CN101125682A - Method for preparing arsenic trioxide by using arsenic-containing waste water - Google Patents
Method for preparing arsenic trioxide by using arsenic-containing waste water Download PDFInfo
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- CN101125682A CN101125682A CNA2007100357042A CN200710035704A CN101125682A CN 101125682 A CN101125682 A CN 101125682A CN A2007100357042 A CNA2007100357042 A CN A2007100357042A CN 200710035704 A CN200710035704 A CN 200710035704A CN 101125682 A CN101125682 A CN 101125682A
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Abstract
The invention relates to a method to produce arsenic trioxide with waste water containing arsenium, which takes waste water containing arsenium as raw material to produce arsenic trioxide. A. alkali is added to remove impurities, cupric salt is added, the pH value of the solution is adjusted to 4-14 by alkali and green copper arsenite or copper arsenate precipitate is prepared; B. the prepared green copper arsenite or copper arsenate precipitate is made into slurry by water or sulphuric acid solution; sulfur dioxide is pumped into or sulphite is added to be reacted, arsenious acid solution and pink filtration residue are obtained after filtration; C. arsenious acid solution is crystallized, filtered and dried to get arsenic trioxide powder. The invention has the advantages of simple process, saving raw materials, reducing cost and high recovery yield.
Description
Technical field
The present invention relates to the recycling and the treatment technology of arsenic-containing waste water, it is to utilize arsenic-containing waste water to prepare the method for white arsenic.
Background technology
Arsenic and compound grievous injury human health thereof are defined as first kind carcinogens by the Center for Disease Control and the international research institution that gives protection against cancer, mainly are detrimental to health by the drinking-water approach.Therefore, a plurality of countries such as China, the U.S., West Europe, Japan classify arsenic as one of water pollutant of preferential control.In recent years, along with the fast development of industries such as mining, metallurgy, pottery, leather, agricultural chemicals, the arsenic-containing waste water amount increases day by day, and arsenic is serious day by day with pollution to the discharging of environment.
Handling the arsenic-containing waste water main method has in extraction process, ion exchange method, absorption method, the lime and methods such as molysite flocculent precipitation and sulfurization-precipitation method.
Extraction process, ion exchange method, absorption method are mainly used in handles the lower concentration arsenic-containing waste water, but the process complexity, the processing cost height, industrial application is less.Arsenic-containing waste water generally adopts the flocculent precipitation and the sodium sulphite precipitator method to handle.Big in the lime with the molysite flocculence processing quantity of slag, need be cured processing, otherwise arsenic easily is dissolved the generation secondary pollution in the flocculated sludge.Sulfidizing has the recyclable utilization of arsenic sulfide slag that reaction is fast, treatment capacity is big, technology is simple, sulfidizing produces.At present, handling with the method that reclaims arsenic sulfide slag has copper sulfate substitution method, oxygen to press lixiviation process, ferric sulfate oxidation style, and foremost method is the copper sulfate substitution method of SUMITOMO CHEMICAL company invention.
The copper sulfate substitution method is to utilize Cu
2+As (III), As (V) in the displacement arsenic sulfide slag, its reaction is:
3CuSO
4+As
2S
3+4H
2O＝3CuS↓+2HAsO
2+3H
2SO
4
5CuSO
4+As
2S
5+8H
2O＝5CuS↓+2H
3AsO
4+5H
2SO
4
2HAsO
2＝H
2O+As
2O
3↓
Because little, the arsenus acid of arsenus acid solubleness is with As
2O
3From solution, separate out with cupric sulfide and together precipitate.In order to make As
2O
3With separate with cupric sulfide, blast air and make arsenus acid be oxidized into the big arsenic acid of solubleness, thereby realize separating of copper and arsenic.Filter the back and in filtrate, feed SO
2, H
3AsO
4Be reduced the generation arsenus acid, obtain As through overcooling, crystallization, drying
2O
3Powder.The melting of filtered filtration residue drying dehydration Returning smelting stove obtains blister copper.Blister copper obtains high purity copper through electrorefining, and high purity copper prepares copper sulfate after being atomized into copper powder, and copper sulfate and arsenic sulfide slag reaction displacement arsenic also produce cupric sulfide.This technology maturation, As
2O
3Purity height, security are good.But flow process complexity, preparation copper sulfate cost height.Simultaneously, owing to contain bismuth sulfide, antimony sulfide etc. in the cupric sulfide that copper sulfate displacement arsenic produces, the cupric sulfide Returning smelting causes Bi, Sb impurity circulation and accumulation in copper is smelted.Therefore, copper sulfate precipitator method recovery arsenic production cost is quite high.
