CN1884116A - Method for processing refuse-burning fly-ash by using magnesium ammonium phosphate sedimentation sludge - Google Patents

Method for processing refuse-burning fly-ash by using magnesium ammonium phosphate sedimentation sludge Download PDF

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Publication number
CN1884116A
CN1884116A CNA2006100287609A CN200610028760A CN1884116A CN 1884116 A CN1884116 A CN 1884116A CN A2006100287609 A CNA2006100287609 A CN A2006100287609A CN 200610028760 A CN200610028760 A CN 200610028760A CN 1884116 A CN1884116 A CN 1884116A
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fly ash
ammonia nitrogen
waste incineration
concentration
ammonium phosphate
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CNA2006100287609A
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Chinese (zh)
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CN100445217C (en
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何品晶
张后虎
邵立明
章骅
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同济大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses

Abstract

The invention discloses a together-disposing method of burnt rubbish ash and high-density ammonia nitrogen waste water, which comprises the following steps: testing density of ammonia nitrogen in the waste water; putting Mg2+ and PO43- in the waste water according to 1:0.9-1.0:1.0-1.2 molar rate for NH4+:Mg2+:PO43-; stirring or aerating for 20-120 min; sedimenting 20-60 min; removing supernatant; adjusting liquid-solid rate at 1:3 for remained mud and burnt rubbish ash; stirring evenly; curing 1-2 day at normal temperature; testing heavy metal immersed density of sample; burying directly or making soil modifier or fertilizer after reaching national standard limit.

