CN106310580B - A kind of cured medicament of High Concentration of Arsenic alkaline residue stabilisation - Google Patents
A kind of cured medicament of High Concentration of Arsenic alkaline residue stabilisation Download PDFInfo
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- CN106310580B CN106310580B CN201610714777.3A CN201610714777A CN106310580B CN 106310580 B CN106310580 B CN 106310580B CN 201610714777 A CN201610714777 A CN 201610714777A CN 106310580 B CN106310580 B CN 106310580B
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- arsenic
- medicament
- conditioner
- arsenic alkaline
- high concentration
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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 kind of High Concentration of Arsenic alkaline residues to stabilize cured medicament, it is composed of the following components that stabilisation solidifies medicament: the oxidant being made of hydrogen peroxide and persulfate, the stabilizer being made of molysite and/or ferrous salt, and the conditioner being made of kaolin and/or attapulgite and red mud and flyash, the synergistic function that the stabilisation solidifies between medicament each component is obvious, it is able to achieve the efficient stableization solidification of High Concentration of Arsenic alkaline residue, it is simple using the method for the medicament, it is at low cost, it is suitble to promote the use of.
Description
Technical field
The present invention relates to a kind of arsenic alkaline slags to stabilize solidification medicament, in particular to a kind of stabilization for High Concentration of Arsenic alkaline residue
Change cured combination medicament, belongs to useless arsenic Slag treatment technical field.
Background technique
Arsenic alkaline slag is the waste residue generated when coarse antimony refining adds soda ash arsenic removal in the process, and slag arsenic content is 5%~7%, wherein
Arsenic mainly exists in the form of natrium arsenicum, and natrium arsenicum is hypertoxic and soluble easily in water, easily pollution environment, is that one kind is very difficult to dispose
Hazardous waste.Arsenic alkaline slag is once reveal, and the arsenic being exposed in environment will enter water body and food chain, and gently then harmful to human is strong
Health, it is heavy then lead to death.Currently, being mainly both at home and abroad that stabilization/solidification, pyrogenic process roasting and wet process are returned to the processing mode of arsenic alkaline slag
Processing modes, each processing methods such as receipts respectively have advantage and disadvantage.
Stabilization/solidification method is the process for changing the engineering characteristic of waste residue using additive, changes the form or valence of heavy metal
State, convert pollutant to not readily dissolve, the state or form that transfer ability or toxicity become smaller.Common stabilization/solidification addition
Agent has molysite, aluminium salt, calcium salt, sulfide, flyash etc., but pollutes for different metal, to stabilization/curing additive
Selection, there are biggish differences for collocation.Currently, the relevant report handled for the solidification and stabilization of arsenic-containing waste residue is fewer.In
State's patent (CN105597262A) is disclosed using H2O2、FeSO4·7H2O, the stabilization of CaO and slag cements as arsenic-containing waste residue
Change curing agent, since arsenic alkaline slag is in strong basicity in arsenic-containing waste residue, cause hydrogen peroxide using low；Especially its arsenic and molysite reaction
The arsenic acid molysite deposition of generation is affected by pH, and under conditions of pH > 7, arsenic acid molysite is unstable to be decomposed, and the patent is solid
Changing CaO and slag cements in stabilization agent, to add ratio higher, is strong basicity, causes arsenic acid molysite to be decomposed, in leachate
The concentration of arsenic increases.In addition, Chinese patent (CN104263949A) selects molysite and clay mineral to stabilize arsenic alkaline slag
Solidification, but arsenic alkaline slag needs to use a large amount of dilute acid for adjusting pH after adding stabilizer, it is at high cost, complicated for operation, in Practical Project complexity
In the case of be difficult to meet the requirements.
Summary of the invention
Defect existing for medicament and method for existing processing arsenic offscum in alkali, the purpose of the invention is to provide one
Kind is able to achieve the cured medicament of efficient stableization of High Concentration of Arsenic alkaline residue, simple using the method for the medicament, at low cost, is suitble to push away
It is wide to use.