The present invention then removes metals such as Bi, Sb in the waste water by regulating arsenic-containing waste water pH value, adds copper sulfate, regulates the pH value, and the arsenical copper co-precipitation feeds SO in containing the sedimentary slurry of arsenical copper
2Or add the sulphite reaction, and arsenic enters solution with the arsenus acid form, and copper is retained in the filter residue.Arsenic chloride solution obtains the white arsenic powder through concentrated, crystallization, drying, and filter residue obtains copper sulfate through oxidation behind the branch arsenical copper.
Summary of the invention
It is simple that purpose of the present invention is intended to propose a kind of flow process, and conservation, cost reduce, and the rate of recovery is high utilizes arsenic-containing waste water to prepare the method for white arsenic, makes arsenic in the waste water be reclaimed effectively and utilize.
The objective of the invention is by following realization:
Utilizing arsenic-containing waste water to prepare the method for white arsenic, is to be the feedstock production white arsenic with the arsenic-containing waste water,
A. adding alkali, remove impurity, add mantoquita, is 4-14 with alkali regulator solution pH again, prepares green cupric arsenite or cupric arsenate throw out;
B. the green cupric arsenite or the cupric arsenate throw out furnishing slurry that adopt water or sulphuric acid soln to prepare; Feed sulfurous gas or add sulphite and react, filter and obtain arsenic chloride solution and pink filter residue;
C. arsenic chloride solution obtains the white arsenic powder through crystallization, filtration, drying.
Described alkali is oxyhydroxide and the oxide compound and the aqueous solution thereof of alkali-metal oxyhydroxide and oxide compound, alkaline-earth metal.
Described alkali is preferably sodium hydroxide, yellow soda ash, lime or its solution,
Described mantoquita is soluble copper salt such as copper sulfate, cupric chloride or cupric nitrate.Can be solid or solution.
Add in the mantoquita, copper is preferably 0.5-4 with the ratio of arsenic amount of substance.
Pink filter residue water or sulphuric acid soln furnishing slurry are after oxidation prepares mantoquita.
Used oxygenant is oxygen, ozone, air, hydrogen peroxide, nitric acid, nitrate, oxynitride, chlorine, hypochlorous acid, hypochlorite, oxymuriate during oxidation redness filter residue.
Mother liquor after the white arsenic crystallization returns for the first time, and filtrate prepares copper arsenic coprecipitate.
Regulate the pH value of filtrate that preparation copper arsenic coprecipitate produces with alkali, discharge after adding bodied ferric sulfate or green vitriol, polymerize aluminum chloride, the polyacrylamide flocculation treatment.
The present invention compares with the copper sulfate substitution method that famous SUMITOMO CHEMICAL company invents, and its distinct advantage is that the present invention has optimized technical process, has done change from mentality of designing.At first metals such as Bi, Sb can obtain reclaiming from the slag that adds the alkali removal of impurities in the arsenic-containing waste water.Directly feed SO again
2Reduction separates arsenical copper, prepares arsenus acid; Only need the red filter residue of simple oxidation in the subsequent technique, with regard to recyclable copper sulfate; Do not need sodium sulphite.Total arsenic rate of recovery is up to more than 90%.
The white arsenic that the present invention utilizes arsenic-containing waste water to be converted into to have important use, make arsenic-containing waste water obtain reclaiming and utilization, utilize arsenic-containing waste water to reclaim the white arsenic method with other and compare, technology of the present invention is simple, conservation, cost reduces, the rate of recovery is high characteristics.
The present invention has controlled arsenic contamination effectively and has contained the discharging of arsenic in environment, can reduce the processing cost of arsenic-containing waste water greatly, and the present invention has tangible economic benefit and significant environmental benefit.
