.
Description
Technical field
The present invention relates to a kind of method of removing dredging bed mud in river heavy metal, be specifically related to a kind of technological method that utilizes microwave-assisted acidifying oxidation style to remove heavy metal Zn, Cu in the dredging bed mud in river.
Background technology
Heavy metal contamination is one of important environmental problem of Present Global in the bed mud in river.Human activity in production such as mine development, industry smelting, electron wastes processing etc. can produce a large amount of waste water, and contain a large amount of heavy metals in the waste water, and its content surpasses several times, tens times even hundreds of times of national standard.If the sewage of any processing of this not process is directly entered the external world, sewage can by a series of channels such as rainwashes, finally come together in the river.When the self-purification capacity in river during much smaller than the speed of anthropogenic discharge's pollutent, plurality of heavy metal accumulates in bed mud in river by settlement action.Drive in behaviors such as nature (stormy waves, trend, morning and evening tides etc.), biological activity (burrow etc.), human activities (excavation adopt sand, ship, drag a net in fishing etc.) that settling suspends again so that the heavy metal of sedimentary particle absorption and combination may discharge into overlying water by absorption-desorption balance and redox reaction, the recontamination water body causes secondary pollution.Heavy metal in the bed mud in river has the advantages that latency period is grown, accumulated easily, is difficult for natural degradation.The biology that pollution substance can be directly or indirectly dwelt in microorganism or the water body end of to produces toxic action, thereby directly affects hydrobiological growth and reproduction.In addition, also can by effects such as biomagnification or amplifications, utilize food chain to affect terrestrial organism and the mankind healthy (such as neural system entanglement, injuries of tissues and organs, destruction immunity system, cancer etc.).Therefore, the heavy metal pollution problem that solves in the bed mud is the task of top priority.
At present, the treatment process of polluted river bed mud is divided into in-situ treatment and showering two large classes.In-situ treatment can be divided into bed mud cap envelope method, phytoremediation etc.Bed mud cap envelope method is to place one or more layers coverture at the bed mud that pollutes, and makes the isolation of polluted bed mud and water body, prevents that pollutants in sediments from moving to water body, and cap closure material commonly used comprises: the sand of cleaning, bed mud, gravel or man-made land sill etc.But this method exists, and quantities is large, cap closure material amount mainly with and the problems such as the difficult control of thickness of cap envelope.The plant growing that phytoremediation refers to have special accumulation ability is in contaminated bed mud, and the absorption by plant or root system of plant district microorganism, metabolism are to reduce or removal of pollutants toxicity.But the weak point of this method is that the cycle is long, it is slow to take effect.For the fast processing bed mud in river pollutes, the most effective and the easiest method is that bed mud in river is dredged.Generally believe, the amino acid and the required multiple element of plant-growth that contain the trace such as abundant N, P, K in the bed mud, Chinese scholars thinks that the dredging bed mud not only can be converted into the agricultural utilization, also can be used as other resource utilization purposes (making the embankment material, material of construction etc.).But because contaminated dredging bed mud in river complicated component and amount are large, directly do not stack if do not take any preprocessing process, easily cause secondary pollution.The showering of bed mud in river can be divided into drip-rinsing process, electrochemical rehabilitation method etc.Drip-rinsing process is to utilize chemical agent or microorganism to promote stripping and the migration of pollutent in the bed mud, then will contain solution extracting from bed mud of pollutent, carries out the process of advanced treatment again.The method has the advantages that technique is simple, processing efficiency is high, but the screening of efficient eluent or bacterium and development difficulty comparatively, and has that secondary pollution etc. is unresolved maybe to need perfect problem.The ultimate principle of electrochemical repair method is that electrode is inserted in the contaminated bed mud, apply galvanic current after, the pollutent in the bed mud is moved to electrode district from treatment zone, and then is removed by galvanic deposit or ion extractuin method, thereby reaches the purpose of reparation.Be difficult in Practical Project, be applied but this method cost of investment and power consumption are higher.
