CN105753218B - A method of removal trivalent arsenic - Google Patents
A method of removal trivalent arsenic Download PDFInfo
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- CN105753218B CN105753218B CN201610228348.5A CN201610228348A CN105753218B CN 105753218 B CN105753218 B CN 105753218B CN 201610228348 A CN201610228348 A CN 201610228348A CN 105753218 B CN105753218 B CN 105753218B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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Abstract
The present invention provides a kind of methods of removal trivalent arsenic, and described method includes following steps：(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9 1.5 using ozone, obtains the solution containing pentavalent arsenic；(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, ferrous iron is oxidized to ferric iron under conditions of temperature is 70 DEG C or more, pH value is less than 1.5, pentavalent arsenic is reacted with ferric iron, is obtained containing scorodite crystalline deposit, goethite precipitation and ferrous solution；(3) pH value of regulating step (2) acquired solution makes ferrous oxidising in solution and forms ferric hydroxide colloid, is separated by solid-liquid separation, is purified solution.The method can thoroughly remove the low-concentration arsenic in waste water, and arsenic content is less than 0.05mg/L in purified solution, and the precipitation generated in arsenic removal process easily removes, easy to operate, can be widely applied to purify the waste water containing low-concentration arsenic.
Description
Technical field
The invention belongs to pollutant process technical fields, are related to a kind of method removing trivalent arsenic more particularly to a kind of profit
The method for removing trivalent arsenic in solution with ozone.
Background technology
Arsenic is a kind of hypertoxic element, and a small amount of intake can cause death, arsenicalism that can cause a variety of diseases such as cancer
Disease.On the other hand, it, than more rich element, is the highest 20 kinds of members of abundance in the earth's crust that arsenic, which is one kind reserves in nature,
One of element, arsenic-containing ores are up to more than 200 kind.Mine development and weathering can result in the dissolving of arsenic-containing ores, and generation contains
Arsenic waste water, caused by large area arsenic pollution.Such usual arsenic concentration of arsenic-containing waste water is not very high, at tens milligrams per liter to several
Between gram per liter, but arsenic mainly exists in the form of the trivalent arsenic of severe toxicity, and pH is relatively low, has stronger acidity, to environmental hazard
It is larger.
The toxicity of trivalent arsenic is significantly larger than pentavalent arsenic, and the mobility of trivalent arsenic is not easy to be adsorbed also above pentavalent arsenic
Precipitation, therefore be typically necessary before heavy arsenic and the trivalent arsenic in solution is oxidized to pentavalent.
Lime precipitation was once the most widely used waste water dearsenicating method.Lime is added into arsenic-containing waste water to be carried
The pH value of high waste water, under the conditions of higher pH, the trivalent arsenic in waste water can oxidation by air be rapidly toxicity lower five
Valence arsenic, and arsenic acid calcium precipitate is formed with calcium ion, achieve the effect that arsenic removal.Since processing cost is low, simple to operate, lime
The precipitation method were once commonly used, but there are some apparent defects for the method.Firstly, since calcium arsenate solubility itself compares
Height causes the waste water arsenic content after arsenic removal still higher, cannot be satisfied existing discharge standard；Secondly, the arsenic acid in sediment
Calcium can generate calcium carbonate, while releasing arsenic again, lead to secondary pollution with the carbon dioxide slow reaction in air.
The oxidation of trivalent arsenic generally will be according to arsenic removal mode and requirement, determine using which kind of mode of oxidizing and oxidation medicine
Agent.The oxidant of currently used trivalent arsenic has air, hydrogen peroxide, ozone, chlorate, potassium permanganate and Mn oxide etc..But
It is when adding by the way of Solid-state Chemistry medicament, oxidation trivalent arsenic always brings new foreign ion into, results even in new
Pollution, limits its use scope.
Ozone is one of known strongest oxidant, is much better than pure oxygen and air to the oxidability of arsenic.Ozone oxidation
Trivalent arsenic does not need the booster action of other chemical substances, is swift in response, and no coupling product generates after reaction, and ozone can be straight
It connects and is made by raw material of air using ozone generator, do not need special warehousing and transportation facilities, it is very easy to use.
