CN106390355A - Preparation method and application of modified zinc hypoxide slag composite particles for arsenic fixation of arsenic alkali slag - Google Patents
Preparation method and application of modified zinc hypoxide slag composite particles for arsenic fixation of arsenic alkali slag Download PDFInfo
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- CN106390355A CN106390355A CN201610784553.XA CN201610784553A CN106390355A CN 106390355 A CN106390355 A CN 106390355A CN 201610784553 A CN201610784553 A CN 201610784553A CN 106390355 A CN106390355 A CN 106390355A
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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 preparation method and application of modified zinc hypoxide slag composite particles for arsenic fixation of arsenic alkali slag. The preparation method of the modified zinc hypoxide slag composite particles for the arsenic fixation of the arsenic alkali slag comprises the steps that zinc hypoxide slag, ferric salt, water and monopotassium phosphate are mixed and granulated, calcination activation and cooling are conducted on the obtained particles, and then the modified zinc hypoxide slag composite particles are obtained. When used as an arsenic fixation additive to be applied to the arsenic fixation of the arsenic alkali slag, the modified zinc hypoxide slag composite particles show the advantages of good arsenic fixation effect and high stability. By the adoption of the preparation method and application of the modified zinc hypoxide slag composite particles for the arsenic fixation of the arsenic alkali slag, waste is treated by waste, and therefore cost is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of modification secondary zinc oxide slag composite particles and its answering in the solid arsenic of arsenic alkaline slag
With belonging to the solid arsenic field of arsenic alkaline slag.
Background technology
Arsenic is widely present in multiple Non-ferrous minerals of nature.In the process exploited, smelt, extract non-ferrous metal
In, arsenic removes usually as a kind of objectionable impurities.Because arsenic is oxidized easily, general employing adds the method arsenic removal that alkali aoxidizes.
Arsenic element is often contained in antimony ore, conventional plus soda arsenic removal in antimony smelting process, the slag containing arsenic obtaining after arsenic removal is referred to as arsenic alkaline slag.Arsenic
In alkaline residue, arsenic is mainly presented in natrium arsenicum, hypertoxic and soluble in water, easily pollutes environment, is that a class is very difficult to dispose
Hazardous waste.Once revealing, the arsenic being exposed in environment will enter water body and food chain to arsenic alkaline slag, and gently then harmful to human is good for
Health, heavy then lead to death.At present, both at home and abroad the processing mode of arsenic alkaline slag is mainly stablized/solidified, pyrogenic process roasting and wet method are returned
The processing modes such as receipts, each processing method respectively has pluses and minuses.
Secondary zinc oxide waste residue is one of main waste residue of smelting Zn Cr coating, its main component be zinc, aluminum, ferrum, magnesium, silicon, antimony,
The compound of the elements such as indium.In secondary zinc oxide slag, Zn content is between 1.5%～12%, aluminium content between 10%～21%,
The content of ferrum is between 8%～17%.Because China's production Technology is more backward, open pit mining rate is low, has quite big
A part of secondary zinc oxide slag becomes pollutant from available resources, not only causes the waste of resource, and causes serious
Environmental pollution.
Content of the invention
For the defect in prior art, the processing method such as arsenic alkaline slag and secondary zinc oxide waste residue being existed, the purpose of the present invention
It is that being to provide a kind of is raw material using secondary zinc oxide slag industrial residue, preparing one kind by simple process can effective fixed arsenic alkali
The method of the modified secondary zinc oxide slag composite particles of arsenic in slag.
Another object of the present invention is to be to provide a kind of modification secondary zinc oxide slag composite particles in the solid arsenic of arsenic alkaline slag
Application, modified secondary zinc oxide slag composite particles are used for the solid arsenic of arsenic alkaline slag, show that arsenic fixation effect is good, the strong advantage of stability,
Realize the treatment of wastes with processes of wastes against one another, cost-effective.
In order to realize above-mentioned technical purpose, the invention provides a kind of modified secondary zinc oxide slag for the solid arsenic of arsenic alkaline slag is multiple
Close the preparation method of granule, the method is by secondary zinc oxide slag, iron salt, water and potassium dihydrogen phosphate mixing granulation, and gained granule exists
300～450 DEG C of roasting temperatures, cooling, obtain final product.