Embodiment
Embodiment 1
Get 5m
3Containing arsenic is 6.2gL
-1Certain smeltery's sulfurous gas washes, regulate wastewater pH to 6.0 with milk of lime, stir 2 hours after-filtration and obtain gypsum tailings and arsenic containing solution.In copper: the ratio of arsenic amount of substance is 1.17 ratio, adds the 120kg cupric sulfate pentahydrate in arsenic containing solution, stirs it is fully dissolved, and adding sodium hydrate regulator solution pH value is 8.0, and dense sedimentation after-filtration, washing obtain green cupric arsenite and precipitate.
With green filter residue cupric arsenite furnishing slurry, feed SO with the water of 4 times of volumes
2, reaction causes the arsenic more than 95% to change the solution after-filtration over to and obtains arsenic chloride solution and copper bearing red filter residue.Arsenic chloride solution evaporation concentration, crystallization, filtration, drying are obtained 28kg white arsenic powder, and direct yield reaches 85%, and arsenic content reaches 95% in the product white arsenic.。
Add hydrogen peroxide with dilution heat of sulfuric acid after with the red filter residue furnishing of cupric slurry, obtain the cupric sulfate pentahydrate mass percent concentration and be 26.75% copper-bath.
Preparing green cupric arsenite post precipitation waste water arsenic is that 78mg/L, pH are 8.Adopt lime to regulate waste water ph greater than 10 and to control endpoint pH be about 7, bubbling air is 4 to add green vitriols by the ratio of iron arsenic amount of substance, contains arsenic 0.47mg/L through the green vitriol processed waste water, and arsenic reaches national waste water comprehensive discharge standard (GB8978-1996).
Embodiment 2
Get 2m
3It is 4.4gL that certain smeltery contains arsenic
-1Sewage, with solid sodium hydroxide 30kg regulator solution pH to 7.0,1 hour after-filtration of stirring reaction obtains filter residue and arsenic containing solution.In copper: the ratio of arsenic amount of substance is 1.20 ratio, toward in arsenic containing solution, adding the 35kg cupric sulfate pentahydrate, stirring is fully dissolved it, and adding sodium hydrate regulator solution pH value is 10.0, and stirring reaction 0.5h after-filtration, washing obtain green cupric arsenite precipitation with this understanding.
Water with 4 times of volumes precipitates the furnishing slurry with green cupric arsenite, feeds SO
2Reaction makes the arsenic more than 96% change solution over to, filters to obtain arsenic chloride solution and copper bearing red filter residue.Arsenic chloride solution evaporation concentration, crystallization, filtration, drying are obtained the 8.9kg white arsenic, and the arsenic direct yield reaches 88%, and arsenic content reaches 98% in the product white arsenic.
To pH=7.0, is 8 adding bodied ferric sulfate flocculation treatment by the ratio by iron arsenic amount of substance with the arsenic-containing waste water after the milk of lime control copper sulfate arsenic precipitation, and it is 0.22mgL that processed waste water contains arsenic
-1, be lower than discharging standards (GB8978-1996).
Embodiment 3
Get 5m
3Containing arsenic is 6.2gL
-1Certain smeltery's sulfurous gas washes, regulate wastewater pH to 2.0 after-filtration with milk of lime and obtain gypsum tailings and contain arsenic filtrate.Re-use solid sodium hydroxide regulator solution pH to 6.0,1 hour after-filtration of stirring reaction obtains arsenic containing solution.
Add the copper-bath of embodiment 1 gained in arsenic containing solution, stirring is fully dissolved it, and adding sodium hydrate regulator solution pH value is 6.0, and dense sedimentation after-filtration, washing obtain green cupric arsenite precipitation.
With green filter residue cupric arsenite furnishing slurry, feed SO with the water of 4 times of volumes
2Reaction makes the arsenic more than 95% change the solution after-filtration over to and obtains arsenic chloride solution and copper bearing red filter residue.Arsenic chloride solution evaporation concentration, crystallization, filtration, drying are obtained 33.3kg white arsenic powder, and total recovery reaches 92%, and arsenic content reaches 97% in the product white arsenic.
Preparing green cupric arsenite post precipitation waste water arsenic is that 80mg/L, pH are 7.8.Adopt lime to regulate waste water ph greater than 10 and to control endpoint pH be about 7, bubbling air is 4 to add green vitriols by the ratio of iron arsenic amount of substance, contains arsenic 0.40mg/L through the green vitriol processed waste water, and arsenic reaches national waste water comprehensive discharge standard (GB8978-1996).