Owing to contain the pollutent that exceeds standard in a large number (such as heavy metal etc.) in the contaminated dredging bed mud, thereby the dredging bed mud belongs to a danger solid wastes.Be innoxious, minimizing, the resource utilization that reaches solid waste, the investigator is devoted to study the technology of the various treatment and disposals of heavy metal in the dredging bed mud in river always, how to address this problem the study hotspot and the direction that have become this area.Naturally high-grade ore of storing along with the whole world day by day reduces, and bed mud in river is the large low-grade ores of a kind of reserves as " source " that Heavy Metals in Waters pollutes, can be considered as the Equations of The Second Kind Mineral resources of heavy metal exploitation.Thereby it is very necessary researching and developing a kind of bed mud in river heavy metal treatment technology of dredging, and can realize that not only contaminated dredging bed mud in river is processed and the purpose of recycling, can also produce preferably economic benefit and social benefit.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides that a kind of technique is simple, easy to operate, less investment, cost is low, treatment cycle is short, treatment effect is good, can realize the method for heavy metal Zn, Cu in the removal dredging bed mud in river of bed mud recycling.
For solving the problems of the technologies described above, the technical solution used in the present invention is heavy metal Zn in a kind of removal dredging bed mud in river, the method of Cu, described method comprises the dredging bed mud in river (is referred to dry bottom mud, dry bottom mud needs to remove in advance leaf wherein, branch and macrobead thing etc.) be mixed into bottom slurry with water by 1: 2～10 mass ratio, after bottom slurry carried out acidification and oxide treatment, the reaction product that obtains is carried out microwave heating to 60 ℃～120 ℃, insulation 5min～10min, filtration after reacting by heating is finished, obtain the bed mud slag and contain Zn, the filtrate of Cu, filtrate is carried out chemical settling, regulating pH is 7.5～8.5, gets clear liquid and contains Zn, the heavy metal slag of Cu.
In the above-mentioned method, described acidification process comprises and adds while stirring acid in the described bottom slurry, regulates pH to 1～3, mixture is stirred to evenly (is generally 5～10min).Described acid is mineral acid or organic acid, wherein, and the preferred vitriol oil of mineral acid, HNO
3Or hydrochloric acid, the more preferably vitriol oil, organic acid optimization citric acid, oxalic acid or acetic acid.
In the above-mentioned method, described oxidation processes comprises in the mixture after the described acidification and adds while stirring hydrogen peroxide or add hydrogen peroxide and FeSO
47H
2The O(ferrous sulfate) combination (FeSO
47H
2O mainly plays katalysis), then be stirred to evenly.The quality of described hydrogen peroxide is 8%～12% of dredging bed mud in river quality, described FeSO
47H
2The quality of O is 0.1%～0.3% of dredging bed mud in river quality.
In the above-mentioned method, the sinking agent that described chemical settling is used is water-soluble metallic sulfide (preferred Na
2S, CaS, BaS, more preferably BaS) (can remove Zn and Cu, be convenient to follow-up recycle).
In the above-mentioned method, the bed mud slag that filters gained can be converted into the agricultural utilization, also can be used as other resource utilization purposes, as making embankment material, material of construction etc.; The recyclable rear portion of the clear liquid of chemical settling gained continues on for the preparation (liquid-solid ratio of control bed mud) of bottom slurry or filters the step of (being used for cleaning instrument), a part directly is delivered to sewage work, and the heavy metal slag of gained can be used as the mineral resource recovery utilization.
Compared with prior art, the invention has the advantages that:
1. the treatment cycle of the inventive method is lacked, and treatment effect is good, and the clearance of dredging heavy metal Zn, Cu in the bed mud in river is distinguished can be up to 90.6% and 81.4%.
2. adopted microwave-assisted acidifying oxidation style among the present invention, this method not only can be removed the heavy metal in the bed mud, also has the functions such as other organic pollutant of water ratio, deodorizing and degraded that reduce bed mud, for follow-up recycling provides favourable condition.
3. the inventive method not only can realize the efficient removal of heavy metal, can also effectively reclaim heavy metal, and the clear liquid reusable edible of gained has certain economic and social profit.
4. simple, easy to operate, the required less investment of equipment of the inventive method technique, and running cost is lower.
Description of drawings
Fig. 1 is the technological line synoptic diagram of removing heavy metal Zn, Cu in the dredging bed mud in river among the present invention.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment the present invention is described in further detail.