Technical scheme, prepares the modified oxidation for the solid arsenic of arsenic alkaline slag first with secondary zinc oxide slag for raw material
Cadmia composite particles, make full use of the particularity of secondary zinc oxide slag itself, and such as its pH is in neutral slant acidity, and containing abundant
CaO、SiO2、Al2O3、Fe2O3Deng material.Technical scheme is passed through to add iron salt, potassium dihydrogen phosphate and water, makes modification
Secondary zinc oxide solid impurity particle simultaneously makes it activate by roasting so that the part of the metal oxide in secondary zinc oxide slag dissolves, such as dissolution
Ferrum, aluminium ion and phosphate radical form iron phosphate aluminum etc., its and arsenate can be made reacts, and to generate precipitated ferric arsenate, al arsenate heavy
Form sediment etc..Meanwhile, the secondary zinc oxide slag composite particles of preparation assume acidity, can neutralize arsenic alkaline slag, adjust pH so that the arsenic that generates
Sour ferrum, arsenic acid aluminum precipitation can stable existence, this is all advantageously implemented the arsenic fixing-stable of arsenic alkaline slag.
Preferably scheme, the quality of described iron salt is the 2～5% of secondary zinc oxide slag quality.
Preferably scheme, the quality of described potassium dihydrogen phosphate is the 2～6% of secondary zinc oxide slag and iron salt gross mass.
Preferably scheme, the particle diameter of described granule is 0.5mm～1.5mm.
Preferably scheme, the time of described roasting is 60～90min.
The iron salt adopting in technical scheme is included in ferrous sulfate heptahydrate, bodied ferric sulfate or iron chloride etc. extremely
Few one kind.
The water one side that in technical scheme, granulation process adds is used for dissolving phosphoric acid potassium dihydrogen, on the one hand plays
Cementation, its consumption be this area routine addition, belong to it will be appreciated by those skilled in the art that category.
Present invention also offers the modified secondary zinc oxide slag composite particles of methods described preparation answering in the solid arsenic of arsenic alkaline slag
With this application process is that in arsenic alkaline slag, modified secondary zinc oxide slag composite particles are consolidated arsenic as solid arsenic additive application.
The modified secondary zinc oxide slag composite particles of the present invention, during the solid arsenic of arsenic alkaline slag, are mainly reacted with arsenic alkaline slag,
On the one hand generate al arsenate, precipitated ferric arsenate with arsenic acid reactant salt, on the one hand provide sour environment that al arsenate, ferric arsenate are sunk
Shallow lake stable existence, reduces arsenic leaching concentration in arsenic alkaline slag.
Preferably scheme, after arsenic alkaline slag, described modification secondary zinc oxide slag composite particles and water are uniformly mixed, supports
Shield.
More preferably scheme, after arsenic alkaline slag is pulverized, screening sieve takes the granule of particle diameter≤1cm.
More preferably scheme, described modification secondary zinc oxide slag composite particles quality is the 10～20% of zinc oxide slag quality.
More preferably scheme, stirring incorporation time is 30～60min.
More preferably scheme, curing time is 3～7d.
During in technical scheme, modified secondary zinc oxide slag composite particles are used for the solid arsenic of arsenic alkaline slag, water is mainly made
For the transmission medium of various ions and each kind of proton, and promote the generation of colloidal compound, its consumption is also conventional amount used, for this
Skilled person may be appreciated category.
Hinge structure, the Advantageous Effects that technical scheme is brought：
1) technical scheme prepare secondary zinc oxide slag composite particles method simple, raw material sources are wide, low cost,
Be conducive to industrialized production.
2) the secondary zinc oxide slag composite particles of technical scheme preparation are used for the solid arsenic of arsenic alkaline slag, and arsenic fixation effect is good,
Stability is strong, can reach《Hazard waste landfill Environmental capacity standard》(GB18598-2001).
3) technical scheme is realized administering arsenic alkaline slag, the treatment of wastes with processes of wastes against one another with secondary zinc oxide slag, decreases environmental pollution,
Reduce controlling waste residue cost, there is important economic and environment-friendly meaning.
Specific embodiment
Following examples are intended to further illustrate present invention, rather than the protection model limiting the claims in the present invention
Enclose.
Embodiment 1
1st, the preparation of modified secondary zinc oxide slag composite particles：
With secondary zinc oxide slag as raw material, add secondary zinc oxide slag quality 5% bodied ferric sulfate, after stirring, become mixing
Thing, adds 10% water and the potassium dihydrogen phosphate of mixture quality 5% in mixture, is prepared into modified oxygen of 0.5mm-1.5mm
Change cadmia composite particles.
