CN106310580A - Stabilization and solidification agent for high-concentration arsenic alkali residues - Google Patents
Stabilization and solidification agent for high-concentration arsenic alkali residues Download PDFInfo
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- CN106310580A CN106310580A CN201610714777.3A CN201610714777A CN106310580A CN 106310580 A CN106310580 A CN 106310580A CN 201610714777 A CN201610714777 A CN 201610714777A CN 106310580 A CN106310580 A CN 106310580A
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- arsenic
- solidification
- medicament
- conditioner
- stabilization
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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
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
Abstract
The invention discloses a stabilization and solidification agent for high-concentration arsenic alkali residues. The stabilization and solidification agent is composed of following components including an oxidizing agent composed of hydrogen peroxide and persulfate, a stabilizing agent composed of molysite and/or ferrite, and a conditioner composed of kaolin and/or attapulgite, red mud and pulverous coal. The synergistic interaction effect between all the components of the stabilization and solidification agent is obvious, efficient stabilization and solidification of the high-concentration arsenic alkali residues can be achieved, a method for using the agent is simple, cost is low, and the stabilization and solidification agent is suitable for application and popularization.
Description
Technical field
The present invention relates to a kind of arsenic alkaline slag stabilisation solidification medicament, particularly to a kind of stablizing for High Concentration of Arsenic alkaline residue
Change the combination medicament of solidification, belong to useless arsenic Slag treatment technical field.
Background technology
The waste residue that arsenic alkaline slag produces when being to add soda arsenic removal during coarse antimony refining, slag arsenic content is 5%～7%, wherein
Arsenic is mainly presented in natrium arsenicum, and natrium arsenicum is hypertoxic and soluble in water, easily pollutes environment, is that a class is very difficult to dispose
Hazardous waste.Arsenic alkaline slag is once revealed, and the arsenic being exposed in environment will enter water body and food chain, the most then harmful to human is good for
Health, heavy then cause death.At present, both at home and abroad to the processing mode of arsenic alkaline slag the most stable/solidification, pyrogenic process roasting and wet method return
The processing modes such as receipts, each processing method is respectively arranged with pluses and minuses.
Stable/solidification method is the process of the engineering characteristic utilizing additive change waste residue, changes form or the valency of heavy metal
State, pollutant are converted into not readily dissolve, state that transfer ability or toxicity diminish or form.Conventional stable/solidification is added
Agent has iron salt, aluminium salt, calcium salt, sulfide, flyash etc., but pollutes for different metal, and it is to stable/curing additive
Selecting, there is bigger difference in collocation.At present, the relevant report processed for the solidification and stabilization of arsenic-containing waste residue is fewer.In
State's patent (CN105597262A) discloses employing H2O2、FeSO4·7H2O, CaO and slag cements stablizing as arsenic-containing waste residue
Change firming agent, owing in arsenic-containing waste residue, arsenic alkaline slag is strong basicity, cause utilizing of hydrogen peroxide low；Particularly its arsenic and iron salt reaction
The arsenic acid molysite deposition generated is affected relatively big by pH, and under conditions of pH ＞ 7, arsenic acid iron salt instability is decomposed, and this patent is solid
Changing CaO and slag cements in stabilization agent, to add ratio higher, is strong basicity, causes arsenic acid iron salt to be decomposed, in leachate
The concentration of arsenic raises.It addition, Chinese patent (CN104263949A) selects iron salt and clay mineral that arsenic alkaline slag is carried out stabilisation
Solidification, but arsenic alkaline slag needs with substantial amounts of dilute acid for adjusting pH after adding stabilizer, and cost is high, operation complexity, in Practical Project complexity
In the case of be difficult to meet requirement.
Summary of the invention
The defect existed for medicament and the method for existing process arsenic offscum in alkali, it is an object of the invention to be to provide one
Planting the medicament of the efficient stableization solidification that can realize High Concentration of Arsenic alkaline residue, the method using this medicament is simple, and low cost is suitable for pushing away
Wide use.
In order to realize above-mentioned technical purpose, the invention provides the medicament of a kind of High Concentration of Arsenic alkaline residue stabilisation solidification, should
Medicament is made up of following content of component:
The oxidant 1 being made up of hydrogen peroxide and persulfate～3 parts；
The stabilizer 15 being made up of iron salt and/or ferrous salt～25 parts；
The conditioner 6 being made up of with red mud and flyash Kaolin and/or attapulgite～15 parts.