The chemical equation that ozone aoxidizes trivalent arsenic in acid condition is as follows：
H3AsO3+O3→H3AsO4+O2
Numerous studies show that the arsenic in solution can be by iron hydroxide adsorption precipitation.Using ferric iron adsorption coprecipitation method
When heavy arsenic, as long as iron arsenic than sufficiently high, can make heavy arsenic slag keep stablizing, ensure to be unlikely to cause arsenic in long term storage again
Secondary release.The method has obtained the approval of most countries environmental protection administration, becomes dearsenicating method more better than lime precipitation.Five
Valence arsenic is easier to be adsorbed than trivalent arsenic, and when carrying out adsorption precipitation, the trivalent arsenic in solution is oxidized to pentavalent by needs in advance.
Since oxidation rate is very slow at low ph conditions for trivalent arsenic, is usually required when carrying out adsorption coprecipitation first plus lime improves pH,
And carrying out air agitation makes trivalent arsenic aoxidize, and suitably heating makes ferric iron hydrolysis generate precipitation.But due in high pH conditions
Lower ferric iron hydrolyzes to form colloid, precipitates filtration difficulty, and water content is high in slag, and storage difficulty is also bigger.Scorodite is that have two
The ferric arsenate of a crystallization water, research shows that its solubility is very low, and chemical property is stablized, and is a kind of more satisfactory solid arsenic
Close object.Compared with ferric iron adsorption precipitation, scorodite precipitation method has the advantages that more：It is to be precipitated as crystalline state first, was easy
Filter；Followed by precipitation arsenic content is high, and the arsenic that sinks is efficient；Simultaneously because precipitated product water content is few, handled convenient for later stage stockpiling.But
Be trivalent arsenic in acid condition in water be oxidized to pentavalent arsenic speed it is very slow therefore smelly in existing industrial process
Green onion stone can only be produced by pressure oxidation method, and equipment investment is high, and production difficulty is big, and Gordon M.Ritcey. are in article
Scorodite is mentioned in (Tailings management in gold plants.Hydrometallurgy, 2005,78,3-20)
Gu arsenic method is only applied in a small number of gold smelting enterprises using pressure leaching process route.Canadian McGill universities
G.P.Demopoulos et al. is in article (The atmospheric scorodite process.COPPER2003-
COBRE2003, Sandiago, Chile, Vol, 4, Hydrometallurgy of Copper (Book 2), 597-616) in carry
The method that arsenic is transformed into scorodite under normal pressure is gone out, to air is passed through in the mixed solution of ferrous iron and pentavalent arsenic, has protected
PH value of solution is held when 1.0 or so, reaction temperature is at 95 DEG C, addition crystal seed can generate scorodite under normal pressure, but the method
It is required that the arsenic concentration in solution is higher, usually to reach 10g/L or more, and part arsenic can only be converted to scorodite, once
Heavy arsenic rate is relatively low, and process object is usually the High Concentration of Arsenic solution by concentrating and pre-oxidation is pentavalent, is not suitable for directly locating
Manage low concentration arsenic-containing waste water.
Invention content
It is described in view of the deficiencies of the prior art, the present invention intends to provide a kind of method of removal trivalent arsenic
Method can thoroughly remove the low-concentration arsenic in waste water, and arsenic content is less than 0.05mg/L in purified solution, is produced in arsenic removal process
Raw precipitation easily removes, easy to operate, can be widely applied to purify the waste water containing low-concentration arsenic.
For this purpose, the present invention uses following technical scheme：
Ferrous iron of the present invention refers to ferrous ion, and the ferric iron refers to ferric ion.The trivalent arsenic
Refer to trivalent arsenic ion, the pentavalent arsenic refers to pentavalent arsenic ion.