The thermal activation treatment of modified secondary zinc oxide slag：By the modified secondary zinc oxide solid impurity particle roasting obtaining, sintering temperature 420
DEG C, roasting time 90min, can use after cooling.
2nd, arsenic alkaline slag Arsenic fixation method：
First arsenic alkaline slag 500g crushed, sieve the granule taking particle diameter≤1cm；Then stir in stirred autoclave；Add
20% modified secondary zinc oxide slag composite particles and 15% water, stir 60min, maintenance 7d.Measure arsenic leaching concentration.The water logging of arsenic
Concentration is dropped to the 1.64mg/L after process by before processing 486mg/L.In arsenic alkaline slag after improvement, arsenic water logging concentration is less than《Dangerous
Waste reclamation Environmental capacity standard》(GB18598-2001) in, hazardous waste allows access into the control limit in landfill area.
Embodiment 2
1st, the preparation of modified secondary zinc oxide slag composite particles：
With secondary zinc oxide slag as raw material, add secondary zinc oxide slag quality 2% iron salt bodied ferric sulfate, after stirring, become mixed
Compound, adds 10% water and the potassium dihydrogen phosphate of mixture quality 3.8% in mixture, is prepared into 0.5mm-1.5mm modified
Secondary zinc oxide slag composite particles.
The thermal activation treatment of modified secondary zinc oxide slag：By the modified secondary zinc oxide solid impurity particle roasting obtaining, sintering temperature 350
DEG C, roasting time 90min, can use after cooling.
2nd, arsenic alkaline slag Arsenic fixation method：
First arsenic alkaline slag 500g crushed, sieve the granule taking particle diameter≤1cm；Then stir in stirred autoclave；Add
12% modified secondary zinc oxide slag composite particles and 15% water, stir 30min, maintenance 7d.Measure arsenic leaching concentration.The water logging of arsenic
Concentration is dropped to the 0.55mg/L after process by before processing 55.1mg/L.In arsenic alkaline slag after improvement, arsenic water logging concentration is less than《Danger
Dangerous waste reclamation Environmental capacity standard》(GB18598-2001) in, hazardous waste allows access into the control limit in landfill area.
Comparative example 1
Potassium dihydrogen phosphate is not added, other preparation methoies and embodiment in the preparation of modified secondary zinc oxide slag composite particles
Consistent in 2.
Same batch arsenic alkaline slag 500g in Example 2, broken, screening takes particle diameter≤1cm；Add in this comparative example
The modified secondary zinc oxide slag composite particles of preparation, other additive amount of medicament arsenic as embodiment 2, after improvement with handling process
In alkaline residue, arsenic water logging concentration is 31.3mg/L, is higher than《Hazard waste landfill Environmental capacity standard》(GB18598-2001) dangerous in
Waste allows access into the control limit in landfill area.
Comparative example 2
Do not carry out thermal activation treatment, other preparation methoies and embodiment 2 after the preparation of modified secondary zinc oxide slag composite particles
In consistent.
Same batch arsenic alkaline slag 500g in Example 2, broken, screening takes particle diameter≤1cm；Add in this comparative example
The modified secondary zinc oxide slag composite particles of preparation, other additive amount of medicament arsenic as embodiment 2, after improvement with handling process
In alkaline residue, arsenic water logging concentration is 13.8mg/L, is higher than《Hazard waste landfill Environmental capacity standard》(GB18598-2001) dangerous in
Waste allows access into the control limit in landfill area.
Claims (10)
1. a kind of preparation method of the modified secondary zinc oxide slag composite particles for the solid arsenic of arsenic alkaline slag it is characterised in that：By secondary oxygen
Change cadmia, iron salt, water and potassium dihydrogen phosphate mixing granulation, gained granule, in 300～450 DEG C of roasting temperatures, cools down, obtains final product.
2. the preparation method of the modified secondary zinc oxide slag composite particles for the solid arsenic of arsenic alkaline slag according to claim 1, its
It is characterised by：
The quality of described iron salt is the 2～5% of secondary zinc oxide slag quality；
Described potassium dihydrogen phosphate quality is the 2～6% of secondary zinc oxide slag and iron salt gross mass.