Stabilisation solidification medicament in technical scheme mainly includes oxidant, stabilizer and conditioner, oxidation
Agent is made up of hydrogen peroxide and persulfate, and oxidability is strong, good stability, substantially increases oxidation efficiency, can guarantee that arsenic alkali
Low price arsenic in waste residue be oxidized to high price arsenic, and high price arsenate such as AsO4 3-Ratio arsenious acid AsO3 3-Stable etc. being more readily formed
Solid；On this basis, in conjunction with iron salt fixed arsenic, stable precipitated ferric arsenate is generated；Additionally, the present invention uses neutral compounding tune
Reason agent, the part aluminium salt in red mud and flyash can generate al arsenate precipitation with pentavalent arsenic, and Kaolin and attapulgite play
Absorption helps heavy effect, produces synergistic function, consolidate arsenic alkaline slag stabilisation solidification effect further between various components
Promote.
Preferably scheme, oxidant 1.0～2.0:0.5～1.0 is made up of in molar ratio hydrogen peroxide and persulfate.Both
Combination uses as oxidant, and synergistic function is obvious, persulfate free radical (SO4 -) and hydroxyl radical free radical (OH) phase
Excite mutually, form the system that performance more oxidizing than single kind is higher.Persulfate generally comprises sodium peroxydisulfate, potassium peroxydisulfate
With Ammonium persulfate. etc..
Preferably scheme, stabilizer is by ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water ferrous chlorides
At least one composition.Stabilizing agent mainly provides iron ion, can generate stable compound with high price arsenic anion, it is achieved
The stabilisation of arsenic.
Preferably scheme, conditioner by Kaolin and/or attapulgite, with red mud and flyash by mass percentage 65～
80%:15～20%:5～15% composition.The composite conditioner pH of the present invention is neutrality, and simultaneously works as precipitation and absorbing synergic
Effect, it is possible to achieve consolidate stabilisation and the solidification of arsenic.Aluminium salt in red mud and flyash can generate al arsenate with pentavalent arsenic
Precipitation, Kaolin and attapulgite play absorption and help heavy effect, arsenic alkaline slag stabilisation solidification effect is consolidated lifting further.
More preferably scheme, conditioner processes through 600～750 DEG C of high-temperature activations.Being processed by high-temperature activation can be effective
Excite the performance of conditioner, improve the stabilisation curing performance of conditioner, the time that high-temperature activation processes be generally 60～
150min。
The hydrogen peroxide that technical solution of the present invention uses is commercially available conventional hydrogen peroxide, and its mass percent concentration is 30% left side
Right.It is use compounding with persulfate after 2% that commercially available hydrogen peroxide is typically diluted to mass percent concentration.
Total content >=the 20000mg/kg of arsenic in the High Concentration of Arsenic alkaline residue of the present invention, according to " solid waste leaching level is shaken
Swing method " (HJ 557-2010), arsenic leaching concentration is 1000～5000mg/L, pH ＞ 11.
The medicament of the High Concentration of Arsenic alkaline residue stabilisation solidification of the present invention is for the method processing High Concentration of Arsenic alkaline residue: first by arsenic
Alkaline residue crushes, is sized to particle diameter≤1cm；It is subsequently adding oxidant stirring 10～30min, obtains mixture；Add in the mixture
Stabilizer, after stirring 10～30min, adds conditioner, stirs 10～20min, maintenance 3～7d.Arsenic alkaline slag after maintenance
The water logging leaching concentration of middle arsenic reaches hazardous waste in " hazard waste landfill Environmental capacity standard " (GB18598-2001) and allows
Enter the control limit (less than 2.5mg/L) in landfill district.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, during the arsenic alkaline slag stabilisation of the present invention solidifies medicament, the synergistic function between each component is obvious, can realize height
In Concentration Arsenic alkaline residue, arsenic is the most fixing, and the water logging leaching concentration of the arsenic alkaline slag arsenic after process is less than 2.5mg/L.Oxidant can be by
Arsenic is oxidized to high price arsenic, at high price arsenate (AsO at a low price4 3-) at stabilizer containing being more readily formed stable arsenic in the presence of iron salt
Acid ferrum precipitation, and conditioner not only can generate al arsenate precipitation with pentavalent arsenic, and there is adsorption function to promote precipitation, right
Arsenic alkaline slag stabilisation solidification effect consolidates lifting further.
2) the arsenic alkaline slag stabilisation solidification medicament of the present invention adjusts pH without employing acid during processing High Concentration of Arsenic alkaline residue,
Simplify step, reduce cost.