A method of removal trivalent arsenic, described method includes following steps：
(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9-1.5 using ozone, obtained
To the solution containing pentavalent arsenic；
(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, in temperature is 70 DEG C or more, pH by ferrous iron
Value is oxidized to ferric iron under conditions of being less than 1.5, and pentavalent arsenic is reacted with ferric iron, is obtained containing scorodite crystalline deposit, needle iron
Mine precipitates and ferrous solution；
(3) pH value of regulating step (2) acquired solution makes ferrous oxidising in solution and forms ferric hydroxide colloid,
It is separated by solid-liquid separation, is purified solution.
Trivalent arsenic in arsenic containing solution is oxidized to pentavalent by step (1) ozone under conditions of pH value is 0.9-1.5
Trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic by arsenic such as under conditions of pH value is 1.0,1.1,1.2,1.3 or 1.4.
The method of removal trivalent arsenic provided by the invention, pentavalent is oxidized to using ozone by trivalent arsenic in acid condition
Arsenic avoids the formation of colloid in trivalent arsenic oxidation process；Divalent is added in the arsenic2 solution of packet generated after to oxidation
Iron, and blowing air makes ferrous iron slowly be oxidized to ferric iron in a heated condition, generates ferric arsenate and goethite crystallization, removes
Most of arsenic, wherein ferrous iron, which is added, can avoid generating unformed precipitated ferric arsenate and ferric hydroxide gel, facilitate the later stage
Precipitation can completely remove；Then add alkali neutralization under the conditions of blowing air, remaining iron in solution is made to generate ferric hydroxide colloid, it will
Remaining arsenic adsorption coprecipitation；Due to thering is the support of ferric arsenate and goethite crystallization, the sediment of formation to be easy to be separated by filtration, from
And obtain the solution after deep purifying.
The content of arsenic is preferably 100mg/L-10g/L in step (1) described arsenic containing solution, as 150mg/L, 200mg/L,
300mg/L, 400mg/L, 500mg/L, 600mg/L, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 8g/L or 9g/L etc..Institute
The method of stating is particularly suitable for low concentration arsenic containing solution.Dope containing arsenic under this concentration is reacted with ferric iron can obtain containing smelly green onion
The solution of stone crystalline deposit, goethite precipitation.
Step (1) described arsenic containing solution is：What natural sewage containing arsenic, the mining of weathering generation generated contains arsenic acid
Property draining or metal smelt generate waste water containing arsenic in any one or at least two combination.It is typical but non-limiting
The arsenic-containing acid that generates of combination natural sewage containing arsenic and mining that such as weathering generates drain, what weathering generated
The waste water containing arsenic that naturally sewage containing arsenic is generated with metal smelt, natural sewage containing arsenic, the mining that weathering generates
The waste water containing arsenic that the arsenic-containing acid draining of generation is generated with metal smelt.The arsenic containing solution can also be other chemical processes
The arsenic-containing waste water of generation.
Preferably, the metal smelt is the smelting of copper, nickel, lead, zinc, gold or silver.
A concentration of 20-150mg/L of step (1) the described ozone in arsenic containing solution, as 30mg/L, 40mg/L, 50mg/L,
60mg/L, 80mg/L, 100mg/L, 120mg/L, 130mg/L or 145mg/L etc..
Preferably, step (1) ozone is made using air and/or air as raw material by ozone generator.
Preferably, the oxidation of step (1) described trivalent arsenic carries out under agitation.
Step (2) the soluble divalent source of iron is ferrous sulfate and/or frerrous chloride, the ferrous sulfate and protochloride
Iron contains or not contain the crystallization water and can be used.Other solubility divalent sources of iron can also use herein, as long as can be in solution
Middle generation ferrous ion.
Step (2) oxidation carries out under conditions of temperature is 70 DEG C or more, pH value is less than 1.5, is such as 75 in temperature
DEG C, 80 DEG C, 85 DEG C, 90 DEG C or 95 DEG C etc., carried out under conditions of pH value 1.3,1.2,1.0,0.9,0.8 or 0.2 etc..
Preferably, described be oxidized to of step (2) is passed through air oxidation.Other oxidable ferrous methods can also make herein
With, since ferrous iron is easily oxidized to ferric iron in air, often select air oxidation.
