CN109205973A - A kind of harmless curing method of complexity heavy metal hazardous waste sludge slag and its cured product - Google Patents
A kind of harmless curing method of complexity heavy metal hazardous waste sludge slag and its cured product Download PDFInfo
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- CN109205973A CN109205973A CN201811168776.9A CN201811168776A CN109205973A CN 109205973 A CN109205973 A CN 109205973A CN 201811168776 A CN201811168776 A CN 201811168776A CN 109205973 A CN109205973 A CN 109205973A
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- heavy metal
- hazardous waste
- waste sludge
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- slag
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of harmless curing methods of complicated heavy metal hazardous waste sludge slag, belong to dangerous waste processing technology field, comprising the following steps: complicated heavy metal hazardous waste sludge slag successively by dehydration, grinding, is obtained complicated heavy metal hazardous waste sludge ground-slag end by the present invention；The complexity heavy metal dangerous waste body refuse includes heavy metal and organic matter；The heavy metal be arsenic, mercury, chromium, cadmium, lead, nickel, beryllium, copper, zinc, selenium and antimony in two kinds and it is two or more；The mass content of the heavy metal is 1~10g/kg of complicated heavy metal hazardous waste sludge；It successively cures, form and conserves after obtained complicated heavy metal hazardous waste sludge ground-slag end, alkaline calcium activator, metal ion mineralizer, solidifying substance and water are mixed.Method provided by the invention can fix various heavy simultaneously, inhibit Leaching of Heavy Metals, toxicity leaching rate is made to reach state specified standards.
Description
Technical field
The present invention relates to dangerous waste processing technology fields, the in particular to a kind of harmless solidification side of complicated heavy metal hazardous waste sludge slag
Method and its cured product.
Background technique
Complicated heavy metal hazardous waste sludge slag refers to the trade waste sludge silt containing various heavy and organic matter, refers to more
Various heavy in arsenic, mercury, chromium, cadmium, lead, nickel, beryllium, copper, zinc, selenium and antimony coexists, this is to complicated heavy metal hazardous waste sludge slag
Non-hazardousization processing cause certain difficulty.
Currently, the processing method of complicated heavy metal hazardous waste sludge slag has absorption stabilization method, elution method, cement solidification method, kiln
Oven process, landfill method etc..Cement solidification technology is that waste and cement mixing are formed hard cement solidification after hydration reaction
Body leaches to achieve the purpose that reduce hazard component in waste.But in various heavy and deposit in the case where can not synchronize
It fixes, especially arsenic, cadmium, copper, selenium.
Summary of the invention
In view of this, the present invention provides a kind of harmless curing method of complicated heavy metal hazardous waste sludge slag, the present invention is provided
Method can fix various heavy simultaneously, inhibit Leaching of Heavy Metals, leaching rate made to reach state specified standards.
The present invention provides a kind of harmless curing methods of complicated heavy metal hazardous waste sludge slag, comprising the following steps:
1) complicated heavy metal hazardous waste sludge slag is obtained into complicated heavy metal hazardous waste sludge ground-slag successively by dehydration, grinding
End；The complexity heavy metal dangerous waste body refuse includes heavy metal and organic matter；The heavy metal be arsenic, mercury, chromium, cadmium, lead, nickel, beryllium,
Two or more in copper, zinc, selenium and antimony；The mass content of the heavy metal be complicated heavy metal hazardous waste sludge 1~
10g/kg；
2) the complicated heavy metal hazardous waste sludge ground-slag end that obtains step 1), alkaline calcium activator, metal ion mineralising
It successively cures, form and conserves after agent, solidifying substance and water mixing, obtain cured product.
Preferably, the moisture content of dewatered complexity heavy metal hazardous waste sludge slag is 0~5% in the step 1).
Preferably, in the step 1) complicated heavy metal hazardous waste sludge ground-slag end granularity≤120 mesh.
Preferably, the calcareous activator of step 2) neutral and alkali is calcium carbonate, calcium hydroxide, calcium oxide, calcium sulfate, phosphoric acid
Calcium, calcium nitrate or calcium chloride.
Preferably, metal ion mineralizer is that extraordinary heavy metal tracks down and arrests agent, humic acid chemicals and length in the step 2)
Chain neutral polymer.
