CN102602994B - Method for preparing arsenic trioxide by utilizing arsenious waste water - Google Patents
Method for preparing arsenic trioxide by utilizing arsenious waste water Download PDFInfo
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- CN102602994B CN102602994B CN 201110431286 CN201110431286A CN102602994B CN 102602994 B CN102602994 B CN 102602994B CN 201110431286 CN201110431286 CN 201110431286 CN 201110431286 A CN201110431286 A CN 201110431286A CN 102602994 B CN102602994 B CN 102602994B
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Abstract
The invention discloses a method for preparing arsenic trioxide by utilizing arsenious waste water. The method comprises the following steps of: adopting the arsenious waste water as a raw material, adding a water-soluble organic reducing agent such as low-grade fatty aldehyde and urea, reacting for 0.5-8 hours under the temperature of 15-150 DEG C and the pressure of 0.1-10MPa, reducing arsenate into arsenite, then adding sulfuric acid for adjusting pH to be acid, enabling the arsenite to be converted into the arsenic trioxide which is precipitated, then evaporating and concentrating solution, filtering, drying, then carrying out heating sublimation or recrystallizing purification on the obtained arsenic trioxide, and then obtaining a high-purity arsenic trioxide product. The method disclosed by the invention has the advantages of simple process, easiness in implementation, lower cost, and high recovery rate and product purity.
Description
Technical field
What the present invention relates to is arsenic-containing waste water or the comprehensive utilization of the arsenic-containing water solution of arsenic-containing material after acid or alkali or water treatment and the method for Processing of Preparation white arsenic that non-ferrous metals smelting works or chemical plant are discharged.
Background technology
Arsenic and compound grievous injury human health thereof are defined as first kind carcinogens by the Center for Disease Control and anti-cancer research institution of country, mainly are detrimental to health by the tap 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.On the other hand, white arsenic is the very important industrial chemicals of a class, has been widely used in industries such as semi-conductor, metallurgy, glass, agricultural chemicals, process hides, printing and dyeing, medicine at present.In recent years, along with a large amount of exploitations of metallic ore and arsenic in industrial widespread use, arsenic-containing waste water, waste residue amount increase day by day, the arsenic environmental pollution is on the rise.Therefore, reclaiming the demand that arsenic is not only environment protection from arsenic-containing water solution, also is the needs of national economy sustainable development.
Handle arsenic-containing waste water main method have in extraction process, ion exchange method, absorption method, the lime and molysite flocculent precipitation and sulphuring treatment intermediate processing.
Extraction process, ion exchange method, absorption method are mainly for the treatment of 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 flocculent precipitation and the sodium sulphite precipitator method to handle.Big with the molysite flocculence processing quantity of slag in the lime, 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.
Obviously, if not necessary, handle arsenic-containing water solution with " waste water " form, be the significant wastage to resource.
The source of arsenic-containing water solution mainly is the waste water that discharge in non-ferrous metals smelting works and chemical plant, and the intermediate material of arsenic-containing material after acid or alkali or water treatment.At present, the method for recovery arsenic mainly is electrolytic process and chemical reduction method from arsenic-containing water solution.The remarkable shortcoming of electrolytic process is that energy consumption generates AsH greatly and easily
3And threat operator life security.Chemical reduction method mainly is to use SO
2Gas is reduced to arsenus acid with arsenate and separates out white arsenic, or earlier through some pre-treatment, these pre-treatment mainly are to add alkali filtering and impurity removing then, or adds copper sulfate and generate and contain the arsenic intermediate product, or adding vulcanizing agent generates As
2S
3Precipitation, thus again with the copper sulfate leaching and with oxygenant oxidation removal of impurities etc., use SO again
2Gas reduction.The core of these methods all is to use SO
2Gas is reduced to arsenate arsenus acid and separates out white arsenic, reacts as follows:
AsO
4 3-+SO
2+H
+→HAsO
2+SO
4 2-
2HAsO
2→As
2O
3+H
2O
SO
2The main drawback of reduction method is SO
2Solubleness is less, and gas-liquid inhomogeneous reaction speed is slow, and equipment and flow process complexity, investment are big, and reaction process is to equipment and operative technique conditional request harshness.
Summary of the invention
The present invention then is to use water-soluble organic class reductive agent that arsenate is reduced to arsenite, and then adding sulfuric acid adjusting pH according to circumstances is that acidity is beneficial to As
2O
3Separate out.Reaction whole process is liquid phase reaction, and flow process is simple, has overcome the shortcoming of gas liquid reaction preferably.
