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 PDFInfo
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- 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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- ammonium phosphate
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- incineration
- refuse flyash
- magnesium ammonium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers 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
Technical field
With the method for magnesium ammonium phosphate sediment sludge treatment incineration of refuse flyash, relate to the coexistence of a kind of incineration of refuse flyash and high-concentration ammonia nitrogenous wastewater and put technology, belong to the waste coexistence and put and utilize technology.
Background technology
MSWI (the Municipal Solid Waste Incineration) flying dust that the waste incineration process produces mainly is made up of basic oxide, and its aqueous solution is strong basicity (solid-to-liquid ratio 1: 10, pH＞12.0).Flying dust is because of enrichment great amount of soluble heavy metal, salt and a small amount of hypertoxic organic pollutant, and is classified as Hazardous wastes, and China's current law stipulates that it can landfill after must stabilized processing disposes or utilize.
The medicament stabilization technique of MSWI flying dust is to adopt chemical agent (as: phosphoric acid salt, ferriferous oxide, sulfide and high-molecular chelating agent etc.) with flying dust in material generation chemical reactions (dissolving, precipitation, chelating etc.) such as heavy metal, generate extremely low, the high stability material of chemical property of solubleness, thereby reach fly-ash heavy metal stabilization treatment purpose.The medicament stabilization technique have increase-volume than low, effect is good, cost is low and advantage such as easy and simple to handle, and broad research and application have been obtained, wherein, adopt soluble phosphate stablize flying dust (" stabilization technology of soluble phosphate processing flying ash ". Jiang Jianguo, Zhang Yan, Xu Xin, Deng. environmental science, 2005,26 (4): 191-194) only add the sodium phosphate that accounts for flying dust weight ratio 3～7%, just can make the leaching concentration of heavy metal in the flying dust (Pb, Zn, Cd etc.) be lower than China's Hazardous wastes judging standard.
On the other hand, high density ammonia nitrogen waste waters such as percolate, coke-oven plant's remained ammonia are the complicated organic waste water of the unmanageable high density of a class, and its ammonia nitrogen concentration can be an example with the percolate: its COD up to thousands of milligrams for every liter
Cr=12000～18000mg/L, BOD
5=4000～8000mg/L, NH
3-N=1200～1600mg/L.And NH
3-N concentration just might produce restraining effect to the aerobic nitrification bacterium greater than 500mg/L; Simultaneously, the BOD of percolate
5Content also is difficult to reach, and presses BOD
5: N: P=100: the requirement of denitrification denitrogenation carbon source is provided at 5: 1.Therefore, such waste water usually must be by physico-chemical process with NH before biochemical treatment
3-N removes.
Magnesium ammonium phosphate (Magnesium Ammonium Phosphate is hereinafter to be referred as the MAP) precipitator method are effectively to remove the physical chemistry method of waste water middle and high concentration ammonia nitrogen.Its principle is: add in the waste water that contains ammonia nitrogen in high density and contain Mg
2+(MgO, MgCl
2Deng) and PO
4 3-(Na
2HPO
412H
2O etc.) ionic medicament is with the NH in the waste water
4 +Reaction generates ammoniomagnesium phosphate crystal (MgNH
4PO
46H
2O is commonly called as struvite), precipitate and separate, thereby the concentration of ammonia nitrogen in the reduction waste water.In addition, if adopt MgO also can regulate the pH value, coagulation is removed part BOD, hardly degraded organic substance and microorganism growth had inhibiting hazardous and noxious substances, thus improve biodegradability (" the magnesium ammonium phosphate sediment method preconditioning technique research of percolate ". Shang Aian of waste water, Zhao Qingxiang, Xu Meiyan, etc. water supply and drainage, 2004,30 (11): 22-25.), the reaction process and the molecular balance coefficient that form magnesium ammonium phosphate are as follows:
Ks＝[Mg
2+][NH
4 +][PO
4 3-]＝2.5*10
-13 (2)
The MAP crystallization of gained is a basic salt in the above-mentioned processing, in the solution environmental of pH＞9.5, and crystallization meeting dissolving, ammonium ion wherein becomes the gaseous ammonia volatilization, simultaneously, Mg
2+With OH
-Generate Mg (OH)
2Precipitation can obtain containing PO
4 3-Solution.Therefore, we attempt the MAP crystalline deposit mud and the flying dust of gained after the wastewater treatment are mixed, and utilize flying dust to be alkaline characteristics in the aqueous solution, and the mud MAP crystallization that obtains after the wastewater treatment is decomposed and the release phosphate anion, thereby combine with heavy metal in the flying dust, make its stabilization.