Preferably, curing agent is silicate, aluminate, aluminium sulfate, ferrous aluminate, fluorite thunder mineral in the step 2)
Or sepiolite class mineral.
Preferably, complicated heavy metal hazardous waste sludge ground-slag end, alkaline calcium activator, metal ion mine in the step 2)
The mass ratio of agent, solidifying substance and water is 1000:0.1~5:0.1~5:200~1000:100~150.
Preferably, the temperature cured in the step 2) is room temperature, and the time of curing is 1~5h.
Preferably, the pressure of green compact is 5MPa~24MPa in the step 2)；The pressure of the powder agglomates be 2MPa~
20MPa。
Preferably, the temperature conserved in the step 2) is 25~30 DEG C；The time of the maintenance is 5~10 days.
The present invention also provides the cured products that the above method is prepared.
The present invention provides a kind of harmless curing methods of complicated heavy metal hazardous waste sludge slag, comprising the following steps: will be complicated
Heavy metal hazardous waste sludge slag successively by dehydration, grinding, obtains complicated heavy metal hazardous waste sludge ground-slag end；The complexity heavy metal
Dangerous waste body refuse includes heavy metal and organic matter；The heavy metal is in arsenic, mercury, chromium, cadmium, lead, nickel, beryllium, copper, zinc, selenium and antimony
Two or more；The mass content of the heavy metal is 1~10g/kg of complicated heavy metal hazardous waste sludge；It is answered what is obtained
It is successively ripe after miscellaneous heavy metal hazardous waste sludge ground-slag end, alkaline calcium activator, metal ion mineralizer, solidifying substance and water mixing
Change, form and conserve, obtains cured product.Method provided by the invention can fix various heavy simultaneously, with chemistry
Solidify and the double effect of physical solidification, Leaching of Heavy Metals can be inhibited, toxicity leaching rate is made to reach state specified standards.
Specific embodiment
The present invention provides a kind of harmless curing methods of complicated heavy metal hazardous waste sludge slag, comprising the following steps:
1) complicated heavy metal hazardous waste sludge slag is obtained into complicated heavy metal hazardous waste sludge ground-slag successively by dehydration, grinding
End；The complexity heavy metal dangerous waste body refuse includes heavy metal and organic matter；The heavy metal include arsenic, mercury, chromium, cadmium, lead, nickel,
Two or more in beryllium, copper, zinc, selenium and antimony；The mass content of the heavy metal is the 1 of complicated heavy metal hazardous waste sludge
~10g/kg；
2) the complicated heavy metal hazardous waste sludge ground-slag end that obtains step 1), alkaline calcium activator, metal ion mineralising
It successively cures, form and conserves after agent, solidifying substance and water mixing, obtain cured product；It is described to be shaped to green compact or powder agglomates.
Complicated heavy metal hazardous waste sludge slag successively by dehydration, grinding, is obtained complicated heavy metal hazardous waste sludge by the present invention
Ground-slag end；The complexity heavy metal dangerous waste body refuse includes heavy metal and organic matter；The heavy metal include arsenic, mercury, chromium, cadmium, lead,
Two or more in nickel, beryllium, copper, zinc and antimony；The mass content of the heavy metal is the 1 of complicated heavy metal hazardous waste sludge
~10g/kg.
In the present invention, the organic matter is preferably the organic matter containing N, S or P.
In the present invention, the heavy metal preferably includes arsenic, cadmium, copper and selenium.
In the present invention, the mass content of the heavy metal is preferably 1~10g/kg of complicated heavy metal hazardous waste sludge, more
Preferably 2~8g/kg, most preferably 5~7g/kg.
In the present invention, the source of the complicated heavy metal hazardous waste sludge slag is preferably melting waste slag, rejects or contains
Sludge after heavy metal containing wastewater treatment.
In the present invention, the moisture content of the dewatered complicated heavy metal hazardous waste sludge slag is preferably 0~5%, more excellent
It is selected as 3%.
The present invention is not particularly limited the method for dehydration, selects dewatering well known to those skilled in the art.
In the present invention, it is preferred to for drying.
In the present invention, the temperature of the drying is preferably 40~300 DEG C, and more preferably 100~250 DEG C, most preferably
150~200 DEG C.
In the present invention, the granularity at the complicated heavy metal hazardous waste sludge ground-slag end is preferably≤120 mesh, more preferably≤
80 mesh.