The ratio between mole of step (2) ferric iron and pentavalent arsenic is (3-15):1, such as 3.5:1、4:1、5:1、6:1、
7:1、8:1、10:1、12:1、13:1 or 14:1 etc..The ferric addition should be excessive so that ferric iron is anti-with pentavalent arsenic
Scorodite precipitation should not only be formed, moreover it is possible to form part goethite precipitation.
The temperature of step (2) described reaction be 70 DEG C or more, as reaction temperature be 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C,
85 DEG C, 88 DEG C, 90 DEG C, 92 DEG C or 95 DEG C etc..
Preferably, in step (2) described reaction process the pH value of solution be 1.5 hereinafter, as the pH value of solution is 1.3,
1.2,1.0,0.9,0.8,0.5 or 0.2 etc..
Preferably, the time of step (2) described reaction be 1-3h, as 1.2h, 1.3h, 1.5h, 1.8h, 2.0h, 2.2h,
2.5h or 2.8h etc..
The soluble divalent source of iron being added in step (2) is excessive, ferrous iron has been there remains in final solution, and can not
What is avoided contains a small amount of ferric iron.
Step (2) uses the pH value of sulfuric acid, hydrochloric acid, calcium hydroxide or sodium hydrate regulator solution, to ensure the pH of solution
Value is for 1.5 hereinafter, first can be reused alkali using acid or first be reused acid using alkali and adjust the pH value of solution.
Using reaction temperature as described above, pH value in reaction and reaction time, ferric iron and pentavalent arsenic are helped to ensure that
Reaction generates scorodite and goethite precipitation.
Step (3) adjusts the pH value of solution to 5.5 or more, such as 5.8,6.0,6.2,6.5,7,7.5,8,8.5,9,10,11,
12,13 or 14 etc..The pH value for adjusting solution is 5.5 or more, and the ferric iron helped to make in solution generates ferric hydroxide colloid, into
And pentavalent arsenic in adsorbent solution or other precipitations, the arsenic in further purified solution.
Preferably, described be oxidized to of step (3) is passed through air oxidation.
Described method includes following steps as a preferred technical solution,：
(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9-1.5 using ozone,
In, in the arsenic containing solution content of arsenic be 100mg/L-10g/L, a concentration of 20-150mg/L of the ozone in arsenic containing solution,
Obtain the solution containing pentavalent arsenic；
(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, keeps solution ph 1.5 hereinafter, temperature
Be 70 DEG C or more, be passed through into solution air by it is ferrous oxidising be ferric iron so that the mole of ferric iron and pentavalent arsenic it
Than for 3-15, pentavalent arsenic reacts 1-3h with ferric iron under conditions of 70 DEG C or more, pH value are less than 1.5, obtains containing scorodite
Crystalline deposit, goethite precipitation and ferrous solution；
(3) pH value of regulating step (2) acquired solution is 5.5 or more, makes ferrous oxidising in solution and forms hydrogen-oxygen
Change iron colloid, is separated by solid-liquid separation, is purified solution.
Compared with prior art, beneficial effects of the present invention are：
The method of removal trivalent arsenic provided by the invention is using ozone in acid condition directly by the trivalent arsenic in solution
It is oxidized to pentavalent arsenic, avoids improving pH in initial reaction stage, the iron in sewage is caused to form the iron hydroxide glue for being difficult to be separated by filtration
Body；And other ions will not be brought into as oxidant using ozone, cause waste component to complicate；
The method of removal trivalent arsenic provided by the invention disposably adds ferrous iron and under heating conditions blowing air oxygen
Change, most arsenic can be made to be converted into scorodite crystallization, and excessive iron can also form a part of goethite crystallization, both
The stability for improving solid product also improves the strainability of product；
The method of removal trivalent arsenic provided by the invention generates ferric hydroxide colloid at a high ph, utilizes ferric hydroxide colloid
Strong suction-operated by the thorough removing of the remaining arsenic in water, solution arsenic concentration is less than 0.05mg/L after arsenic removal, since early period is heavy
Shallow lake product is the scorodite and goethite of crystalline state, therefore the water content of precipitated product is relatively low, and strainability is good.
