CN105597262A - Medicament and method for stabilizing and solidifying high-concentration arsenic-containing waste residue - Google Patents
Medicament and method for stabilizing and solidifying high-concentration arsenic-containing waste residue Download PDFInfo
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- CN105597262A CN105597262A CN201510957453.8A CN201510957453A CN105597262A CN 105597262 A CN105597262 A CN 105597262A CN 201510957453 A CN201510957453 A CN 201510957453A CN 105597262 A CN105597262 A CN 105597262A
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- arsenic
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
Abstract
The invention discloses a medicament for stabilizing and solidifying high-concentration arsenic-containing waste residue and application thereof. The medicament comprises H2O2, FeSO4.7H2O, CaO and slag cement. The medicament has simple composition and wide source of raw materials, and can be used for treating high-concentration arsenic-containing waste residue to stabilize and solidify high-concentrations arsenic-containing refractory waste residue; and the treated arsenic-containing waste residue reaches the hazardous waste landfill pollution control standards (GB 18598-2001), and meets the environmental requirements.
Description
Technical field
The present invention relates to a kind of medicament for high concentration arsenic-containing waste residue stable curing, and this medicament is for the treatment of heightThe method of concentration arsenic-containing waste residue, belongs to high concentration arsenic-containing waste residue processing technology field.
Background technology
Arsenic-containing waste residue mainly comes from containing of melting waste slag, the sediment of processing arsenic-containing waste water and spent acid, electronics industryIn arsenic refuse and electrolytic process, produce containing the arsenic earth of positive pole etc., belong to dangerous solid waste. For a long time, enterprise pairArsenic-containing waste residue adopts the method for hoarding storage to dispose mostly, to such an extent as to high concentration arsenic-containing waste residue is cumulative. At present,To the processing mode of poisonous arsenic-containing waste residue be mainly both at home and abroad stable/solidify, pyrogenic process roasting and hydrometallurgic recovery etc. locateReason mode, each processing method respectively has pluses and minuses.
Stable/solidification method is to utilize engineering characteristic that additive changes waste residue (as permeability, compressibility and strongDegree etc.) process, even if refuse is transformed into the not process of flowable solid. Conventional stable/curing interpolationAgent is calcium salt, molysite, magnesium salts, aluminium salt and sulfide etc., and reaction condition is generally in the aqueous solution, generatesStable arsenic calcium slag, arsenic scum, arsenic magnesium slag etc. The stability of arsenic calcium slag is lower higher with dissolubility, therefore singleSolely use dearsenification effect bad. Arsenic scum is more stable, in the time of the arsenic of processing in waste water with FeCl3For molysite, rightThe removal effect of arsenic is relatively better.
Summary of the invention
The defect existing for the technology of existing processing arsenic-containing waste residue, the object of the present invention is to provide a kind of energyMake high concentration arsenic-containing waste residue obtain effective stabilisation and immobilized medicament, this medicament stock source is wide, is conducive toApply.
The present invention also provide a kind of by described medicament the method for high concentration arsenic-containing waste residue stable curing, the partyMethod cost is low, simple to operate, can make the difficult arsenic-containing waste residue of high concentration obtain stabilisation and solidify, after treatmentArsenic-containing waste residue reaches " hazard waste landfill pollution control criterion " (GB18598-2001), meets environmental protection and wantsAsk.
In order to realize above-mentioned technical purpose, the invention provides a kind of for high concentration arsenic-containing waste residue stable curingMedicament, this medicament is made up of following mass component: the H that mass percent concentration is 10%2O21～3 part;
FeSO4·7H2O1～5 part; CaO1～5 part; 1～8 part of slag cements.
According to great many of experiments, summary of experience obtains formula of the present invention, and its action principle is arsenic-containing waste residue processH2O2Process trivalent arsenic stronger toxicity is changed into the relatively weak pentavalent arsenic of toxicity, and arsenate (AsO4 3-)Than arsenious acid (AsO3 3-) more easily form stable solid, meanwhile, by ferrous salt FeSO4·7H2O is steadyFixedization processed, and employing CaO coordinates the pH value of sinking arsenic and regulating waste residue, and (alkali condition is more conducive to solidGeneration), be more conducive to fixed arsenic, and after slag cements is cured, thoroughly reach stable/solidify arsenicObject.