Description

Method for treating waste incineration fly ash by using magnesium ammonium phosphate precipitated sludge
Technical Field
A method for treating waste incineration fly ash by using magnesium ammonium phosphate to precipitate sludge relates to a co-disposal technology of waste incineration fly ash and high-concentration ammonia nitrogen wastewater, and belongs to a waste co-disposal and utilization technology.
Background
MSWI (bacterial Solid Waste addition) fly ash generated in the garbage incineration process mainly consists of alkaline oxides, and the aqueous solution of the MSWI (bacterial Solid Waste addition) fly ash is strong alkaline (the Solid-to-liquid ratio is 1: 10, and the pH value is more than 12.0). The fly ash is classified as dangerous waste because of enriching a large amount of soluble heavy metals, salts and a small amount of highly toxic organic pollutants, and the fly ash can be landfilled or utilized after being subjected to stabilization treatment according to the current regulations in China.
The MSWI fly ash medicament stabilizing technology adopts chemical medicaments (such as phosphates, iron oxides, sulfides, polymer chelating agents and the like) to perform chemical reaction (dissolution, precipitation, chelation and the like) with substances such as heavy metals and the like in fly ash to generate substances with extremely low solubility and high chemical stability, thereby achieving the aim of stabilizing treatment of the heavy metals in the fly ash. The medicament stabilizing technology has the advantages of low capacity-increasing ratio, good effect, low cost, simple and convenient operation and the like, and is widely researched and applied, wherein the soluble phosphate stabilized fly ash (the stabilizing technology for treating incineration fly ash by soluble phosphate) is adopted, the environment science is achieved in Jiang nations, Zhangan, Xin, and the like, 2005, 26 (4): 191-194) only sodium phosphate accounting for 3-7% of the weight of the fly ash is added, and the leaching concentration of heavy metals (Pb, Zn, Cd and the like) in the fly ash can be lower than the identification standard of hazardous wastes in China.
On the other hand, high-concentration ammonia nitrogen wastewater such as landfill leachate, residual ammonia water of coking plant and the like is a kind of high-concentration complex organic wastewater which is difficult to treat, and the ammonia nitrogen concentration can reach thousands of milligrams per liter, taking the landfill leachate as an example: its CODcr=12000~18000mg/L,BOD5=4000~8000mg/L,NH3-N is 1200-1600 mg/L. And NH3The N concentration of more than 500mg/L can possibly inhibit the aerobic nitrobacteria; at the same time, the BOD of the percolate5The content is also difficult to achieve, according to BOD5N and P are 100: 5: 1 to provide a denitrification denitrogenation carbon source. Therefore, such waste water is usually treated by physical and chemical methods to remove NH before biochemical treatment3-N removal.
The precipitation method of Magnesium Ammonium Phosphate (hereinafter referred to as MAP) is a physical and chemical method capable of effectively removing high-concentration ammonia nitrogen in wastewater. The principle is as follows: adding Mg into waste water containing high-concentration ammonia nitrogen2+(MgO,MgCl2Etc.) and PO4 3-(Na2HPO4·12H2O, etc.) ionic agents, and in waste waterNH4 +Reacting to generate magnesium ammonium phosphate crystal (MgNH)4PO4·6H2O, commonly known as struvite), and precipitating and separating, thereby reducing the concentration of ammonia nitrogen in the wastewater. In addition, if MgO is used, the pH value can be adjusted, and partial BOD, refractory organic matters and toxic and harmful substances with the effect of inhibiting the growth of microorganisms can be removed by coagulation, so that the biodegradability of the wastewater is improved (research on the magnesium ammonium phosphate precipitation method pretreatment technology of landfill leachate, Shang ai' an, Zhao Qing Xiang, Xumei Yan, and the like, water supply and drainage, 2004, 30 (11): 22-25.), and the reaction process and the reaction balance coefficient for forming magnesium ammonium phosphate are as follows:
(1)
Ks=[Mg2+][NH4 +][PO4 3-]=2.5*10-13(2)
MAP crystals obtained in the above treatment are alkaline salts, and in the solution environment with pH>9.5, the crystals are dissolved, ammonium ions in the crystals become gaseous ammonia and volatilize, and Mg2+With OH-Generation of Mg (OH)2Precipitating to obtain PO4 3-The solution of (1). Therefore, the MAP crystal precipitated sludge obtained after wastewater treatment and the fly ash are mixed, and the characteristic that the fly ash is strong in alkalinity in aqueous solution is utilized to decompose the MAP crystal of the sludge obtained after wastewater treatment and release phosphate ions, so that the MAP crystal is combined withheavy metals in the fly ash to stabilize the MAP crystal precipitated sludge.
In this process, phosphate can be utilized twice: the method has the advantages that MAP precipitates are generated by participating in magnesium ammonium phosphate precipitation reaction in high-concentration ammonia nitrogen wastewater treatment, and then the MAP precipitates are mixed with fly ash to dissolve the MAP precipitates and release phosphate radicals to stabilize heavy metals, so that the aims of effectively treating wastes and reducing the treatment cost of wastewater and fly ash are fulfilled.
Disclosure of Invention