Description of the drawings
Fig. 1 is the process flow chart for the removal trivalent arsenic that one embodiment of the present invention provides.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
A method of removal trivalent arsenic, the method is as shown in Figure 1, include the following steps：
(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9-1.5 using ozone, obtained
To the solution containing pentavalent arsenic；
(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, by ferrous iron solution ph be 1.5 with
Under, temperature be 70 DEG C or more be oxidized to ferric iron, pentavalent arsenic is reacted with ferric iron, is obtained containing scorodite crystalline deposit, needle iron
Mine precipitates and ferrous solution；
(3) pH value of regulating step (2) acquired solution is to 5.5 or more, makes ferrous oxidising in solution and forms hydrogen-oxygen
Change iron colloid, is separated by solid-liquid separation, is purified solution.
Embodiment 1
A method of trivalent arsenic during removal simulation mine is drained containing arsenic, simulation mine draining containing arsenic is by by arsenous
Sour sodium (Na3AsO3) and ferric sulfate (Fe2(SO4)3) be dissolved in water and be formulated, wherein trivalent arsenic concentration 300mg/L, concentration of iron are
1g/L, described method includes following steps：
(1) it takes 1000 milliliters of simulation mines to be drained containing arsenic, is to be passed through to be occurred by ozone at 1.0,20 DEG C with sulphur acid for adjusting pH
(the concentration about 40mg/L) containing ozone gas that device generates, and be stirred, after ventilating 10-40 minutes, obtain arsenic2 molten
Liquid；
(2) 5g ferrous sulfate heptahydrates (FeSO is added into the solution containing pentavalent arsenic4·7H2O), heat up after stirring and dissolving
To 70 DEG C and blowing air reaction, addition sulfuric acid and sodium hydroxide control pH between 0.9-1.5 in reaction process, react 3 hours
Afterwards, it obtains containing scorodite crystalline deposit, goethite precipitation and ferrous solution；
(3) sodium hydroxide is added in the solution obtained to step (2) and improves its pH value to 5.5 or more, continue to be passed through air
And be stirred to react 1 hour, it is separated by filtration after being cooled to 20 DEG C, is purified solution.Arsenic concentration is 0 in purified solution.
Embodiment 2
A method of trivalent arsenic in removal arsenic gold concentrate Bioleaching waste liquid, the arsenic-containing gold concentrate Bioleaching waste liquid
In 2.8g/L containing arsenic, iron 3.6g/L, initial pH are 2.2, and described method includes following steps：
(1) 1000 milliliters of arsenic-containing gold concentrate Bioleaching waste liquids are taken, are to be passed through by smelly at 1.3,25 DEG C with sulphur acid for adjusting pH
(the concentration about 40mg/L) containing ozone gas that Oxygen Generator generates, and be stirred, after ventilating 10-40 minutes, obtain containing five
The solution of valence arsenic；
(2) 10g ferrous sulfate heptahydrates (FeSO is added into the solution containing pentavalent arsenic4·7H2O), heat up after stirring and dissolving
To 70 DEG C and blowing air reaction, addition sulfuric acid and sodium hydroxide control pH between 0.9-1.5 in reaction process, react 3 hours
Afterwards, it obtains containing scorodite crystalline deposit, goethite precipitation and ferrous solution；
(3) sodium hydroxide is added in the solution obtained to step (2), improves its pH to 5.5 or more, continues to be passed through air simultaneously
It is stirred to react 1 hour, is separated by filtration after being cooled to 20 DEG C, is purified solution.Arsenic concentration is 0.03mg/L in purified solution.
Embodiment 3
A method of trivalent arsenic in the arsenic-containing waste water that removal zinc abstraction generates, wherein the arsenic-containing waste water that zinc abstraction generates
0.5g/L containing arsenic, iron 1.0g/L, initial pH are 2.2.