In this course, phosphate radical can obtain twice utilization: participate in the magnesium ammonium phosphate sediment reaction earlier and produce the MAP precipitation in high-concentration ammonia nitrogenous wastewater is handled, mix with flying dust again make the MAP resolution of precipitate, discharge phosphate radical and come stabilizing heavy metal, reach effective processing of waste, reduce the purpose of waste water and flying dust processing cost simultaneously.
Summary of the invention
The objective of the invention is to disclose the method that the coexistence of a kind of fly ash from burning city domestic garbage and high-concentration ammonia nitrogenous wastewater is put.Specifically be to utilize the derive MAP crystalline deposit mud and the flying dust of gained of wastewater treatment to mix, stablize the heavy metal in the flying dust.
For reaching above-mentioned purpose, the present invention finds that by the characteristic research to incineration of refuse flyash incineration of refuse flyash contains a large amount of alkaline metal salts (CaO, K
2O and Na
2O etc.), its pH value generally is higher than 12.0 in 1: 10 the aqueous solution of solid-to-liquid ratio.This mixes with alkali-soluble wastewater treatment MAP (magnesium ammonium phosphate) crystalline deposit of deriving for it, discharges phosphate anion wherein, be used further to flying dust in heavy metal react the compound of generation insoluble, reaction conditions is provided.We have found 2 basic steps implementing this process through long-term experiment: 1) high-concentration ammonia nitrogenous wastewater is denitrogenated to handle with the MAP precipitating sludge and is formed.Working method is that at first, according to the starting point concentration of ammonia nitrogen in the waste water, the stoichiometric equation according to forming MAP quantitatively adds dissociable generation Mg in waste water
2+And PO
4 3-The ionic chemical agent; Restir fully dissolves medicament and reacts; Then, carry out precipitate and separate, discharge the waste water after handling and reclaim the MAP precipitating sludge.Wherein, to producing Mg
2+And PO
4 3-The requirement of ion chemistry medicament is can be water-soluble fully, makes contained Mg
2+And PO
4 3-Can be fully used.2) reaction of MAP precipitating sludge and flying dust discharges solvability PO
4 3-Ion, again with flying dust in heavy metal generate the indissoluble material, finish stabilizing fly ashization.Working method is, at first, and according to a certain percentage with flying dust and MAP precipitating sludge thorough mixing; Again mixture is carried out the maintenance of some cycles, make to react completely.Wherein, the blending ratio of flying dust and MAP precipitating sludge must guarantee mixture pH greater than 10, simultaneously PO among the MAP
4 3-The ionic mole number needs the heavy metal in the flying dust is kept excessive more than 10 times; Because the heavy metal content in the flying dust less (less than 0.5%w/w), CaO content are then greater than 10%w/w, therefore, MAP precipitating sludge and incineration of refuse flyash butt mass ratio all can meet the demands more than or equal to 1: 10 o'clock.
To the checking of above-mentioned treatment step, employing is taken to the percolate in disposal site, emperor mountain range, Hangzhou and the flying dust of Shanghai City municipal solid waste incinerator carries out.The ammonia nitrogen starting point concentration of actual measurement percolate is 1000～1400mg/L, according to Mg
2+: NH
4 +: PO
4 3-Mol ratio 0.9～1.0: 1: 1.0～1.2 ratio adds medicament, and waste water stirring or aeration mixed the waste water quiescent setting after will handling again 20～60 minutes 20～200 minutes after the dosing.After supernatant liquor was removed in water outlet, remaining mud was stand-by.
According to the requirement that the blending ratio (butt) and the liquid-solid ratio of gained MAP precipitating sludge and incineration of refuse flyash 1: 1～9 is about 1: 3, adjust 2 kinds of material's proportion, evenly mix, the normal temperature maintenance is 1～2 day in air, makes sufficient reacting; Then, got wherein mud and flying dust ratio of mixture and be 1: 9,1: 4 and the processing product of 1: 1.5 each group is measured the leaching concentration of heavy metal ion, result's (table 1) shows that the heavy metal in the incineration of refuse flyash is effectively stablized, the limit value (GB 5086.1-1997) that is up to state standards can directly send the landfill yard landfill to dispose or recycling.