The invention aims to disclose a method for co-treating municipal solid waste incineration fly ash and high-concentration ammonia nitrogen wastewater. Particularly, MAP crystal precipitated sludge derived from wastewater treatment is mixed with fly ash to stabilize heavy metals in the fly ash.
In order to achieve the above object, the present invention found out through the characteristic study of the fly ash from waste incineration, that the fly ash from waste incineration contains a large amount of alkali metal salts (CaO, K)2O and Na2O, etc.) in an aqueous solution having a solid-to-liquid ratio of 1: 10, the pH value of the aqueous solution is generally higher than 12.0. The method provides reaction conditions for mixing the crystal precipitate with alkali-soluble wastewater treatment derived MAP (magnesium ammonium phosphate), releasing phosphate ions in the crystal precipitate, and reacting the crystal precipitate with heavy metals in fly ash to generate insoluble compounds. We found 2 basic steps to implement this process through long-term experiments: 1) high-concentration ammonia nitrogen wastewater denitrification treatment and MAP precipitated sludge formation. Firstly, according to the initial concentration of ammonia nitrogen in the waste water and the formed MAP stoichiometric formula, quantitatively adding Mg which can be dissociated to produce Mg into the waste water2+And PO4 3-An ionic chemical agent; stirring to make the medicine fully dissolved and react; then, performing sedimentationAnd (4) precipitating and separating, discharging the treated wastewater and recovering MAP precipitated sludge. Wherein, for the generation of Mg2+And PO4 3-The ionic chemical agent is required to be sufficiently soluble in water to contain Mg2+And PO4 3-Can be fully utilized. 2) MAP precipitated sludge reacts with fly ash to release soluble PO4 3-The ions and the heavy metals in the fly ash generate insoluble substances, and the stabilization of the fly ash is completed. Firstly, fully mixing fly ash and MAP precipitated sludge according to a certain proportion; then the mixture is maintained for a certain period to ensure that the reaction is complete. Wherein, the mixing proportion of the fly ash and the MAP precipitated sludge must ensure that the pH of the mixture is more than 10, and PO in MAP4 3-The mole number of the ions needs to keep more than 10 times of excess for heavy metals in the fly ash; because the heavy metal content in the fly ash is small (less than 0.5% w/w) and the CaO content is more than 10% w/w, the dry basis mass ratio of MAP precipitated sludge to the waste incineration fly ash is more than or equal to 1: 10.
The verification of the treatment steps is carried out by taking the garbage percolate from the Hangzhou Tianziling garbage disposal plant and the fly ash from a certain domestic garbage incineration plant in Shanghai city. Actually measuring the ammonia nitrogen initial concentration of the leachate to be 1000-1400 Mg/L according to Mg2+∶NH4 +∶PO4 3-Adding a medicament according to the molar ratio of 0.9-1.0: 1: 1.0-1.2, stirring or aerating and mixing the wastewater after adding the medicament for 20-200 minutes, and then standing and precipitating the treated wastewater for 20-60 minutes. And after the supernatant liquid is removed from the effluent, the remaining sludge is ready for use.
Adjusting the proportion of 2 materials according to the mixing proportion (dry basis) of the obtained MAP precipitated sludge and the waste incineration fly ash of 1: 1-9 and the requirement that the liquid-solid ratio is about 1: 3, uniformly stirring and mixing, and curing in the air at normal temperature for 1-2 days to ensure that the reaction is sufficient; then, the treated products in which the mixing ratio of the sludge to the fly ash is 1: 9, 1: 4 and 1: 1.5 are taken to measure the leaching concentration of the heavy metal ions, and the result (table 1) shows that the heavy metals in the waste incineration fly ash are effectively stabilized and reach the national standard limit value (GB 5086.1-1997), and the waste incineration fly ash can be directly sent to a landfill site for landfill disposal or resource utilization.
Table 1: heavy metal leaching concentration (mg/L) of mixed ash samples with different proportions
Heavy metal species Ni Cu Zn Cd Pb Cr Hg
Undisturbed fly ash 10 g sludge/90 g fly ash 20 g sludge/80 g fly ash 40 g sludge/60 g fly ash National standard 0 0 0 0 10 0 0 0 0.086 50 3.286 0.266 0.01 0 50 0.001 0 0 0 0.3 26.93 1.619 0.134 0 3.0 0.229 0.079 0.046 0.024 1.5 0.031 0.0067 0 0 0.05
The specific technical scheme and measures of the invention are as follows:
firstly, measuring the initial concentration of ammonia nitrogen in the high-concentration ammonia nitrogen wastewater, and then, according to NH4 +∶Mg2+∶PO4 3-The Mg is metered and added according to the mol ratio of 0.9-1.0: 1: 1.0-1.22+And PO4 3-The chemical agent of (1), wherein Mg2+To comeMagnesium salts derived from strong inorganic acids and magnesium oxide (MgO), PO4 3-Derived from phosphoric acid or its sodium and potassium salts; will contain Mg2+And PO4 3-After the chemical agent is added into the high-concentration ammonia nitrogen wastewater, stirring or aerating and mixing for 20-200 minutes, and then standing and precipitating for 20-60 minutes; and removing the supernatant, mixing the residual precipitated sludge and the waste incineration fly ash in a dry basis of 1: 1-9, adjusting the liquid-solid ratio of the precipitated sludge to the waste incineration fly ash to be 1: 3, uniformly stirring and mixing, maintaining in the air at normal temperature for 1-2 days to fully react, sampling to determine the leaching concentration of the heavy metal, and directly conveying the heavy metal to a landfill to be buried or used as a soil conditioner or a fertilizer after reaching the limit of the national standard.