3) conditioner that the arsenic alkaline slag stabilisation solidification medicament of the present invention uses is neutrality, the arsenic generated in stabilization procedures
Acid ferrum, al arsenate precipitation can stable existence, preferable to the removal effect of arsenic.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the protection model of the claims in the present invention
Enclose.
1, stabilisation solidification medicament preparation:
High Concentration of Arsenic alkaline residue stabilisation of the present invention solidification medicament is made up of oxidant, stabilizer and conditioner, according to arsenic alkali
Slag character is added according to a definite sequence, certain proportion.
Oxidant is hydrogen peroxide (2%) and persulfate.Hydrogen peroxide (30%) be diluted to 2% after and persulfate according to
(1.0～2.0): (0.5～1.0) mol ratio multiplicity reactivation forms oxidant；
Stabilizer is the one or many in ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water ferrous chlorides
Kind；
Described conditioner is made up of red mud, Kaolin or attapulgite, flyash.By each for conditioner composition according to red mud 15
～20%, Kaolin or attapulgite 65～80%, flyash 5～15% ratio mix, cross 100 mesh sieves, obtain conditioner powder
End；The thermal activation treatment of conditioner: the conditioner powder roasting that will obtain, sintering temperature 600～750 DEG C, roasting time 60～
150min, is i.e. prepared as conditioner after cooling.
2, stabilisation solidification medicament using method:
First arsenic alkaline slag crushed, be sized to particle diameter≤1cm；Be subsequently adding 1～3% oxidant stirring 10～30min, obtain mixed
Compound；Addition 15～25% stabilizer, stir 10～30min in the mixture；Addition 6～15% conditioner in the mixture,
Stirring 10～20min, maintenance 3～7d.
Embodiment 1
Prepared by oxidant: after using the hydrogen peroxide of commercially available 30% to be diluted to 2%, with sodium peroxydisulfate according to the mol ratio of 2:1
Example is uniformly mixedly configured into oxidant；
Prepared by stabilizer: by ferrous sulfate heptahydrate and bodied ferric sulfate according to the mixing of 5:1 mass ratio stabilizer；
Prepared by conditioner: red mud 15%, Kaolin or attapulgite 78%, the mixing of flyash 7% ratio, crosses 100 mesh sieves,
Obtain conditioner powder；The thermal activation treatment of conditioner: the conditioner powder roasting that will obtain, sintering temperature 630 DEG C, during roasting
Between 60min, can use after cooling.
Embodiment 2
The medicament in embodiment 1 is used to carry out arsenic alkaline slag process.
Taking certain arsenic pollution concentration is 21520mg/kg arsenic alkaline slag 500g, adds the oxidant stirring 10min of 1.5%, then
Add the stabilizer stirring 10min of 15%, be eventually adding after 10% conditioner stirring 10min maintenance 5d under room temperature, measure arsenic leaching
Go out concentration.The water logging concentration of arsenic is by processing the 0.93mg/L after front 1950mg/L drops to process.Arsenic in arsenic alkaline slag after improvement
Water logging concentration allows access into landfill district less than hazardous waste in " hazard waste landfill Environmental capacity standard " (GB18598-2001)
Control limit, less than 2.5mg/L.
Embodiment 3
The medicament in embodiment 1 is used to carry out arsenic alkaline slag process.
Taking certain arsenic pollution concentration is 30550mg/kg arsenic alkaline slag 500g, adds the oxidant stirring 15min of 2%, then adds
Enter the stabilizer stirring 15min of 20%, be eventually adding after 12% conditioner stirring 15min maintenance 7d under room temperature, measure arsenic and leach
Concentration.The water logging concentration of arsenic is by processing the 1.53mg/L after front 2625mg/L drops to process.Arsenic water in arsenic alkaline slag after improvement
Leaching concentration allows access into landfill district less than hazardous waste in " hazard waste landfill Environmental capacity standard " (GB18598-2001)
Control limit, less than 2.5mg/L.
Comparative example 1
Same batch arsenic alkaline slag 500g in Example 3, oxidant addition is 0.8%, other additive amount of medicament and place
Science and engineering skill is as embodiment 3, and in the arsenic alkaline slag after improvement, arsenic water logging concentration is 53.01mg/L, higher than " hazard waste landfill is dirty
Dye control standard " hazardous waste allows access into the control limit in landfill district in (GB18598-2001).
Comparative example 2
Same batch arsenic alkaline slag 500g in Example 3, stabilizer addition is 30%, other additive amount of medicament and process
Technique is as embodiment 3, and in the arsenic alkaline slag after improvement, arsenic water logging concentration is 4.56mg/L, higher than " hazard waste landfill pollutes
Control standard " hazardous waste allows access into the control limit in landfill district in (GB18598-2001).