Medicament described in the present invention also provides is for the method for high concentration arsenic-containing waste residue stable curing, and the method isArsenic-containing waste residue is passed through to H2O2After pre-oxidation treatment, add FeSO4·7H2O stabilization processes, then add CaOWith cement solidification processing, obtain firming body.
Technical scheme of the present invention first trivalent arsenic stronger arsenic-containing waste residue Poisoning is oxidized to toxicity low fiveValency arsenic, reduces the murder by poisoning of arsenic, and arsenate (AsO4 3-) precipitate than arsenious acid (AsO3 3-) precipitation more steadyFixed, be more conducive to fixed arsenic; Arsenic-containing waste residue after oxidation molysite FeSO4·7H2O stabilisation, then use CaOCoordinate the pH value (alkali condition is more conducive to the generation of precipitation) of sinking arsenic and regulating waste residue, finally use slag waterMud is cured, to reach the thoroughly object of stable/curing arsenic.
Preferred scheme, arsenic-containing waste residue and H2O2Mass ratio be 10:1～6, described hydrogen peroxide is with quality hundredDivide the H that specific concentration is 10%2O2Metering.
Preferred scheme, arsenic-containing waste residue reaches 5000mg/L by sulfuric acid-nitrate method leaching concentration.
Preferred scheme, arsenic-containing waste residue passes through H2O2The time of pre-oxidation treatment is 25～35min.
Preferred scheme, arsenic-containing waste residue carries out H successively2O2Pre-oxidation treatment, FeSO4·7H2O stabilization processes,CaO and cement solidification repeat after processing, and carry out secondary H2O2Pre-oxidation treatment, FeSO4·7H2OStabilization processes, CaO and cement solidification processing.
Prior art relatively, the useful technique effect that technical scheme of the present invention is brought:
1, the raw material that the medicament in technical solution of the present invention adopts are cheap and easy to get, are conducive to apply, rightEnvironment can not cause secondary pollution.
2, the synergistic function between the various medicaments in technical solution of the present invention is obvious, can realize high concentrationArsenic in arsenic waste residue obtains effectively thoroughly stable/curing, makes it reach " hazard waste landfill pollution control criterion "(GB18598-2001)。
3, technical solution of the present invention Chinese medicine is simple, easy for the method for high concentration arsenic-containing waste residue stable curingOperation, meets industrial applications.
Brief description of the drawings
[Fig. 1] is the XRD analysis collection of illustrative plates of the waste residue of embodiment of the present invention employing.
[Fig. 2] is the XRD analysis figure of arsenic total amount in the waste residue of embodiment of the present invention employing.
Detailed description of the invention
Following examples are intended to further illustrate content of the present invention, instead of restriction the claims in the present invention protection modelEnclose.
Below implement the content of beary metal testing result of the original arsenic-containing waste residue adopting:
| Test item | Pb | As | Cu | Cd | Zn |
| Concentration (μ g/mL) | 0.114 | 4641.80 | 0.010 | 0.136 | 0.088 |
Waste residue censorship is made to XRD analysis, and obtaining main component is As2O3, as shown in Figure 1; Arsenic total amount asShown in Fig. 2.