The waste incineration fly ash and the sludge are mixed according to a high proportion, and the obtained product can be sent to a landfill site for landfill treatment, so that the method has the advantage of low cost; the obtained product can not only adjust the pH value of the soil, but also be an efficient slow-release fertilizer, and the slow-release nitrogen, phosphorus and other elements can improve the nutritional structure of the soil,
the invention has the following advantages and effects:
1. the adopted magnesium ammonium phosphate sediment and the fly ash are mixed for treatment, so that one dose of phosphate is used, and the medicament cost is greatly reduced. In addition, in the mixture with the weight of 100 g, the magnesium ammonium phosphate precipitate can reach the standard only by adding about 10 g (see table 1), the weight gain ratio is only slightly higher than 10%, and compared with 40-50% of a cement curing method, the method has the advantage of low landfill cost.
2. The magnesium ammonium phosphate precipitated sludge has high water content, and the sludge before transportation is difficult to dehydrate if the magnesium ammonium phosphate precipitated sludge is singly buried or utilized; and the fly ash is mixed with the waste incineration fly ash, so that the process can be omitted: the fly ash has large moisture absorption capacity, can absorb a part of percolate by mixing with sludge, not only reduces the treatment capacity of the percolate, but also saves water resources, and has multiple advantages compared with the simple medicament stable waste incineration fly ash.
3. Research results on utilization of waste incineration fly ash or magnesium ammonium phosphate precipitated sludge as fertilizer or soil conditioner are reported at home and abroad. The waste incineration fly ash can adjust the pH value of soil, and soluble salts such as calcium, magnesium and the like contained in the waste incineration fly ash have positive effects on plant growth, but have the hidden danger of heavy metal pollution; the magnesium ammonium phosphate precipitated sludge is used as a good slow-release fertilizer, and the rich elements such as nitrogen, phosphorus and the like can enhance the nutrient content of soil. The two substances are mixed for use, so that various advantages are integrated, and meanwhile, the phosphate stabilizes heavy metal ions, so that the defects of the waste incineration fly ash in the aspect of being applied to soil conditioners and fertilizers are overcome, and the effects of strengthening the advantages and making up for the disadvantages are achieved.
Detailed Description
Example 1
Firstly, determining the initial concentration of ammonia nitrogen in high-concentration ammonia nitrogen wastewater according to Mg2+∶NH4 +∶PO4 3-Mole ofAdding medicament (MgSO) at a ratio of 1: 1.14,NaH2PO4·2H2O), adding the medicine, stirring or aerating and mixing the wastewater for 40 minutes, and then standing and precipitating the treated wastewater for 30 minutes. And after the supernatant liquid of the effluent is removed, the residual precipitated sludge is ready for use.
The proportion of 2 materials is adjusted according to the requirements that the proportion (dry basis) of precipitated sludge and waste incineration fly ash is 1: 9 and the liquid-solid ratio is about 1: 3, the materials are uniformly stirred and mixed, the mixture is maintained in the air at normal temperature for 1 day to ensure that the reaction is full, the leaching concentration of heavy metal ions is measured, and the heavy metal ions can be directly sent to a landfill site for landfill after reaching the standard.
Example 2
Firstly, determining the initial concentration of ammonia nitrogen in high-concentration ammonia nitrogen wastewater according to Mg2+∶NH4 +∶PO4 3-Adding medicament (MgO, Na) with the molar ratio of 0.9: 12HPO4·12H2O), adding the medicine, stirring or aerating and mixing the wastewater for 100 minutes, and then standing and precipitating the treated wastewater for 40 minutes. And after the supernatant liquid of the effluent is removed, the residual precipitated sludge is ready for use.
According to the requirements of 1: 8 ratio (dry basis) of precipitated sludge and refuse incineration fly ash and 1: 3 of liquid-solid ratio, the proportion of 2 materials is regulated, uniformly stirred and mixed, maintained in air at normal temperature for 1 day to make reaction fully, and the leaching concentration of heavy metal ions is measured, and can be directly sent to a landfill site for landfill after reaching the standard.
Example 3
Firstly, determining the initial concentration of ammonia nitrogen in high-concentration ammonia nitrogen wastewater according to Mg2+∶NH4 +∶PO4 3-Adding medicament (MgO, K) with the molar ratio of 1: 1.22HPO4·3H2O), adding the medicine, stirring or aerating and mixing the wastewater for 150 minutes, and then standing and precipitating the treated wastewater for 60 minutes. And after the supernatant liquid is removed from the effluent, the remaining sludge is ready for use.
The method comprises the steps of adjusting the proportion of 2 materials according to the requirements of 1: 1 (dry basis) of precipitated sludge and waste incineration fly ash and 1: 3 of liquid-solid ratio, stirring and mixing, maintaining for 2 days in air at normal temperature to ensure that the reaction is full, measuring the leaching concentration of heavy metal ions, and using the heavy metal ions as a soil conditioner or a fertilizer after reaching the standard.