Comparative example 3
Same batch arsenic alkaline slag 500g in Example 3, the hydrogen peroxide of interpolation 2% is as oxidant, and other medicaments add
Measuring with process technique as embodiment 3, in the arsenic alkaline slag after improvement, arsenic water logging concentration is 30.22mg/L, higher than " hazardous waste
Landfill Environmental capacity standard " hazardous waste allows access into the control limit in landfill district in (GB18598-2001).
Comparative example 4
Same batch arsenic alkaline slag 500g in Example 3, conditioner does not carries out activation processing, other additive amount of medicament and place
Science and engineering skill is as embodiment 3, and in the arsenic alkaline slag after improvement, arsenic water logging concentration is 10.43mg/L, higher than " hazard waste landfill is dirty
Dye control standard " hazardous waste allows access into the control limit in landfill district in (GB18598-2001).
Claims (5)
1. the medicament of a High Concentration of Arsenic alkaline residue stabilisation solidification, it is characterised in that: it is made up of following content of component:
The oxidant 1 being made up of hydrogen peroxide and persulfate～3 parts；
The stabilizer 15 being made up of iron salt and/or ferrous salt～25 parts；
The conditioner 6 being made up of with red mud and flyash Kaolin and/or attapulgite～15 parts.
The medicament of High Concentration of Arsenic alkaline residue stabilisation the most according to claim 1 solidification, it is characterised in that: described oxidant
By hydrogen peroxide and persulfate (1.0～2.0) in molar ratio: (0.5～1.0) form.
The medicament of High Concentration of Arsenic alkaline residue stabilisation the most according to claim 1 solidification, it is characterised in that: described stabilizer
It is made up of at least one in ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water ferrous chlorides.
The medicament of High Concentration of Arsenic alkaline residue stabilisation the most according to claim 1 solidification, it is characterised in that: described conditioner
By Kaolin and/or attapulgite, and red mud and flyash (65～80%) by mass percentage: (15～20%): (5～
15%) composition.
The medicament of High Concentration of Arsenic alkaline residue stabilisation the most according to claim 4 solidification, it is characterised in that: described conditioner
Process through 600～750 DEG C of high-temperature activations.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106734175A (en) * | 2017-01-20 | 2017-05-31 | 湖南艾布鲁环保科技有限公司 | Solidification and stabilization medicament that a kind of As polluted soil is repaired and its preparation method and application |
| 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 |
| CN109432686A (en) * | 2019-01-02 | 2019-03-08 | 湖南省环境保护科学研究院 | Stabilize the method for solidifying medicament and handling arsenic alkaline slag using it |
| CN109499340A (en) * | 2019-01-02 | 2019-03-22 | 湖南省环境保护科学研究院 | The method of arsenic alkaline slag and flue gas desulfurization combined processing |
| CN109943340A (en) * | 2019-05-13 | 2019-06-28 | 河南川萍环保科技有限公司 | For administering the passivator and its preparation and application of high arsenic waste residue |
| CN111035882A (en) * | 2019-11-21 | 2020-04-21 | 扬州杰嘉工业固废处置有限公司 | Method for the synergistic treatment of arsenic-containing waste and barium-containing waste for stabilization and solidification |
| CN111544822A (en) * | 2020-04-13 | 2020-08-18 | 上海圣珑环境修复技术有限公司 | Barium slag stabilizing treatment method |
| CN112546530A (en) * | 2020-11-20 | 2021-03-26 | 李开春 | Harmless treatment and resource utilization method for alkali slag generated in preparation of soda ash by ammonia-soda process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111035882A (en) * | 2019-11-21 | 2020-04-21 | 扬州杰嘉工业固废处置有限公司 | Method for the synergistic treatment of arsenic-containing waste and barium-containing waste for stabilization and solidification |
| CN111544822A (en) * | 2020-04-13 | 2020-08-18 | 上海圣珑环境修复技术有限公司 | Barium slag stabilizing treatment method |
| CN112546530A (en) * | 2020-11-20 | 2021-03-26 | 李开春 | Harmless treatment and resource utilization method for alkali slag generated in preparation of soda ash by ammonia-soda process |
| CN112546530B (en) * | 2020-11-20 | 2022-03-29 | 李开春 | Harmless treatment and resource utilization method for alkali slag generated in preparation of soda ash by ammonia-soda process |
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