3. the preparation method of the modified secondary zinc oxide slag composite particles for the solid arsenic of arsenic alkaline slag according to claim 1, its
It is characterised by：The particle diameter of described granule is 0.5mm～1.5mm.
4. the system of the modified secondary zinc oxide slag composite particles for the solid arsenic of arsenic alkaline slag according to any one of claims 1 to 3
Preparation Method it is characterised in that：The time of described roasting is 60～90min.
5. the modified secondary zinc oxide slag composite particles of the preparation method preparation described in any one of Claims 1 to 4 are solid in arsenic alkaline slag
Application in arsenic it is characterised in that：Modified secondary zinc oxide slag composite particles are as solid arsenic additive application in the solid arsenic of arsenic alkaline slag.
6. the modified secondary zinc oxide slag composite particles of preparation method preparation according to claim 5 are in the solid arsenic of arsenic alkaline slag
Application it is characterised in that：After arsenic alkaline slag, described modification secondary zinc oxide slag composite particles and water are uniformly mixed, maintenance.
7. the modified secondary zinc oxide slag composite particles of preparation method preparation according to claim 6 are in the solid arsenic of arsenic alkaline slag
Application it is characterised in that：After arsenic alkaline slag is pulverized, screening sieve takes the granule of particle diameter≤1cm.
8. the modified secondary zinc oxide slag composite particles of preparation method preparation according to claim 6 are in the solid arsenic of arsenic alkaline slag
Application it is characterised in that：The quality of described modification secondary zinc oxide slag composite particles is the 10～20% of zinc oxide slag quality.
9. the modified secondary zinc oxide slag composite particles of preparation method preparation according to claim 6 are in the solid arsenic of arsenic alkaline slag
Application it is characterised in that：Stirring incorporation time is 30～60min.
10. the modified secondary zinc oxide slag composite particles of preparation method preparation according to claim 6 are in the solid arsenic of arsenic alkaline slag
Application it is characterised in that：Curing time is 3～7d.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5688827A (en) * | 1979-12-21 | 1981-07-18 | Nippon Mining Co Ltd | Separation and recovery of arsenic |
| JP2001327979A (en) * | 2000-05-24 | 2001-11-27 | Natl Inst Of Advanced Industrial Science & Technology Meti | Method for treating wastewater containing arsenic and removing agent |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN102557222A (en) * | 2012-02-15 | 2012-07-11 | 天津理工大学 | Method for removing trace arsenic from aqueous solution |
| CN104056854A (en) * | 2014-06-25 | 2014-09-24 | 湖南新九方科技有限公司 | United stable mineralizing repairing agent for treating soil with combined pollution of Pb, As, Cu, and Cd and application method of repairing agent |
| CN104174634A (en) * | 2014-08-15 | 2014-12-03 | 江苏理工学院 | Stable curing method of strongly acidic arsenic sulfide waste residues |
-
2016
- 2016-08-31 CN CN201610784553.XA patent/CN106390355B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5688827A (en) * | 1979-12-21 | 1981-07-18 | Nippon Mining Co Ltd | Separation and recovery of arsenic |
| JP2001327979A (en) * | 2000-05-24 | 2001-11-27 | Natl Inst Of Advanced Industrial Science & Technology Meti | Method for treating wastewater containing arsenic and removing agent |
| CN102249609A (en) * | 2011-04-29 | 2011-11-23 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN102557222A (en) * | 2012-02-15 | 2012-07-11 | 天津理工大学 | Method for removing trace arsenic from aqueous solution |
| CN104056854A (en) * | 2014-06-25 | 2014-09-24 | 湖南新九方科技有限公司 | United stable mineralizing repairing agent for treating soil with combined pollution of Pb, As, Cu, and Cd and application method of repairing agent |
| CN104174634A (en) * | 2014-08-15 | 2014-12-03 | 江苏理工学院 | Stable curing method of strongly acidic arsenic sulfide waste residues |
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Effective date of registration: 20170407 Address after: 410100 Changsha economic and Technological Development Zone, Hunan, Xingsha Road, No. 15, No. Applicant after: Aerospace Kay environmental Polytron Technologies Inc Address before: Changsha County City, Hunan province 410000 Changsha Bamboo Road No. 59 Kaitian Industrial Park Applicant before: Hunan Kaitian Heavy Metal Pollution Control Engineering Co., Ltd. |
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