Embodiment 1:
A kind ofly remove the method (technological line is referring to Fig. 1) that Xiang River Xia Wan port, Zhuzhou enters heavy metal Zn, Cu in the bed mud of Jiangkou, may further comprise the steps:
(1) preparation of bottom slurry: the Xiang River Xia Wan port, Zhuzhou of getting the 50g oven dry enters the bed mud at Jiangkou, and the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: choose mass concentration and be 98% the technical grade vitriol oil, while stir slowly the vitriol oil is added in the above-mentioned bottom slurry, until pH is 2.
(3) oxide treatment: add concentration in the mixture that obtains to acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%), be stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 60 ℃ in the microwave reactor, insulation 10min after reacting by heating is finished, is cooled to room temperature.
(5) filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: in above-mentioned filtrate, add Na
2S, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measure process before and after the content of Zn, Cu in the dredging bed mud in river, learn that as calculated the clearance of heavy metal Zn and Cu is respectively 89.11% and 74.88% to the method in the bed mud of Jiangkou to entering.This shows that the inventive method is very high to the removal efficient of heavy metal Zn, Cu.In above-mentioned steps, other organic pollutant in the bed mud of can also degrading, deodorizing, recovery heavy metal have certain economic and social profit, for follow-up recycling is laid a good foundation.
Embodiment 2:
A kind of method (technological line is referring to Fig. 1) of removing heavy metal Zn, Cu in the sewage draining exit bed mud of Xiang River Xia Wan port, Zhuzhou may further comprise the steps:
(1) preparation of bottom slurry: get the bed mud of Xiang River Xia Wan port, the Zhuzhou sewage draining exit of 50g oven dry, the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: choose mass concentration and be 98% the technical grade vitriol oil, while stir slowly the vitriol oil is added in the above-mentioned bottom slurry, until pH is 2.
(3) oxide treatment: add concentration in the mixture after the acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%), be stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 60 ℃ in the microwave reactor, insulation 10min after reacting by heating is finished, is cooled to room temperature.
(5) filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: in above-mentioned filtrate, add Na
2S, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measuring the content of processing Zn, Cu in the front and back dredging bed mud in river, learn that as calculated the method is respectively 79.4% and 60.5% to the clearance of heavy metal Zn and Cu in the sewage draining exit bed mud.
Embodiment 3:
A kind ofly remove the method (technological line is referring to Fig. 1) that Xiang River Xia Wan port, Zhuzhou enters heavy metal Zn, Cu in the bed mud of Jiangkou, may further comprise the steps:
(1) preparation of bottom slurry: the Xiang River Xia Wan port, Zhuzhou of getting the 50g oven dry enters the bed mud at Jiangkou, and the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: choose mass concentration and be 98% the technical grade vitriol oil, while stir slowly the vitriol oil is added in the above-mentioned bottom slurry, until pH is 2.
(3) oxide treatment: add concentration in the mixture after the acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%) and 0.08g FeSO
47H
2O is stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 60 ℃ in the microwave reactor, insulation 10min after reacting by heating is finished, is cooled to room temperature.
(5) filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: in heavy metal filtrate, add Na
2S, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measure process before and after the content of Zn, Cu in the dredging bed mud in river, learn that as calculated the clearance of heavy metal Zn and Cu is respectively 90.6% and 81.4% to the method in the bed mud of Jiangkou to entering.
Embodiment 4:
A kind of method (technological line is referring to Fig. 1) of removing heavy metal Zn, Cu in the sewage draining exit bed mud of Xiang River Xia Wan port, Zhuzhou may further comprise the steps:
(1) preparation of bottom slurry: get the bed mud of Xiang River Xia Wan port, the Zhuzhou sewage draining exit of 50g oven dry, the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: choose mass concentration and be 98% the technical grade vitriol oil, while stir slowly the vitriol oil is added in the above-mentioned bottom slurry, until pH is 2.
(3) oxide treatment: add concentration in the mixture after the acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%) and 0.08g FeSO
47H
2O is stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 60 ℃ in the microwave reactor, insulation 10min after reacting by heating is finished, is cooled to room temperature.