Claims (6)
1. utilizing arsenic-containing waste water to prepare the method for white arsenic, is to be the feedstock production white arsenic with the arsenic-containing waste water, it is characterized in that:
A. adding alkali, remove impurity, add mantoquita, is 4-14 with alkali regulator solution pH again, prepares green cupric arsenite or cupric arsenate throw out;
B. the green cupric arsenite or the cupric arsenate throw out furnishing slurry that adopt water or sulphuric acid soln to prepare; Feed sulfurous gas or add sulphite and react, filter and obtain arsenic chloride solution and pink filter residue;
C. arsenic chloride solution obtains the white arsenic powder through crystallization, filtration, drying.
2. the method for utilizing arsenic-containing waste water to prepare white arsenic according to claim 1 is characterized in that: described alkali is oxyhydroxide and the oxide compound and the aqueous solution thereof of alkali-metal oxyhydroxide and oxide compound, alkaline-earth metal.
3. the method for utilizing arsenic-containing waste water to prepare white arsenic according to claim 1 is characterized in that: described mantoquita is copper sulfate, cupric chloride or cupric nitrate.
4. the method for utilizing arsenic-containing waste water to prepare white arsenic according to claim 1 is characterized in that: add in the mantoquita, copper is 0.5-4 with the ratio of arsenic amount of substance.
5. the method for utilizing arsenic-containing waste water to prepare white arsenic according to claim 1 is characterized in that: pink filter residue water or sulphuric acid soln furnishing slurry are after oxidation prepares mantoquita.
6. the method for utilizing arsenic-containing waste water to prepare white arsenic according to claim 5 is characterized in that: used oxygenant is oxygen, ozone, air, hydrogen peroxide, nitric acid, nitrate, oxynitride, chlorine, hypochlorous acid, hypochlorite or oxymuriate during oxidation redness filter residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100357042A CN100572286C (en) | 2007-09-07 | 2007-09-07 | Utilize arsenic-containing waste water to prepare the method for white arsenic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100357042A CN100572286C (en) | 2007-09-07 | 2007-09-07 | Utilize arsenic-containing waste water to prepare the method for white arsenic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101125682A true CN101125682A (en) | 2008-02-20 |
| CN100572286C CN100572286C (en) | 2009-12-23 |
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|---|---|---|---|
| CNB2007100357042A Expired - Fee Related CN100572286C (en) | 2007-09-07 | 2007-09-07 | Utilize arsenic-containing waste water to prepare the method for white arsenic |
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Cited By (18)
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|---|---|---|---|---|
| CN101767822A (en) * | 2008-12-31 | 2010-07-07 | 江西铜业集团公司 | Method for recovering arsenic from scrap material containing arsenic and copper produced in process of copper smelting |
| CN102115164A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN102115165A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102517449A (en) * | 2011-12-16 | 2012-06-27 | 山东方圆有色金属技术服务有限公司 | Comprehensive recycling technique of valuable elements in smelting soot |
| CN102602994A (en) * | 2011-12-20 | 2012-07-25 | 湖南展泰有色金属有限公司 | Method for preparing arsenic trioxide by utilizing arsenious waste water |
| CN102718259A (en) * | 2012-06-18 | 2012-10-10 | 中南大学 | Method for depositing and converting arsenic wastewater into arsenic trioxide |
| CN103288133A (en) * | 2012-02-27 | 2013-09-11 | 兰州理工大学 | Method for preparing arsenic trioxide from black copper sludge |
| CN103484693A (en) * | 2013-10-10 | 2014-01-01 | 郴州市金贵银业股份有限公司 | Harmlessness method for treating arsenic in antimony oxide |
| CN104496000A (en) * | 2014-12-16 | 2015-04-08 | 浙江工业大学 | Method for removing and recovering arsenic and antimony in water body by replacement of copper powder |
| RU2574449C2 (en) * | 2013-11-13 | 2016-02-10 | Александр Михайлович Ченцов | Method of removing arsenic (v) compounds from technological solutions |