Table 1: the heavy metal of row mixing ash sample does not leach concentration (mg/L) on year-on-year basis
| The heavy metal kind | Ni | Cu | Zn | Cd | Pb | Cr | Hg |
| Original state flying dust 10 gram mud/90 gram flying dusts, 20 gram mud/80 gram flying dusts, 40 gram mud/60 gram flying dust national standards | 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 |
Concrete technical scheme of the present invention and measure are as follows:
After measuring the starting point concentration of ammonia nitrogen in the high-concentration ammonia nitrogenous wastewater earlier, according to NH
4 +: Mg
2+: PO
4 3-=0.9～1.0: 1: 1.0～1.2 mol ratios, metering adds and contains Mg
2+And PO
4 3-Chemical agent, Mg wherein
2+Derive from the magnesium salts and the magnesium oxide (MgO) of inorganic acid, PO
4 3-Derive from phosphoric acid or its sodium, sylvite; To contain Mg
2+And PO
4 3-Chemical agent be added in the high-concentration ammonia nitrogenous wastewater after, stir or aeration mixed 20～200 minutes, quiescent setting is 20～60 minutes again; After removing supernatant liquor, with remaining precipitating sludge according to precipitating sludge: incineration of refuse flyash=1: 1～9 (butt) mixes, the liquid-solid ratio of adjusting both is 1: 3, mixes, and maintenance is 1～2 day in normal temperature air, make sufficient reacting, then, the sampling and measuring heavy metal leaches concentration, behind the limit value that is up to state standards, directly send the landfill yard landfill, or as soil improvement agent or fertilizer.
Incineration of refuse flyash of the present invention and mud are according to mixing at high proportion, and products therefrom can be delivered to the landfill yard landfill disposal, has advantage cheaply; According to low mixed, products therefrom not only can be regulated the potential of hydrogen of soil, a kind of especially slow release fertilizer efficiently, and slowly elements such as the nitrogen that discharges, phosphorus improve the trophic structure of soil,
The present invention has following advantage and effect:
1. magnesium ammonium phosphate sediment of Cai Yonging and flying dust combination treatment make and have reduced medicament expense usefulness largely by phosphoric acid salt potion double-purpose.In addition, be in the mixtures of 100 grams in weight, magnesium ammonium phosphate sediment only need add just can (seeing Table 1) up to standard about 10 grams, and its weightening finish is than only a little more than 10%, and 40～50% of relative cement solidification method has the lower-cost advantage of landfill.
2. the own water ratio height of magnesium ammonium phosphate sediment mud, if landfill disposal or utilization separately, the sludge dewatering before the transportation is difficult point; And mix with incineration of refuse flyash, can save this process: flying dust moisture absorption capacity is big, can by with mud blended absorbent part percolate, not only reduced the treatment capacity of percolate, and saved water resources, simple relatively medicament is stablized incineration of refuse flyash, has multiple advantage.
3. all reported about utilizing the achievement in research of incineration of refuse flyash or magnesium ammonium phosphate sediment mud as fertilizer sources or soil improvement agent both at home and abroad.Incineration of refuse flyash can be regulated the potential of hydrogen of soil, and solubility salts such as its calcium that contains, magnesium are grown up to plant and had active effect, but have the hidden danger of heavy metal contamination; Magnesium ammonium phosphate sediment mud is as a kind of good slow-releasing fertilizer, and elements such as its nitrogen that is rich in, phosphorus can strengthen the nutritive ingredient of soil.With above-mentioned two kinds of material mixing uses, make that above-mentioned various advantage obtains integrating, simultaneously phosphoric acid salt is to the stabilization of heavy metal ion, and perfect incineration of refuse flyash is applied to the existing defective of soil improvement agent and fertilizer aspect, has reinforcing edge, remedies the effect of inferior position.
Embodiment
Embodiment 1
At first measure the starting point concentration of ammonia nitrogen in the high-concentration ammonia nitrogenous wastewater, according to Mg
2+: NH
4 +: PO
4 3-1: 1: 1.1 ratio of mol ratio adds medicament (MgSO
4, NaH
2PO
42H
2O), waste water stirring or aeration mixed the waste water quiescent setting after will handling again 30 minutes 40 minutes after the dosing.After supernatant liquor was removed in water outlet, remaining precipitating sludge was stand-by.