The present invention is not particularly limited the method for grinding, selects grinding method well known to those skilled in the art.
In the present invention, it is preferred to carry out grinding in flour mill.
Obtain the complicated heavy metal hazardous waste sludge ground-slag that complicated heavy metal hazardous waste sludge ground-slag is last, and the present invention will obtain
It successively cures, form and conserves after end, alkaline calcium activator, metal ion mineralizer, solidifying substance and water mixing, solidified
Product.
In the present invention, the alkaline calcium activator is preferably calcium carbonate, calcium hydroxide, calcium oxide, calcium sulfate, phosphoric acid
Calcium, calcium nitrate or calcium chloride.
In the present invention, the metal ion mineralizer is preferably that extraordinary heavy metal tracks down and arrests agent, humic acid chemicals and length
Chain neutral polymer.
In the present invention, it is preferably heavy metal complexing agent, heavy metal chelant or organic that the extraordinary heavy metal, which tracks down and arrests agent,
Sulphur ammonium biological carbon long chain macromolecule structural compounds；The humic acid chemicals are preferably humic acid ion exchangers；The length
Chain neutral polymer is preferably phenolic resin or epoxy resin.
In the present invention, the curing agent is preferably silicate, aluminate, aluminium sulfate, ferrous aluminate, fluorite thunder mineral
Or sepiolite class mineral.
In the present invention, the complicated heavy metal hazardous waste sludge ground-slag end, alkaline calcium activator, metal ion mineralising
The mass ratio of agent, solidifying substance and water is preferably 1000:0.1~5:0.1~5:100~500:100~150；More preferably 1000:
2~3:2~3:200~400:120~140.
The present invention is not particularly limited mixed method, selects mixed method well known to those skilled in the art.
In the present invention, it is preferred to be mixed in a manner of stirring.The present invention is not particularly limited the rate of stirring and time, selects this
Rate known to the technical staff of field and time.
The present invention is not particularly limited mixed sequence, selects order by merging well known to those skilled in the art.
The present invention preferably successively added in complicated heavy metal dangerous waste sludge powder alkaline calcium activator, metal ion mineralizer,
Solidifying substance and water are mixed.
In the present invention, the temperature of the curing is preferably room temperature, and the time of curing is preferably 1~5h, more preferably
3h。
The present invention is not particularly limited the method for curing, selects ageing method well known to those skilled in the art.
In the present invention, it is preferred to be stored at room temperature curing.
In the present invention, the molding is preferably green compact or powder agglomates.
In the present invention, the pressure of the green compact is preferably 5~24MPa, more preferably 10~20MPa.
In the present invention, the pressure of the powder agglomates is preferably 2~20MPa.
In the present invention, the temperature of the maintenance is preferably 25~30 DEG C, and more preferably 27 DEG C；The time of the maintenance is excellent
It is selected as 5~10 days, more preferably 8 days.
The present invention is not particularly limited the method for maintenance, selects maintenance process well known to those skilled in the art.
The present invention also provides the cured products that the above method is prepared.
Gained cured product is without secondary pollution to environment, and solidifying idiosome can be used for the building block of industrial building and basis,
Powder agglomeration can be used for mine filling.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) Zhuzhou factory contains complicated heavy metal desulfurization tail ash, the tail lime-ash 5kg after taking drying, and toxicity leaches Testing index and is
Containing arsenic 2.35%, contain antimony 0.5%, leaded 0.75%, mercurous 0.15%；
By in the tail lime-ash investment sealing flour mill after drying, tail ash powder is obtained within grinding to 80 mesh.
2) tail ash powder is put into blender and is mixed slowly, successively add 100 grams of calcium oxide, 150 grams of metal-chelator,
Stir 5min；Add 1500 grams of magnesate, aluminate mixed curing agent stirring 5min；Add 900 grams of stirring 10min of water；At room temperature
Cure 150min.Curing material half is taken to be pressed into idiosome under 21mPa pressure, the other half squeezes out pressure in 12MPa and agglomerates at powder.
Two kinds conserve 7 days at 25 DEG C of natural curing temperature simultaneously.Make the harmful ions such as arsenic, antimony, lead, mercury mineralising in dangerous waste slag, chelating,
Stablize.By the green body after solidification and inspection of agglomerating, result is as follows.