In order to achieve the above technical purposes, the present invention provides a kind of High Concentration of Arsenic alkaline residues to stabilize cured medicament, should
Medicament is made of following content of component:
1~3 part of oxidant be made of hydrogen peroxide and persulfate；
15~25 parts of stabilizer be made of molysite and/or ferrous salt；
6~15 parts of conditioner be made of kaolin and/or attapulgite and red mud and flyash.
Stabilisation solidification medicament in technical solution of the present invention mainly includes oxidant, stabilizer and conditioner, oxidation
Agent is made of hydrogen peroxide and persulfate, and oxidability is strong, stability is good, substantially increases oxidation efficiency, can guarantee arsenic alkali
Low price arsenic in waste residue is oxidized to high price arsenic, and high price arsenate such as AsO4 3-Than arsenious acid AsO3 3-It is stable etc. being more readily formed
Solid；On this basis, in conjunction with molysite fixed arsenic, stable precipitated ferric arsenate is generated；In addition, the present invention is adjusted using neutral compounding
Agent is managed, the part aluminium salt in red mud and flyash can generate arsenic acid aluminum precipitation with pentavalent arsenic, and kaolin and attapulgite play
Absorption helps heavy effect, generates synergistic function between various components, stabilizes solidification effect to arsenic alkaline slag and further consolidates
It is promoted.
Preferred scheme, by hydrogen peroxide and persulfate, 1.0~2.0:0.5~1.0 form oxidant in molar ratio.The two
Combination is used as oxidant, and synergistic function is obvious, over cure acid group free radical (SO4 -) and hydroxyl radical free radical (OH) phase
Mutually excitation forms than the single kind stronger system of oxidizing performance.Persulfate generally comprises sodium peroxydisulfate, potassium peroxydisulfate
With ammonium persulfate etc..
Preferred scheme, stabilizer is by ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water frerrous chlorides
At least one composition.Stabilizing agent mainly provides iron ion, and stable compound can be generated with high price arsenic anion, realizes
The stabilisation of arsenic.
Preferred scheme, conditioner by kaolin and/or attapulgite, with red mud and flyash by mass percentage 65~
80%:15~20%:5~15% is formed.Composite conditioner pH of the invention is in neutrality, and plays precipitating and absorbing synergic simultaneously
Effect, may be implemented the stabilisation for consolidating arsenic and solidification.Aluminium salt in red mud and flyash can generate al arsenate with pentavalent arsenic
Precipitating, kaolin and attapulgite play absorption and help heavy effect, stabilize solidification effect to arsenic alkaline slag and further consolidate promotion.
More preferably scheme, conditioner is by 600~750 DEG C of high-temperature activation processing.Being handled by high-temperature activation can be effective
The performance for exciting conditioner, improves the stabilisation curing performance of conditioner, and the time of high-temperature activation processing is generally 60~
150min。
For the hydrogen peroxide that technical solution of the present invention uses for commercially available conventional hydrogen peroxide, mass percent concentration is 30% left
It is right.Commercially available hydrogen peroxide is generally diluted to after mass percent concentration is 2% and is used in compounding with persulfate.
Total content >=20000mg/kg of arsenic in High Concentration of Arsenic alkaline residue of the invention, according to " solid waste leaches horizontal vibration
Swing method " (HJ 557-2010), arsenic leaching concentration is 1000~5000mg/L, pH > 11.
High Concentration of Arsenic alkaline residue of the invention stabilizes method of the cured medicament for handling High Concentration of Arsenic alkaline residue: first by arsenic
Alkaline residue is crushed, is sized to partial size≤1cm；Then oxidant is added and stirs 10~30min, obtains mixture；It is added in the mixture
Stabilizer after stirring 10~30min, adds conditioner, stirs 10~20min, conserves 3~7d.The arsenic alkaline slag after maintenance
The water logging leaching concentration of middle arsenic reaches hazardous waste in " hazard waste landfill contamination control standard " (GB18598-2001) and allows
Into the control limit (being less than 2.5mg/L) in landfill area.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1, the synergistic function that arsenic alkaline slag of the invention stabilisation solidifies in medicament between each component is obvious, is able to achieve height
The water logging leaching concentration of effective fixation of arsenic in concentration arsenic alkaline slag, treated arsenic alkaline slag arsenic is less than 2.5mg/L.Oxidant can incite somebody to action
Low price arsenic is oxidized to high price arsenic, high price arsenate (AsO4 3-) in stabilizer in the presence of containing molysite stable arsenic is more readily formed
Sour iron precipitating, and conditioner can not only generate arsenic acid aluminum precipitation with pentavalent arsenic, and with adsorption function to promote to precipitate, it is right
Arsenic alkaline slag stabilizes solidification effect and carries out further consolidating promotion.