(1) arsenic-containing waste water for taking 1000 milliliters of zinc abstractions to generate is to be passed through by ozone at 1.3,15 DEG C with sulphur acid for adjusting pH
(the concentration about 40mg/L) containing ozone gas that generator generates, and be stirred, after ventilating 10-40 minutes, obtain containing pentavalent
The solution of arsenic；
(2) 5g ferrous sulfate heptahydrates (FeSO is added into the solution containing pentavalent arsenic4·7H2O), heat up after stirring and dissolving
To 70 DEG C and blowing air reaction, addition sulfuric acid and sodium hydroxide control pH between 0.9-1.5 in reaction process, react 3 hours
Afterwards, it obtains containing scorodite crystalline deposit, goethite precipitation and ferrous solution；
(3) sodium hydroxide is added in the solution obtained to step (2), improves its pH to 5.5 or more, continues to be passed through air simultaneously
It is stirred to react 1 hour, is separated by filtration after being cooled to 20 DEG C, is purified solution.Arsenic concentration is 0.02mg/L in purified solution.
Embodiment 4
A kind of method of trivalent arsenic in removal arsenic-containing waste water, wherein 100mg/L containing arsenic in arsenic-containing waste water, iron 200mg/L,
Initial pH is 2.0.
(1) 1000 milliliters of arsenic-containing waste waters are taken, are to be passed through to be generated by ozone generator at 0.9,15 DEG C with sulphur acid for adjusting pH
It containing ozone gas (concentration about 20mg/L), and is stirred, after ventilating 50 minutes, obtains the solution containing pentavalent arsenic；
(2) 5g ferrous sulfate heptahydrates (FeSO is added into the solution containing pentavalent arsenic4·7H2O), heat up after stirring and dissolving
To 80 DEG C and blowing air reaction, addition sulfuric acid and sodium hydroxide control pH between 0.7-1.2 in reaction process, react 1 hour
Afterwards, it obtains containing scorodite crystalline deposit, goethite precipitation and ferrous solution；
(3) sodium hydroxide is added in the solution obtained to step (2), improves its pH to 6-7, continue to be passed through air and stir
Reaction 1 hour, is separated by filtration after being cooled to 20 DEG C, is purified solution.Arsenic concentration is 0.01mg/L in purified solution.
Embodiment 5
A kind of method of trivalent arsenic in removal arsenic-containing waste water, wherein 10g/L containing arsenic in arsenic-containing waste water, iron 5g/L, initial pH
It is 2.0.
(1) 1000 milliliters of arsenic-containing waste waters are taken, are to be passed through to be generated by ozone generator at 1.5,15 DEG C with sulphur acid for adjusting pH
It containing ozone gas (concentration about 150mg/L), and is stirred, ventilation after forty minutes, obtains the solution containing pentavalent arsenic；
(2) 40g frerrous chlorides (FeCl is added into the solution containing pentavalent arsenic2), 90 DEG C are warming up to simultaneously after stirring and dissolving
Blowing air reacts, and addition hydrochloric acid and sodium hydroxide control pH between 0.7-1.3 in reaction process, after reacting 2 hours, are contained
There are scorodite crystalline deposit, goethite precipitation and ferrous solution；
(3) sodium hydroxide is added in the solution obtained to step (2), improves its pH to 7-7.5, continue to be passed through air and stir
Reaction 1 hour is mixed, is separated by filtration after being cooled to 20 DEG C, is purified solution.Arsenic concentration is 0.05mg/L in purified solution.
Comparative example 1
After being 2-3 with the pH of sulfuric acid regulation solution in step (1), then it is passed through ozone and trivalent arsenic is oxidized to pentavalent arsenic
Outside, remaining is same as Example 2.Arsenic concentration is 8.6mg/L in purified solution.
Comparative example 2
Except the reaction in step (2) 65 DEG C, pH value be 2-3 under conditions of carry out, remaining is same as Example 2.Purification
Arsenic concentration is 0.07mg/L in solution, and filtering is slow, and the sticky water content of filter residue is high.
Applicant states, the foregoing is merely the specific implementation mode of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can be readily occurred in are all fallen within protection scope of the present invention and the open scope.