| CN106396202A (en) * | 2016-12-07 | 2017-02-15 | 武汉工程大学 | Method for resource utilization of waste acid with arsenic and fluorine import |
| CN108640390A (en) * | 2018-05-31 | 2018-10-12 | 阳谷祥光铜业有限公司 | A kind of processing method of stibium-containing wastewater |
| CN110627179A (en) * | 2019-11-05 | 2019-12-31 | 深圳市长隆科技有限公司 | Method for treating arsenic-containing wastewater by using recyclable composite salt precipitator |
| CN113413925A (en) * | 2021-06-25 | 2021-09-21 | 郑州大学 | Method for recovering As and compounds thereof in waste SCR denitration catalyst |
| CN114133059A (en) * | 2021-11-08 | 2022-03-04 | 广西南国铜业有限责任公司 | Purification method for washing waste acid from copper smelting flue gas |
| CN114506937A (en) * | 2021-12-30 | 2022-05-17 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Regeneration method of dechlorination slag, regeneration dechlorination circulating slag and regeneration circulating dechlorination method |
| CN115159659A (en) * | 2022-07-05 | 2022-10-11 | 西部黄金伊犁有限责任公司 | Arsenic removal device and method for ozone treatment of waste acid stock solution |
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2007
- 2007-09-07 CN CNB2007100357042A patent/CN100572286C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767822A (en) * | 2008-12-31 | 2010-07-07 | 江西铜业集团公司 | Method for recovering arsenic from scrap material containing arsenic and copper produced in process of copper smelting |
| CN102115164A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN102115165A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by arsenic-containing waste water |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102517449A (en) * | 2011-12-16 | 2012-06-27 | 山东方圆有色金属技术服务有限公司 | Comprehensive recycling technique of valuable elements in smelting soot |
| CN102602994A (en) * | 2011-12-20 | 2012-07-25 | 湖南展泰有色金属有限公司 | Method for preparing arsenic trioxide by utilizing arsenious waste water |
| CN103288133A (en) * | 2012-02-27 | 2013-09-11 | 兰州理工大学 | Method for preparing arsenic trioxide from black copper sludge |
| CN102718259A (en) * | 2012-06-18 | 2012-10-10 | 中南大学 | Method for depositing and converting arsenic wastewater into arsenic trioxide |
| CN102718259B (en) * | 2012-06-18 | 2014-01-01 | 中南大学 | Method for depositing and converting arsenic wastewater into arsenic trioxide |
| CN103484693A (en) * | 2013-10-10 | 2014-01-01 | 郴州市金贵银业股份有限公司 | Harmlessness method for treating arsenic in antimony oxide |
| RU2574449C2 (en) * | 2013-11-13 | 2016-02-10 | Александр Михайлович Ченцов | Method of removing arsenic (v) compounds from technological solutions |
| CN104496000A (en) * | 2014-12-16 | 2015-04-08 | 浙江工业大学 | Method for removing and recovering arsenic and antimony in water body by replacement of copper powder |
| CN106396202A (en) * | 2016-12-07 | 2017-02-15 | 武汉工程大学 | Method for resource utilization of waste acid with arsenic and fluorine import |
| CN108640390A (en) * | 2018-05-31 | 2018-10-12 | 阳谷祥光铜业有限公司 | A kind of processing method of stibium-containing wastewater |
| CN110627179A (en) * | 2019-11-05 | 2019-12-31 | 深圳市长隆科技有限公司 | Method for treating arsenic-containing wastewater by using recyclable composite salt precipitator |
| CN110627179B (en) * | 2019-11-05 | 2022-02-22 | 深圳市长隆科技有限公司 | Method for treating arsenic-containing wastewater by using recyclable composite salt precipitator |
| CN113413925A (en) * | 2021-06-25 | 2021-09-21 | 郑州大学 | Method for recovering As and compounds thereof in waste SCR denitration catalyst |
| CN114133059A (en) * | 2021-11-08 | 2022-03-04 | 广西南国铜业有限责任公司 | Purification method for washing waste acid from copper smelting flue gas |
| CN114506937A (en) * | 2021-12-30 | 2022-05-17 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Regeneration method of dechlorination slag, regeneration dechlorination circulating slag and regeneration circulating dechlorination method |
| CN114506937B (en) * | 2021-12-30 | 2023-08-29 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for regenerating dechlorinated slag, regenerated dechlorinated cyclic slag and regenerated cyclic dechlorination method |
| CN115159659A (en) * | 2022-07-05 | 2022-10-11 | 西部黄金伊犁有限责任公司 | Arsenic removal device and method for ozone treatment of waste acid stock solution |
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