2) arsenic alkaline slag of the invention stabilizes solidification medicament and adjusts pH during handling High Concentration of Arsenic alkaline residue without acid,
Step is simplified, is reduced costs.
3) conditioner that arsenic alkaline slag of the invention stabilisation solidifies medicament use is in neutrality, the arsenic generated in stabilization procedures
Sour iron, arsenic acid aluminum precipitation can be stabilized, preferable to the removal effect of arsenic.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
1, solidification medicament is stabilized to prepare:
High Concentration of Arsenic alkaline residue of the present invention stabilizes solidification medicament and is made of oxidant, stabilizer and conditioner, according to arsenic alkali
Slag property is added according to certain 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) molar ratio multiplicity reactivation forms oxidant；
Stabilizer is one of ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water frerrous chlorides or more
Kind；
The conditioner is made of red mud, kaolin or attapulgite, flyash.By each ingredient of conditioner according to red mud 15
~20%, kaolin or attapulgite 65~80%, the mixing of 5~15% ratio of flyash, sieve with 100 mesh sieve, obtain conditioner powder
End；The thermal activation treatment of conditioner: obtained conditioner powder being roasted, 600~750 DEG C of maturing temperature, and calcining time 60~
150min is prepared into conditioner after cooling.
2, solidification medicament application method is stabilized:
First arsenic alkaline slag is crushed, is sized to partial size≤1cm；Then 1~3% oxidant is added and stirs 10~30min, obtains mixed
Close object；15~25% stabilizers are added in the mixture, stir 10~30min；6~15% conditioners are added in the mixture,
10~20min is stirred, 3~7d is conserved.
Embodiment 1
Oxidant preparation: after being diluted to 2% using commercially available 30% hydrogen peroxide, with sodium peroxydisulfate according to the molar ratio of 2:1
Example is uniformly mixedly configured into oxidant；
Stabilizer preparation: by ferrous sulfate heptahydrate and bodied ferric sulfate according to 5:1 mass ratio mixing stabilizer；
Conditioner preparation: red mud 15%, kaolin or attapulgite 78%, the mixing of 7% ratio of flyash sieve with 100 mesh sieve,
Obtain conditioner powder；The thermal activation treatment of conditioner: obtained conditioner powder is roasted, 630 DEG C of maturing temperature, when roasting
Between 60min, can be used after cooling.
Embodiment 2
Arsenic alkaline slag processing is carried out using the medicament in embodiment 1.
Taking certain arsenic pollution concentration is 21520mg/kg arsenic alkaline slag 500g, 1.5% oxidant stirring 10min is added, then
The stabilizer for being added 15% stirs 10min, and 5d, measurement arsenic leaching are conserved under room temperature after being eventually adding 10% conditioner stirring 10min
Concentration out.The water logging concentration of arsenic is by the 0.93mg/L that drops to that treated of 1950mg/L before handling.Arsenic in arsenic alkaline slag after improvement
Water logging concentration allows access into landfill area lower than hazardous waste in " hazard waste landfill contamination control standard " (GB18598-2001)
Control limit, be less than 2.5mg/L.
Embodiment 3
Arsenic alkaline slag processing is carried out using the medicament in embodiment 1.