The object of the present invention is to provide a kind of flow process simple, cost is lower, high-level efficiency, high-recovery, and the arsenic-containing waste water that utilizes of safe and feasible prepares the method for white arsenic.
The objective of the invention is to realize by following step:
Be raw material with the arsenic-containing waste water, adding water the organic class reductive agent of dissolubility reacts 0.5～8h arsenate is reduced to arsenite under 15～150 ℃ of temperature and pressure 0.1～10MPa, add sulfuric acid then and transfer to acidity, making arsenite be converted into white arsenic separates out, again solution evaporation is concentrated, filtration, drying, get the white arsenic crude product; Described arsenic-containing waste water is arsenic-containing waste water or the arsenic-containing water solution of arsenic-containing material after acid or alkali or water treatment that discharge in non-ferrous metals smelting works or chemical plant; At least a in the lower aliphatic aldehyde that described water-soluble organic class reductive agent is C1-C4, its halides, the urea; Arsenic content is not less than 1g/L in the described arsenic-containing waste water.
The white arsenic crude product is further purified through heating sublimation or recrystallization.
1～5 times by the required theoretical amount of substance of reaction that arsenate is reduced to arsenite adds water the organic class reductive agent of dissolubility.
The described sulfuric acid that adds transfers to acidity, and pH is not higher than 4.
The concrete implementation process of the present invention is:
1, be raw material with arsenic-containing water solution, 1～5 times by the required theoretical amount of substance of reaction that arsenate is reduced to arsenite adds water the organic class reductive agent of dissolubility, as lower aliphatic aldehyde, urea, under 15～150 ℃ and pressure 0.1～10MPa, react 0.5～8h arsenate is reduced to arsenite, add sulfuric acid then and regulate pH to 0～4.
2, with gained solution evaporation condensing crystal, filtration, drying, again gained white arsenic heating sublimation is purified, can obtain purity and be the white arsenic product more than 99%.
In the reaction, organic class reductive agent is oxidized to lower fatty acid or carbonate or nitrogen, and after the adding acid, carbonate and acid-respons generate harmless carbonic acid gas.Be example with formaldehyde, reaction formula is as follows:
2AsO
4 3-+4H
++HCHO→2AsO
2 -+CO
2↑+3H
2O
Filtrate filtered is returned Recycling Mother Solution or otherwise processed according to circumstances.
The white arsenic that the present invention utilizes the arsenic-containing waste water preparation to have important use makes arsenic obtain reclaiming and utilization, with present SO
2Reduction method is compared, and remarkable advantage is that flow process is simple, has reduced equipment requirements and facility investment, and liquid phase homogeneous reaction efficient is higher, and omnidistance no obnoxious flavour produces simple and safe operation.
The present invention can effectively control arsenic contamination and the containment discharging of arsenic in environment, makes to contain arsenic waste solution or waste residue obtains comprehensive utilization of resources, has remarkable economic efficiency and environmental benefit.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
Get the aqueous solution 200ml of certain high arsenic flue dust after acidleach has also been reclaimed valuable metal of arsenic content 23.2g/L, by formaldehyde: the ratio of the amount of substance of arsenic is 3: 2, in arsenic-containing water solution, add the formalin that 7.52g contains formaldehyde 37%, under the normal temperature and pressure, stirring reaction 1.5 hours with gained arsenic chloride solution evaporation concentration, crystallization, filtration, drying, obtains the 5.75g white arsenic again, white arsenic purity is 91.5% in the product, and the rate of recovery reaches 86.32%.The white arsenic heating sublimation is purified again, obtain the 5.16g white arsenic, product purity reaches 99.1%.Filtrate is returned Recycling Mother Solution and is used.
Embodiment 2:
Get 1m
3Arsenic content is the alkaline waste liquor (pH is about 9) of 6.2g/L, and by urea: the ratio of the amount of substance of arsenic is 12: 1, adds 6.0kg urea in arsenic containing solution, and under 55 ℃, normal pressure, stirring reaction 2 hours adds the 15kg vitriol oil again and regulates dissolving pH to 2.5.With gained arsenic chloride solution evaporating, concentrating and crystallizing, filtration, drying, obtain the 7.72kg white arsenic again, white arsenic purity is 94.5% in the product, and the rate of recovery is 89.9%.The white arsenic heating sublimation is purified again, obtain the 7.19kg white arsenic, product purity reaches 99.4%.Filtrate is harmless treatment separately.