Comparative example 1
The direct stabilisation of waste residue is solidified processing:
Experiment A: adopt FeSO4·7H2The about 30min of O stabilisation, wherein, adding distil water is until stir,Add again CaO and cement solidification. Waste residue: 10%H2O2：FeSO4·7H2O:CaO: cement quality ratio is about1:0:1:1:0, maintenance 3～5 days, sulfuric acid nitrate method leaching arsenic concentration is down to by about 4641.80mg/l562.23mg/L。
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | 4641.80 | 562.23 | 87.89 |
Experiment B: adopt FeCl3The about 30min of stabilisation, wherein adding distil water is until stir, then adds CaOAnd cement solidification. Waste residue: 10%H2O2：FeCl3: CaO: cement quality ratio is about 1:0:1:1:0, maintenance 3～5 days, sulfuric acid nitrate method leaching arsenic concentration was down to 1470mg/L by about 4641.80mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | 4641.80 | 1470 | 68.33 |
Experiment C: adopt Na2The about 30min of S stabilisation, wherein adding distil water is until stir, then adds CaOAnd cement solidification. Waste residue: 10%H2O2：Na2S:CaO: cement quality ratio is about 1:0:1:1:0, maintenance 3～5 days, sulfuric acid nitrate method leaching arsenic concentration was down to 1610.77mg/L by about 4641.80mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | 4641.80 | 1610.77 | 65.30 |
From this group, comparative example can find out, without hydrogen peroxide pre-oxidation treatment containing arsenic slag treatment effeciencyLow, the stabilisation solidification effect of arsenic is poor. Adopt in addition the relatively traditional Na of ferrous sulfate stabilizing agent2S andFeCl3Stabilizing agent, stabilization effect has clear superiority.
Embodiment 1
Waste residue pre-oxidation arsenic rear stabilization solidifies to be processed:
Experiment A (control group): adopt H2O2The about 30min of pre-oxidation, wherein original 10%H2O2Should diluteCertain multiple, and then add FeSO4·7H2O solid stabilizing, finally adds CaO and cement solidification. UselessSlag: 10%H2O2：FeSO4·7H2O:CaO: cement quality ratio is about 5:3:5:5:0, maintenance 3～5 days,Sulfuric acid nitrate method leaching arsenic concentration is down to 120.46mg/L by about 4641.80mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | 4641.80 | 120.46 | 97.40 |
Experiment B (experimental group): adopt H2O2The about 30min of pre-oxidation, wherein original 10%H2O2Should diluteCertain multiple, and then add FeSO4·7H2O solid stabilizing, finally adds CaO and cement solidification. UselessSlag: 10%H2O2：FeSO4·7H2O:CaO: cement quality ratio is about 5:3:5:5:5, maintenance 3～5 days,Sulfuric acid nitrate method leaching arsenic concentration is down to 10.32mg/L by about 4641.80mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | 4641.80 | 10.32 | 99.78 |
Can find out from this group embodiment 1, after hydrogen peroxide pre-oxidation treatment, the more curing processing of stabilisation, locateThe rear sulfuric acid nitrate method leaching concentration of reason is minimum is 10.32mg/L, and treatment effeciency reaches as high as 99.78%, approaches " dangerDanger refuse landfill pollutes control criterion " (GB18598-2001) the total arsenic content 2.5mg/L of regulation.
Can find out by this group experiment, after pre-oxidation, stabilization processes, further adopt lime and cementSolidify and process, can further improve the immobilization effect of arsenic.
Embodiment 2
Waste residue, through embodiment 1 (experiment B) mixture after treatment, carries out Quadratic Stabilityization and solidifies processing:
H2O2The about 30min of pre-oxidation, FeSO4·7H2O stabilisation, CaO and cement solidification. After treatment uselessSlag: 10%H2O2：FeSO4·7H2O:CaO: cement quality ratio is about 10:1:1:1:5, maintenance 3～5 days,Sulfuric acid nitrate method leaching arsenic concentration is down to 2.36mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | ≈400 | 2.36 | 99.41 |
Embodiment 3
H2O2The about 30min of pre-oxidation, FeSO4·7H2O stabilisation, CaO and cement solidification. After treatment uselessSlag: 10%H2O2：FeSO4·7H2O:CaO: cement quality ratio is about 10:1:1:1:8, maintenance 3～5 days,Sulfuric acid nitrate method leaching arsenic concentration is down to 1.78mg/L.
| Before processing | After processing | Treatment effeciency (%) | |
| Arsenic concentration in leachate (mg/L) | ≈400 | 1.78 | 99.56 |
Can find out from this group embodiment 2, through embodiment 1 mixture after treatment, embodiment is added in circulation1 medicament carries out after-treatment (medicament proportion of composing is suitably adjusted), and its result reaches " hazardous wasteLandfill pollute control criterion " (GB18598-2001) regulation total arsenic content 2.5mg/L.