Take certain arsenic pollution concentration be 30550mg/kg arsenic alkaline slag 500g, be added 2% oxidant stirring 15min, then plus
The stabilizer stirring 15min for entering 20% conserves 7d under room temperature after being eventually adding 12% conditioner stirring 15min, and measurement arsenic leaches
Concentration.The water logging concentration of arsenic is by the 1.53mg/L that drops to that treated of 2625mg/L before handling.Arsenic water in arsenic alkaline slag after improvement
Leaching concentration allows access into landfill area lower than hazardous waste in " hazard waste landfill contamination control standard " (GB18598-2001)
Control limit is less than 2.5mg/L.
Comparative example 1
Same batch arsenic alkaline slag 500g in Example 3, oxidant additional amount are 0.8%, other additive amount of medicament and place
Science and engineering skill is as embodiment 3, and arsenic water logging concentration is 53.01mg/L in the arsenic alkaline slag after improvement, is higher than " hazard waste landfill dirt
Dye control standard " hazardous waste allows access into the control limit in landfill area in (GB18598-2001).
Comparative example 2
Same batch arsenic alkaline slag 500g in Example 3, stabilizer additional amount are 30%, other additive amount of medicament and processing
Technique is as embodiment 3, and arsenic water logging concentration is 4.56mg/L in the arsenic alkaline slag after improvement, is higher than " hazard waste landfill pollution
Control standard " hazardous waste allows access into the control limit in landfill area in (GB18598-2001).
Comparative example 3
Same batch arsenic alkaline slag 500g in Example 3 adds 2% hydrogen peroxide as oxidant, the addition of other medicaments
Amount is with treatment process as embodiment 3, and arsenic water logging concentration is 30.22mg/L in the arsenic alkaline slag after improvement, is higher than " hazardous waste
Landfill contamination control standard " hazardous waste allows access into the control limit in landfill area in (GB18598-2001).
Comparative example 4
Same batch arsenic alkaline slag 500g, conditioner are not activated in Example 3, other additive amount of medicament and place
Science and engineering skill is as embodiment 3, and arsenic water logging concentration is 10.43mg/L in the arsenic alkaline slag after improvement, is higher than " hazard waste landfill dirt
Dye control standard " hazardous waste allows access into the control limit in landfill area in (GB18598-2001).
Claims (2)
1. a kind of High Concentration of Arsenic alkaline residue stabilizes cured medicament, it is characterised in that: be made of following content of component:
1~3 part of oxidant be made of hydrogen peroxide and persulfate；
15~25 parts of stabilizer be made of molysite and/or ferrous salt；
6~15 parts of conditioner be made of kaolin and/or attapulgite and red mud and flyash；
The oxidant by hydrogen peroxide and persulfate in molar ratio (1.0~2.0): (0.5~1.0) forms；
The conditioner is by kaolin and/or attapulgite, by mass percentage (65~80%) with red mud and flyash:
(15~20%): (5~15%) composition；
The conditioner is by 600~750 DEG C of high-temperature activation processing.
2. High Concentration of Arsenic alkaline residue according to claim 1 stabilizes cured medicament, it is characterised in that: the stabilizer
It is made of at least one of ferrous sulfate heptahydrate, bodied ferric sulfate, Iron trichloride hexahydrate, four water frerrous chlorides.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN109439911B (en) * | 2019-01-02 | 2021-03-23 | 湖南省环境保护科学研究院 | Arsenic alkaline residue treatment system and method for treating arsenic alkaline residue by using same |
| 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 |
| 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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| JP2007038113A (en) * | 2005-08-02 | 2007-02-15 | Kobe Steel Ltd | Organic arsenic compound-containing water treatment method |
| WO2012154498A2 (en) * | 2011-05-06 | 2012-11-15 | Advanced Technology Materials, Inc. | Removal of metal impurities from silicon surfaces for solar cell and semiconductor applications |
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| US3939249A (en) * | 1974-11-07 | 1976-02-17 | Engelhard Minerals & Chemicals Corporation | Purification of talc |
| CN101503239A (en) * | 2009-03-23 | 2009-08-12 | 中国科学院生态环境研究中心 | Multicomponent composite flocculating setting agent and use in arsenic contamination water treatment |
| CN104624621A (en) * | 2014-12-22 | 2015-05-20 | 广西大学 | Reparation medicament applied to arsenic polluted soil and using method |
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