Claims (4)

1. The method for treating the waste incineration fly ash by using magnesium ammonium phosphate to precipitate sludge is characterized by comprising the following steps of: firstly, measuring the initial concentration of ammonia nitrogen in the high-concentration ammonia nitrogen wastewater, and then, according to NH4 +∶Mg2+∶PO4 3-The Mg is added according to the molar ratio of 1: 0.9-1.0: 1.0-1.22+And PO4 3-The chemical agent of (1); will contain Mg2+And PO4 3-After the chemical agent is added into the high-concentration ammonia nitrogen wastewater, stirring or aerating and mixing for 20-200 minutes, and then standing and precipitating for 20-60 minutes; removing supernatant, mixing the residual precipitated sludge and waste incineration fly ash according to the dry-basis mass ratio of 1: 1-9, adjusting the liquid-solid ratio of the precipitated sludge to the waste incineration fly ash to be 1: 3, stirring and mixing uniformly, maintaining for 1-2 days in normal-temperature air to fully react, sampling to determine the leaching concentration of heavy metal, and directly conveying to a landfill site after reaching the limit value of the national standardLandfills, or as soil conditioners or fertilizers.
2. The method for treating fly ash from waste incineration with magnesium ammonium phosphate precipitated sludge as claimed in claim 1, wherein: the high-concentration ammonia nitrogen wastewater has ammonia nitrogen concentration of more than 1000mg/L and BOD5/CODcrThe ratio is lower than 0.2, and the garbage percolate and the sewage of a coking plant with poor biochemical treatment performance can be treated.
3. The method for treating fly ash from waste incineration with magnesium ammonium phosphate precipitated sludge as claimed in claim 1, wherein: said Mg-containing2+The chemical agent is derived from magnesium salt of inorganic strong acid or magnesium oxide.
4. The method for treating fly ash from waste incineration with magnesium ammonium phosphate precipitated sludge as claimed in claim 1, wherein: said PO containing4 3-The chemical agent is derived from phosphoric acid or its sodium or potassium salt.
CNB2006100287609A 2006-07-10 2006-07-10 Method for processing refuse-burning fly-ash by using magnesium ammonium phosphate sedimentation sludge CN100445217C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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WO2009024014A1 (en) * 2007-08-21 2009-02-26 Nanjing University Method for removing ammonia from coking waste water
CN101830568A (en) * 2010-05-10 2010-09-15 南京大学 Functional biological fixation in-situ remediation method for underground water polluted by nitrogen
CN101838061A (en) * 2010-05-17 2010-09-22 赣州华兴钨制品有限公司 Method for treating ammonia-nitrogen wastewater and recovering the same into ammonium salt
CN101875526B (en) * 2010-05-13 2011-09-07 宜兴蓝星化工环保研究院有限公司 Method for treating coking waste water after ammonia removal
CN102319721A (en) * 2011-07-21 2012-01-18 广州环投技术设备有限公司 Method for simultaneously treating domestic garbage burning fly ash and domestic garbage leachate
CN102838223A (en) * 2011-06-20 2012-12-26 四川环美能科技有限公司 Advanced treatment process for coking wastewater by using resin in multistage fluidized-bed
CN106435192A (en) * 2016-09-13 2017-02-22 南京大学 Method for removing and recycling copper from magnesium ammonium phosphate sludge
CN106613476A (en) * 2016-11-10 2017-05-10 陈建峰 Method for cultivating matrix nutrient soil by means of household waste incineration fly ash
CN107739219A (en) * 2017-10-10 2018-02-27 安徽工业大学 A kind of method that potash fertilizer raw material is prepared with house refuse burning flying dust
CN108191320A (en) * 2018-03-14 2018-06-22 清华大学 A kind of method that waterproof chlorine oxygen magnesium refractory brick is made using domestic garbage incineration flyash