(5) mechanical filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: in heavy metal filtrate, add Na
2S, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measuring the content of processing Zn, Cu in the front and back dredging bed mud in river, learn that as calculated the method is respectively 81.2% and 62.5% to the clearance of heavy metal Zn and Cu in the sewage draining exit bed mud.
Embodiment 5:
A kind ofly remove the method (technological line is referring to Fig. 1) that Xiang River Xia Wan port, Zhuzhou enters heavy metal Zn, Cu in the bed mud of Jiangkou, may further comprise the steps:
(1) preparation of bottom slurry: the Xiang River Xia Wan port, Zhuzhou of getting the 50g oven dry enters the bed mud at Jiangkou, and the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: Analysis on Selecting level citric acid adds citric acid in the above-mentioned bottom slurry while stir slowly, until pH is 2.
(3) oxide treatment: add concentration in the mixture after the acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%) and 0.08g FeSO
47H
2O is stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 70 ℃ in the microwave reactor, insulation 8min after reacting by heating is finished, is cooled to room temperature.
(5) filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: add BaS in heavy metal filtrate, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measure process before and after the content of Zn, Cu in the dredging bed mud in river, learn that as calculated the clearance of heavy metal Zn and Cu is respectively 77.5% and 65.4% to the method in the bed mud of Jiangkou to entering.
Embodiment 6:
A kind of method (technological line is referring to Fig. 1) of removing heavy metal Zn, Cu in the sewage draining exit bed mud of Xiang River Xia Wan port, Zhuzhou may further comprise the steps:
(1) preparation of bottom slurry: get the bed mud of Xiang River Xia Wan port, the Zhuzhou sewage draining exit of 50g oven dry, the leaf in the removal bed mud, branch, macrobead thing etc. add the 200mL deionized water, are stirred to evenly, get bottom slurry.
(2) acidification: Analysis on Selecting level oxalic acid adds oxalic acid in the above-mentioned bottom slurry while stir slowly, until pH is 2.
(3) oxide treatment: add concentration in the mixture after the acidification and be 30% hydrogen peroxide (quality of hydrogen peroxide be dry bottom shale amount 11%) and 0.08g FeSO
47H
2O is stirred to evenly.
(4) microwave heating: the reaction product after the oxide treatment is positioned over carries out microwave heating to 80 ℃ in the microwave reactor, insulation 6min after reacting by heating is finished, is cooled to room temperature.
(5) filter: the product after the microwave heating is carried out solid-liquid separation, obtain bed mud slag and the filtrate that contains Zn, Cu.
(6) extraction of heavy metal and recovery: add BaS in heavy metal filtrate, regulating pH is 8.0, obtains clear liquid and the heavy metal slag that contains Zn, Cu.
Utilize Xray fluorescence spectrometer by measuring the content of processing Zn, Cu in the front and back dredging bed mud in river, learn that as calculated the method is respectively 62.2% and 53.4% to the clearance of heavy metal Zn and Cu in the sewage draining exit bed mud.
The above only is preferred implementation of the present invention, and protection scope of the present invention also not only is confined to above-described embodiment.All technical schemes that belongs under the thinking of the present invention all belong to protection scope of the present invention.Be noted that for those skilled in the art in the improvements and modifications that do not break away under the principle of the invention prerequisite, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. remove the method for dredging heavy metal Zn, Cu in the bed mud in river for one kind, it is characterized in that, described method comprises dredging bed mud in river and water is mixed into bottom slurry by 1: 2～10 mass ratio, after bottom slurry carried out acidification and oxide treatment, the reaction product that obtains is carried out microwave heating to 60 ℃～120 ℃, insulation 5min～10min, filtration after reacting by heating is finished, obtain bed mud slag and the filtrate that contains Zn, Cu, filtrate is carried out chemical settling, regulating pH is 7.5～8.5, gets clear liquid and the heavy metal slag that contains Zn, Cu.
2. the method for heavy metal Zn, Cu in the removal according to claim 1 dredging bed mud in river is characterized in that, described acidification process comprises in described bottom slurry and adds while stirring mineral acid or organic acid, regulates pH to 1～3.