According to precipitating sludge and 1: 9 ratio of incineration of refuse flyash (butt), liquid-solid ratio is that 2 kinds of material's proportion are adjusted in about 1: 3 requirement, evenly mix, maintenance is 1 day in normal temperature air, react fully, measure the leaching concentration of heavy metal ion, can directly send the landfill yard landfill after up to standard.
Embodiment 2
At first measure the starting point concentration of ammonia nitrogen in the high-concentration ammonia nitrogenous wastewater, according to Mg
2+: NH
4 +: PO
4 3-0.9: 1: 1 ratio of mol ratio adds medicament (MgO, Na
2HPO
412H
2O), waste water stirring or aeration mixed the waste water quiescent setting after will handling again 40 minutes 100 minutes after the dosing.After supernatant liquor was removed in water outlet, remaining precipitating sludge was stand-by.
It according to precipitating sludge and 1: 8 ratio of incineration of refuse flyash (butt), liquid-solid ratio about 1: 3 requirement, adjust 2 kinds of material's proportion, evenly mix, maintenance is 1 day in normal temperature air, react fully, measure the leaching concentration of heavy metal ion, can directly send the landfill yard landfill after up to standard.
Embodiment 3
At first measure the starting point concentration of ammonia nitrogen in the high-concentration ammonia nitrogenous wastewater, according to Mg
2+: NH
4 +: PO
4 3-1: 1: 1.2 ratio of mol ratio adds medicament (MgO, K
2HPO
43H
2O), waste water stirring or aeration mixed the waste water quiescent setting after will handling again 60 minutes 150 minutes after the dosing.After supernatant liquor was removed in water outlet, remaining mud was stand-by.
It according to precipitating sludge and 1: 1 ratio of incineration of refuse flyash (butt), liquid-solid ratio about 1: 3 requirement, adjust 2 kinds of material's proportion, mix, maintenance is 2 days in normal temperature air, react fully, measure the leaching concentration of heavy metal ion, can be used as soil improvement agent or fertilizer after up to standard.
Claims (4)
1. with the method for magnesium ammonium phosphate sediment sludge treatment incineration of refuse flyash, it is characterized in that: after measuring the starting point concentration of ammonia nitrogen in the high-concentration ammonia nitrogenous wastewater earlier, according to NH
4 +: Mg
2+: PO
4 3-=1: 0.9～1.0: 1.0～1.2 mol ratios are measured the Mg that contains that adds
2+And PO
4 3-Chemical agent; To contain Mg
2+And PO
4 3-Chemical agent be added in the high-concentration ammonia nitrogenous wastewater after, stir or aeration mixed 20～200 minutes, quiescent setting is 20～60 minutes again; After removing supernatant liquor, is precipitating sludge with remaining precipitating sludge according to the butt mass ratio: mix incineration of refuse flyash=1: 1～9, the liquid-solid ratio of adjusting both is 1: 3, mixes, and maintenance is 1～2 day in normal temperature air, make sufficient reacting, then, the sampling and measuring heavy metal leaches concentration, behind the limit value that is up to state standards, directly send the landfill yard landfill, or as soil improvement agent or fertilizer.
2. the method with magnesium ammonium phosphate sediment sludge treatment incineration of refuse flyash according to claim 1 is characterized in that: described high-concentration ammonia nitrogenous wastewater be ammonia nitrogen concentration greater than 1000mg/L, BOD
5/ COD
CrRatio is lower than 0.2, the percolate of biochemical treatment difference, coke-oven plant's sewage.
3. the method with magnesium ammonium phosphate sediment sludge treatment incineration of refuse flyash according to claim 1 is characterized in that: the described Mg of containing
2+Chemical agent derives from the magnesium salts or the magnesium oxide of inorganic acid.
4. the method with magnesium ammonium phosphate sediment sludge treatment incineration of refuse flyash according to claim 1 is characterized in that: the described PO of containing
4 3-Chemical agent derives from phosphoric acid or its sodium, sylvite.
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Cited By (11)
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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 |
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| CN106435192A (en) * | 2016-09-13 | 2017-02-22 | 南京大学 | Method for removing and recycling copper from magnesium ammonium phosphate sludge |
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| 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 |
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