The testing result of green body and agglomeration after solidifying in 1 embodiment 1 of table (toxicity leaches mg/L)
| Detect ingredient | As | Pb | Sb | Hg | Compression strength (MPa) |
| Standard value | 5 | 5 | / | 0.1 | ≧15 |
| Idiosome | 0.049 | 0.001 | 0.009 | 0.001 | 17 |
| Powder agglomeration | 0.054 | 0.001 | 0.0096 | 0.001 | / |
As shown in Table 1, the solid waste Leaching standard value referring to listed by HJ/T299, detection result are far below its limit value, because
This solidification idiosome, powder agglomeration will not generate secondary pollution.The compression strength for solidifying idiosome meets JC239-2001 flyash brick
The strength criterion of MU15 can be used for wall and the basis of industrial building；Powder agglomeration can be used for mine filling.
Embodiment 2
1) from Changsha, chromic salts landfill yard is taken containing complicated heavy metal-polluted acid body refuse, and 2kg is sampled after drying, and toxicity leaches detection
Index: 2030mg/kg containing beryllium, arsenic 41.6mg/kg, sulphur 714000mg/kg；
Dangerous waste body refuse is put into sealing flour mill, within grinding to 80 mesh, obtains complicated heavy metal dangerous waste sludge powder；
2) complicated heavy metal dangerous waste sludge powder is put into blender and is mixed slowly, successively add activator calcium carbonate
100 grams, 2 grams of metal chelating agent, stir 5min；Add 600 grams of stirring 5min of silicate solidification agent；Add 400 grams of water stirrings
10min；120min is cured at room temperature.Curing material half is taken to be pressed into idiosome under 21mPa pressure, the other half is squeezed out in 12MPa
Powder is depressed into agglomerate.Two kinds conserve 7 days at 27 DEG C of natural curing temperature simultaneously.Make arsenic in dangerous waste, beryllium metal ion mineralising, chela
It closes, stablize.By the green body after solidification and inspection of agglomerating, result is as follows.
The testing result of green body and agglomeration after solidifying in 2 embodiment 2 of table (toxicity leaches mg/L)
| Detect ingredient | Arsenic | Beryllium | Sulphur | Compression strength (MPa) |
| Standard value | 5 | 0.02 | / | ≧15 |
| Idiosome | 0.0001 | It is not detected | / | 20.3 |
| Powder agglomeration | 0.00012 | It is not detected | / | / |
As shown in Table 2, the solid waste Leaching standard value referring to listed by HJ/T299, detection result are far below its limit value, because
This solidification idiosome, powder agglomeration will not generate secondary pollution.The compression strength for solidifying idiosome meets JC239-2001 flyash brick
The strength criterion of MU15 can be used for wall and the basis of industrial building；Powder agglomeration can be used for mine filling.
Embodiment 3
1) the complicated heavy metal hazardous waste sludge slag for generating Xiangtan County electroplate factory is dried, the complicated heavy metal after taking drying
Hazardous waste sludge slag 5kg, toxicity leach Testing index: cupric 516mg/kg, chromium 1523mg/kg, nickel 287mg/kg, zinc 3642mg/
Kg, lead 8.5mg/kg；
By in the complicated heavy metal hazardous waste sludge slag investment sealing flour mill after drying, within grinding to 80 mesh, answered
Miscellaneous heavy metal hazardous waste sludge ground-slag end.
2) complicated heavy metal hazardous waste sludge ground-slag end is put into blender and is mixed slowly, successively add calcium hydroxide
180 grams, 25 grams of humic acid ion exchangers, stir 5min；Add 1000 grams of stirring 5min of fluorite thunder mineral；1000 grams of water are added to stir
Mix 10min；120min is cured at room temperature.It takes Curing material to squeeze out pressure in 12MPa to agglomerate at powder.Two kinds simultaneously in natural curing temperature
It is conserved 7 days at 30 DEG C of degree.Make the metal ions such as copper, chromium, nickel, lead, zinc mineralising, chelating, stabilization.By after solidification green body and agglomeration
Inspection, result are as follows.