Claims (17)
1. a kind of method of removal trivalent arsenic, which is characterized in that described method includes following steps：
(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9-1.5 using ozone, is contained
There is the solution of pentavalent arsenic；
(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, by ferrous iron temperature be 70 DEG C or more, pH value it is small
Ferric iron is oxidized under conditions of 1.5, pentavalent arsenic is reacted with ferric iron, and it is heavy containing scorodite crystalline deposit, goethite to obtain
It forms sediment and ferrous solution；
(3) pH value of regulating step (2) acquired solution makes ferrous oxidising in solution and forms ferric hydroxide colloid, solid-liquid
Separation, is purified solution.
2. according to the method described in claim 1, it is characterized in that, the content of arsenic is in step (1) described arsenic containing solution
100mg/L-10g/L。
3. according to the method described in claim 1, it is characterized in that, step (1) described arsenic containing solution is：What weathering generated
It is any one in the waste water containing arsenic that the arsenic-containing acid draining or metal smelt that naturally sewage containing arsenic, mining generate generate
Kind or at least two combination.
4. according to the method described in claim 3, it is characterized in that, the metal smelt is the smelting of copper, nickel, lead, zinc, gold or silver
Refining.
5. according to the method described in claim 1, it is characterized in that, step (1) described ozone is a concentration of in arsenic containing solution
20-150mg/L。
6. according to the method described in claim 1, it is characterized in that, step (1) described ozone by ozone generator with air
And/or air is made for raw material.
7. according to the method described in claim 1, it is characterized in that, the oxidation of step (1) described trivalent arsenic under agitation
It carries out.
8. according to the method described in claim 1, it is characterized in that, step (2) the soluble divalent source of iron is ferrous sulfate
And/or frerrous chloride.
9. according to the method described in claim 1, it is characterized in that, described be oxidized to of step (2) is passed through air oxidation.
10. according to the method described in claim 1, it is characterized in that, the mole of step (2) ferric iron and pentavalent arsenic it
Than for 3-15.
11. according to the method described in claim 1, it is characterized in that, the temperature of step (2) described reaction is 70 DEG C or more.
12. according to the method described in claim 1, it is characterized in that, the pH value of solution is in step (2) described reaction process
1.5 following.
13. according to the method described in claim 1, it is characterized in that, the time of step (2) described reaction is 1-3h.
14. according to the method described in claim 1, it is characterized in that, step (2) uses sulfuric acid, hydrochloric acid, calcium hydroxide or hydrogen-oxygen
Change the pH value that sodium adjusts solution.
15. according to the method described in claim 1, it is characterized in that, step (3) adjusts the pH value of solution to 5.5 or more.
16. according to the method described in claim 1, it is characterized in that, described be oxidized to of step (3) is passed through air oxidation.
17. method according to claim 1, which is characterized in that described method includes following steps：
(1) trivalent arsenic in arsenic containing solution is oxidized to pentavalent arsenic under conditions of pH value is 0.9-1.5 using ozone, wherein
The content of arsenic is 100mg/L-10g/L in the arsenic containing solution, and a concentration of 20-150mg/L of the ozone in arsenic containing solution is obtained
Solution containing pentavalent arsenic；
(2) soluble divalent source of iron is added into the solution containing pentavalent arsenic, keeps solution ph 1.5 hereinafter, temperature is 70
DEG C or more, be passed through into solution air by it is ferrous oxidising be ferric iron so that the ratio between the mole of ferric iron and pentavalent arsenic is
3-15, pentavalent arsenic react 1-3h under conditions of 70 DEG C or more, pH value are less than 1.5 with ferric iron, obtain crystallizing containing scorodite
Precipitation, goethite precipitation and ferrous solution；
(3) pH value of regulating step (2) acquired solution is 5.5 or more, makes ferrous oxidising in solution and forms iron hydroxide
Colloid is separated by solid-liquid separation, is purified solution.
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| CN116443943A (en) * | 2023-04-27 | 2023-07-18 | 江西铜业技术研究院有限公司 | Method for preparing high-stability scorodite seed crystal |
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