Claims (6)
1. for a medicament for high concentration arsenic-containing waste residue stable curing, it is characterized in that: divided into groups by following quality groupBecome:
Mass percent concentration is 10% H2O21～3 part;
FeSO4·7H2O1～5 part;
CaO1～5 part;
1～8 part of slag cements.
2. medicament claimed in claim 1, for the method for high concentration arsenic-containing waste residue stable curing, is characterized in that:Arsenic-containing waste residue passes through H2O2After pre-oxidation treatment, add FeSO4·7H2O stabilization processes, then add CaO andCement solidification processing, obtains firming body.
3. medicament according to claim 2 is for the method for high concentration arsenic-containing waste residue stable curing, and its feature existsIn: described arsenic-containing waste residue and H2O2Mass ratio be 10:1～6, described hydrogen peroxide is dense with mass percentDegree is 10% H2O2Metering.
4. medicament according to claim 3 is for the method for high concentration arsenic-containing waste residue stable curing, and its feature existsIn: described arsenic-containing waste residue reaches 5000mg/L by sulfuric acid-nitrate method leaching concentration.
5. the method for high concentration arsenic-containing waste residue stable curing according to the medicament described in claim 2～4 any one,It is characterized in that: described arsenic-containing waste residue passes through H2O2The time of pre-oxidation treatment is 25～35min.
6. medicament according to claim 2 is for the method for high concentration arsenic-containing waste residue stable curing, and its feature existsIn: arsenic-containing waste residue carries out H successively2O2Pre-oxidation treatment, FeSO4·7H2O stabilization processes, CaO and waterMud solidifies after processing, repeats, and carries out secondary H2O2Pre-oxidation treatment, FeSO4·7H2O stabilization processes,CaO and cement solidification processing.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106310580A (en) * | 2016-08-24 | 2017-01-11 | 湖南凯天重金属污染治理工程有限公司 | Stabilization and solidification agent for high-concentration arsenic alkali residues |
| CN106422151A (en) * | 2016-08-24 | 2017-02-22 | 湖南凯天重金属污染治理工程有限公司 | Method for achieving stabilized solidification of high-concentration arsenic soda slag |
| CN107010800A (en) * | 2016-12-19 | 2017-08-04 | 北京矿冶研究总院 | Chemical stabilizing agent and chemical stabilizing method for arsenic and selenium in lead-zinc smelting wastewater treatment sludge |
| CN107285581A (en) * | 2017-07-25 | 2017-10-24 | 云南大地绿坤环保科技有限公司 | A kind of processing method of multivalent state dreg containing arsenic |
| CN108203271A (en) * | 2016-12-19 | 2018-06-26 | 北京矿冶研究总院 | Baking-free and steaming-free brick prepared by treating sludge with lead-zinc smelting wastewater and preparation method thereof |
| CN108467236A (en) * | 2018-03-13 | 2018-08-31 | 湖南恒凯环保科技投资有限公司 | A kind of stable curing continuous processing technique of heavy metal waste slag |
| CN108620409A (en) * | 2018-03-14 | 2018-10-09 | 中南大学 | A method of fixing arsenic-containing waste using high-temperature liquid furnace slag |
| CN108751878A (en) * | 2018-08-22 | 2018-11-06 | 中国有色桂林矿产地质研究院有限公司 | A kind of curing agent and curing process of zinc abstraction waste residue |
| CN109439911A (en) * | 2019-01-02 | 2019-03-08 | 湖南省环境保护科学研究院 | Arsenic alkaline slag disposal system and the method for handling arsenic alkaline slag using it |