3. the method for heavy metal Zn, Cu in the removal dredging bed mud in river according to claim 2 is characterized in that described mineral acid is the vitriol oil, HNO
3Or hydrochloric acid, described organic acid is citric acid, oxalic acid or acetic acid.
4. the method for heavy metal Zn, Cu in the removal dredging bed mud in river according to claim 3 is characterized in that described mineral acid is the vitriol oil.
5. the method for heavy metal Zn, Cu according to claim 1 and 2 or in the 3 described removals dredging bed mud in river is characterized in that, described oxidation processes comprises in the mixture after the described acidification and adds while stirring hydrogen peroxide or add hydrogen peroxide and FeSO
47H
2The combination of O.
6. the method for heavy metal Zn, Cu in the removal dredging bed mud in river according to claim 5 is characterized in that the quality of described hydrogen peroxide is 8%～12% of dredging bed mud in river quality, described FeSO
47H
2The quality of O is 0.1%～0.3% of dredging bed mud in river quality.
7. the method for heavy metal Zn, Cu according to claim 1 and 2 or in the 3 described removals dredging bed mud in river is characterized in that the sinking agent that described chemical settling is used is water-soluble metallic sulfide.
8. the method for heavy metal Zn, Cu in the removal dredging bed mud in river according to claim 7 is characterized in that described metallic sulfide is Na
2S, BaS or CaS.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449694A (en) * | 2013-09-16 | 2013-12-18 | 湖南大学 | Method for removing heavy metal lead in water sediment |
| CN104341080A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院沈阳应用生态研究所 | Method for removing and recovering Zn in sludge |
| CN104342554A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院沈阳应用生态研究所 | Method for removing and recovering copper in municipal excess sludge |
| CN104386889A (en) * | 2014-06-09 | 2015-03-04 | 何晋勇 | Efficient leaching processing method for composite heavy-metal-polluted bottom sediment |
| CN104962949A (en) * | 2015-06-09 | 2015-10-07 | 中国科学院兰州化学物理研究所 | Method for removing copper in nickel electrolysis anode solution for purification |
| CN110922202A (en) * | 2019-12-10 | 2020-03-27 | 福建省明能新型建材有限公司 | Preparation method of novel regenerated ceramsite, novel regenerated ceramsite and application thereof |
| CN111547963A (en) * | 2020-04-01 | 2020-08-18 | 泉州市洋屿土壤科技有限公司 | Method for removing heavy metal in organic sludge by pulping |
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| CN101948225A (en) * | 2010-09-14 | 2011-01-19 | 长沙洁湘环保工程有限公司 | Method for quickly dewatering and effectively removing heavy metals from primary sludge |
| CN102583916A (en) * | 2012-02-09 | 2012-07-18 | 湖北鼎鑫环保科技有限公司 | Method for removing heavy metal from sludge |
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| CN101948225A (en) * | 2010-09-14 | 2011-01-19 | 长沙洁湘环保工程有限公司 | Method for quickly dewatering and effectively removing heavy metals from primary sludge |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341080A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院沈阳应用生态研究所 | Method for removing and recovering Zn in sludge |
| CN104342554A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院沈阳应用生态研究所 | Method for removing and recovering copper in municipal excess sludge |
| CN103449694A (en) * | 2013-09-16 | 2013-12-18 | 湖南大学 | Method for removing heavy metal lead in water sediment |
| CN104386889A (en) * | 2014-06-09 | 2015-03-04 | 何晋勇 | Efficient leaching processing method for composite heavy-metal-polluted bottom sediment |
| CN104962949A (en) * | 2015-06-09 | 2015-10-07 | 中国科学院兰州化学物理研究所 | Method for removing copper in nickel electrolysis anode solution for purification |
| CN110922202A (en) * | 2019-12-10 | 2020-03-27 | 福建省明能新型建材有限公司 | Preparation method of novel regenerated ceramsite, novel regenerated ceramsite and application thereof |
| CN111547963A (en) * | 2020-04-01 | 2020-08-18 | 泉州市洋屿土壤科技有限公司 | Method for removing heavy metal in organic sludge by pulping |
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Application publication date: 20130313 |