The testing result of green body and agglomeration after solidifying in 3 embodiment 3 of table (toxicity leaches mg/L)
As shown in Table 3, the solid waste Leaching standard value referring to listed by HJ/T299, detection result are far below its limit value, because
This solid idiosome, powder agglomeration will not generate secondary pollution.The compression strength for solidifying idiosome meets JC239-2001 flyash brick
The strength criterion of MU15 can be used for wall and the basis of industrial building.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of harmless curing method of complexity heavy metal hazardous waste sludge slag, comprising the following steps:
1) complicated heavy metal hazardous waste sludge slag is obtained into complicated heavy metal hazardous waste sludge ground-slag end successively by dehydration, grinding；Institute
State includes heavy metal and organic matter in complicated heavy metal dangerous waste body refuse；The heavy metal include arsenic, mercury, chromium, cadmium, lead, nickel, beryllium,
Two or more in copper, zinc, selenium and antimony；The mass content of the heavy metal be complicated heavy metal hazardous waste sludge 1~
10g/kg；
2) the complicated heavy metal hazardous waste sludge ground-slag end that obtains the step 1), alkaline calcium activator, metal ion mineralising
It successively cures, form and conserves after agent, solidifying substance and water mixing.
2. harmless curing method according to claim 1, which is characterized in that a dewatered complicated huge sum of money in the step 1)
The moisture content for belonging to hazardous waste sludge slag is 0~5%.
3. harmless curing method according to claim 1, which is characterized in that complicated heavy metal dangerous waste is dirty in the step 1)
The granularity of sludge powder≤120 mesh.
4. harmless curing method according to claim 1, which is characterized in that the calcareous activator of step 2) neutral and alkali is
Calcium carbonate, calcium hydroxide, calcium oxide, calcium sulfate, calcium phosphate, calcium nitrate or calcium chloride.
5. harmless curing method according to claim 1, which is characterized in that metal ion mineralizer is in the step 2)
Extraordinary heavy metal tracks down and arrests agent, humic acid and long-chain neutral polymer.
6. harmless curing method according to claim 1, which is characterized in that in the step 2) curing agent be silicate,
Aluminate, aluminium sulfate, ferrous aluminate, fluorite thunder mineral or sepiolite class mineral.
7. harmless curing method described in any one according to claim 1~6, which is characterized in that complicated in the step 2)
The mass ratio at heavy metal hazardous waste sludge ground-slag end, alkaline calcium activator, metal ion mineralizer, solidifying substance and water is 1000:
0.1~5:0.1~5:200~1000:100~150.
8. harmless curing method according to claim 1, which is characterized in that the temperature cured in the step 2) is room
Temperature, the time of curing are 1~5h.
9. harmless curing method according to claim 1, which is characterized in that the temperature conserved in the step 2) is 25~
30 DEG C, the time of the maintenance is 5~10 days.
10. the cured product that harmless curing method described in any one of claim 1 to 9 obtains.
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| CN201811168776.9A CN109205973A (en) | 2018-10-08 | 2018-10-08 | A kind of harmless curing method of complexity heavy metal hazardous waste sludge slag and its cured product |
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| CN201811168776.9A CN109205973A (en) | 2018-10-08 | 2018-10-08 | A kind of harmless curing method of complexity heavy metal hazardous waste sludge slag and its cured product |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926435A (en) * | 2019-04-11 | 2019-06-25 | 北京净界新宇环保科技有限公司 | A kind of processing method of heavy metal cadmium |
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| CN104230242A (en) * | 2014-09-14 | 2014-12-24 | 湖南馨湘碧浪环保科技有限公司 | Preparation method of harmless high-arsenic sludge cured brick |
| CN104844126A (en) * | 2015-04-29 | 2015-08-19 | 重庆大学 | Method for dissolving poison solidified chromium slag |
| CN106180134A (en) * | 2016-07-08 | 2016-12-07 | 重庆百世星程环境科技有限公司 | The curing of the produced chromium residue of electroplating wastewater technique |
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| EP0845306A1 (en) * | 1995-07-05 | 1998-06-03 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Wastes disposing material and method for disposing of wastes |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN104230242A (en) * | 2014-09-14 | 2014-12-24 | 湖南馨湘碧浪环保科技有限公司 | Preparation method of harmless high-arsenic sludge cured brick |
| CN104844126A (en) * | 2015-04-29 | 2015-08-19 | 重庆大学 | Method for dissolving poison solidified chromium slag |
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Application publication date: 20190115 |