| CN112717319A (en) * | 2020-12-16 | 2021-04-30 | 陕西新天地固体废物综合处置有限公司 | Harmless treatment method for arsenic-containing waste reagent |
| CN112718793A (en) * | 2020-12-15 | 2021-04-30 | 紫金矿业集团股份有限公司 | Method for directly vitrifying arsenic-fixing material containing arsenite |
| CN114920529A (en) * | 2022-05-31 | 2022-08-19 | 湖南现代环境科技股份有限公司 | Composite curing agent and treatment process of arsenic-containing waste residue |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106422151A (en) * | 2016-08-24 | 2017-02-22 | 湖南凯天重金属污染治理工程有限公司 | Method for achieving stabilized solidification of high-concentration arsenic soda slag |
| CN106310580A (en) * | 2016-08-24 | 2017-01-11 | 湖南凯天重金属污染治理工程有限公司 | Stabilization and solidification agent for high-concentration arsenic alkali residues |
| CN106422151B (en) * | 2016-08-24 | 2019-07-12 | 航天凯天环保科技股份有限公司 | A kind of cured method of realization High Concentration of Arsenic alkaline residue stabilisation |
| CN106310580B (en) * | 2016-08-24 | 2019-07-12 | 航天凯天环保科技股份有限公司 | A kind of cured medicament of High Concentration of Arsenic alkaline residue stabilisation |
| CN107010800A (en) * | 2016-12-19 | 2017-08-04 | 北京矿冶研究总院 | Chemical stabilizing agent and chemical stabilizing method for arsenic and selenium in lead-zinc smelting wastewater treatment sludge |
| CN108203271A (en) * | 2016-12-19 | 2018-06-26 | 北京矿冶研究总院 | Baking-free and steaming-free brick prepared by treating sludge with lead-zinc smelting wastewater and preparation method thereof |
| CN107010800B (en) * | 2016-12-19 | 2020-12-04 | 北京矿冶研究总院 | Chemical stabilizing agent and chemical stabilizing method for arsenic and selenium in lead-zinc smelting wastewater treatment sludge |
| CN107285581A (en) * | 2017-07-25 | 2017-10-24 | 云南大地绿坤环保科技有限公司 | A kind of processing method of multivalent state dreg containing arsenic |
| CN108467236A (en) * | 2018-03-13 | 2018-08-31 | 湖南恒凯环保科技投资有限公司 | A kind of stable curing continuous processing technique of heavy metal waste slag |
| CN108620409A (en) * | 2018-03-14 | 2018-10-09 | 中南大学 | A method of fixing arsenic-containing waste using high-temperature liquid furnace slag |
| CN108751878B (en) * | 2018-08-22 | 2021-08-03 | 中国有色桂林矿产地质研究院有限公司 | Curing agent and curing treatment process for zinc smelting waste residues |
| CN108751878A (en) * | 2018-08-22 | 2018-11-06 | 中国有色桂林矿产地质研究院有限公司 | A kind of curing agent and curing process of zinc abstraction waste residue |
| CN109439911A (en) * | 2019-01-02 | 2019-03-08 | 湖南省环境保护科学研究院 | Arsenic alkaline slag disposal system and the method for handling arsenic alkaline slag using it |
| CN112718793A (en) * | 2020-12-15 | 2021-04-30 | 紫金矿业集团股份有限公司 | Method for directly vitrifying arsenic-fixing material containing arsenite |
| CN112717319A (en) * | 2020-12-16 | 2021-04-30 | 陕西新天地固体废物综合处置有限公司 | Harmless treatment method for arsenic-containing waste reagent |
| CN112717319B (en) * | 2020-12-16 | 2022-04-08 | 陕西新天地固体废物综合处置有限公司 | Harmless treatment method for arsenic-containing waste reagent |
| CN114920529A (en) * | 2022-05-31 | 2022-08-19 | 湖南现代环境科技股份有限公司 | Composite curing agent and treatment process of arsenic-containing waste residue |
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| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: He Zhiguo Inventor after: Shi Weihua Inventor after: Li Juan Inventor after: Jiang Yi Inventor before: Luo Wenlian Inventor before: Li Juan Inventor before: He Zhiguo Inventor before: Jiang Yi Inventor before: Shi Weihua Inventor before: Li Jing |