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JP3985096B2 (en) * 2002-12-26 2007-10-03 日立造船株式会社 Method for stabilizing heavy metals in fly ash
CN1623924A (en) * 2003-12-04 2005-06-08 中国科学院生态环境研究中心 Process for removing ammonia of treating waste water containing high contentrition ammonia
CN1695832A (en) * 2005-04-29 2005-11-16 清华大学 Method for stabilizing flying ash from burn by using soluble medicament of phosphate

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8329040B2 (en) 2007-08-21 2012-12-11 Nanjing University Method for removing ammonia nitrogen in coking wastewater
WO2009024014A1 (en) * 2007-08-21 2009-02-26 Nanjing University Method for removing ammonia from coking waste water
CN101830568A (en) * 2010-05-10 2010-09-15 南京大学 Functional biological fixation in-situ remediation method for underground water polluted by nitrogen
CN101875526B (en) * 2010-05-13 2011-09-07 宜兴蓝星化工环保研究院有限公司 Method for treating coking waste water after ammonia removal
CN101838061A (en) * 2010-05-17 2010-09-22 赣州华兴钨制品有限公司 Method for treating ammonia-nitrogen wastewater and recovering the same into ammonium salt
CN101838061B (en) * 2010-05-17 2012-01-04 赣州华兴钨制品有限公司 Method for treating ammonia-nitrogen wastewater and recovering the same into ammonium salt
CN102838223A (en) * 2011-06-20 2012-12-26 四川环美能科技有限公司 Advanced treatment process for coking wastewater by using resin in multistage fluidized-bed
CN102319721A (en) * 2011-07-21 2012-01-18 广州环投技术设备有限公司 Method for simultaneously treating domestic garbage burning fly ash and domestic garbage leachate
CN106435192A (en) * 2016-09-13 2017-02-22 南京大学 Method for removing and recycling copper from magnesium ammonium phosphate sludge
CN106435192B (en) * 2016-09-13 2018-06-26 南京大学 Removal and the method for recycling copper in a kind of ammonium magnesium phosphate sludge
CN106613476A (en) * 2016-11-10 2017-05-10 陈建峰 Method for cultivating matrix nutrient soil by means of household waste incineration fly ash
CN107739219A (en) * 2017-10-10 2018-02-27 安徽工业大学 A kind of method that potash fertilizer raw material is prepared with house refuse burning flying dust
CN108191320A (en) * 2018-03-14 2018-06-22 清华大学 A kind of method that waterproof chlorine oxygen magnesium refractory brick is made using domestic garbage incineration flyash
CN108191320B (en) * 2018-03-14 2019-09-27 清华大学 A method of waterproof chlorine oxygen magnesium refractory brick is made using domestic garbage incineration flyash

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