Embodiment 3:
Get the neutral arsenate aqueous solution 200ml of arsenic content 23.0g/L, by formaldehyde: the ratio of the amount of substance of arsenic is 2: 1, add the formalin that 10g contains formaldehyde 37% in the arsenic-containing water solution, under 120 ℃, 0.15MPa pressure, stirring reaction 0.5 hour, adding sulfuric acid adjustment system pH again is 1.5, with gained arsenic chloride solution evaporation concentration to 40ml, the crystallization filtration, the drying that obtain, crude product 6.5g, wherein white arsenic purity is 90.3%, and the rate of recovery reaches 97.5%.Thick white arsenic heating sublimation is purified again, obtain the 5.9g white arsenic, product purity reaches 99.5%.
Embodiment 4:
Get acidity (pH is 2.0) the arsenate aqueous solution 1000ml that contains arsenic 45g/L, press 1,2-dichloro propionic aldehyde: the ratio of the amount of substance of arsenic is 1.2: 1, adds 91.4g1 in arsenic-containing water solution, 2-dichloro propionic aldehyde, under 20 ℃, normal pressure, stirring reaction 4.5 hours, again with gained arsenic chloride solution evaporation concentration to 400ml, the crystallization filtration, the drying that obtain, crude product 6.5g, wherein white arsenic purity is 63.9%, the rate of recovery reaches 92.5%.Thick white arsenic heating sublimation is purified again, obtain the 55.5g white arsenic, product purity reaches 99.0%.
Claims (2)
1. method of utilizing arsenic-containing waste water to prepare white arsenic, be raw material with the arsenic-containing waste water, adding water the organic class reductive agent of dissolubility reacts 0.5～8h arsenate is reduced to arsenite under 15～150 ℃ of temperature and pressure 0.1～10MPa, add sulfuric acid then and transfer to acidity, making arsenite be converted into white arsenic separates out, again solution evaporation is concentrated, filtration, drying, get the white arsenic crude product; Described arsenic-containing waste water is arsenic-containing waste water or the arsenic-containing water solution of arsenic-containing material after acid or alkali or water treatment that discharge in non-ferrous metals smelting works or chemical plant; At least a in the lower aliphatic aldehyde that described water-soluble organic class reductive agent is C1-C4, its halides, the urea; Arsenic content is not less than 1g/L in the described arsenic-containing waste water; 1～5 times by the required theoretical amount of substance of reaction that arsenate is reduced to arsenite adds water the organic class reductive agent of dissolubility; The described sulfuric acid that adds transfers to acidity, and pH is not higher than 4.
2. method according to claim 1 is characterized in that: the white arsenic crude product is further purified through heating sublimation or recrystallization.
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| CN107012340B (en) * | 2017-03-30 | 2018-10-12 | 郴州金山冶金化工有限公司 | A kind of technique that Whote-wet method extracts arsenic from arsenones waste residue |
| CN111377478A (en) * | 2018-12-29 | 2020-07-07 | 东泰高科装备科技有限公司 | Purification method of arsenic trioxide |
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| JPS4943892A (en) * | 1972-08-31 | 1974-04-25 | ||
| JPS60125292A (en) * | 1983-12-12 | 1985-07-04 | Mitsubishi Monsanto Chem Co | Treatment of arsenic-containing waste water |
| JPH0943892A (en) * | 1995-08-03 | 1997-02-14 | Minolta Co Ltd | Electrostatic latent image developer |
| US6254312B1 (en) * | 1998-06-18 | 2001-07-03 | Rmt, Inc. | Stabilization of arsenic-contaminated materials |
| CN100572286C (en) * | 2007-09-07 | 2009-12-23 | 中南大学 | Utilize arsenic-containing waste water to prepare the method for white arsenic |
| CN101168450B (en) * | 2007-09-27 | 2010-09-01 | 中国黄金集团公司技术中心 | Method for separating and reclaiming arsenic and iron from acidic waste liquid containing arsenic acid and ferric sulfate |
| RU2371391C1 (en) * | 2008-05-15 | 2009-10-27 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии (ФГУП "ГосНИИОХТ") | Method of obtaining elementary arsenic from aqueous and aqueous-organic solutions of arsenic-containing compounds |
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