CN109607886A - The method for innocent treatment of arsenic in a kind of arsenic-containing waste water - Google Patents
The method for innocent treatment of arsenic in a kind of arsenic-containing waste water Download PDFInfo
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- CN109607886A CN109607886A CN201910122709.1A CN201910122709A CN109607886A CN 109607886 A CN109607886 A CN 109607886A CN 201910122709 A CN201910122709 A CN 201910122709A CN 109607886 A CN109607886 A CN 109607886A
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention belongs to environment protection field, it is related to a kind of method for innocent treatment of arsenic in arsenic-containing waste water, described method includes following steps: adding ferrous salt in arsenic-containing waste water after adjusting the pH to 2-7 of arsenic-containing waste water using pH adjusting agent, obtains premixed liquid；Oxidant is added into gained premixed liquid, and maintaining the pH of premixed liquid by addition pH adjusting agent is 2-7, obtains mixed liquor；Gained mixed liquor is stirred, arsenic slag is obtained after separation of solid and liquid and arsenic removal produces water；Mixing gained arsenic slag and inorganic sol, excessive moisture is separated by solid-liquid separation after stirring, filter residue obtains stablizing solid waste after drying, the additional amount of this method iron is few, Leaching is down to 0.2mg/L after treatment for gained arsenic slag, and arsenic-containing waste water gained arsenic removal after treatment produces the concentration of arsenic in water down to 0.2mg/L.
Description
Technical field
The invention belongs to environment protection field, it is related to arsenic in the processing method more particularly to a kind of arsenic-containing waste water of a kind of waste water
Method for innocent treatment.
Background technique
Arsenic is a kind of extremely toxic substance, has very strong carcinogenicity.Having in mining and metallurgy production process and chemical production process can
Arsenic-containing waste water can be generated, if direct emission necessarily will cause serious environmental pollution.Therefore, it is necessary to be carried out to arsenic-containing waste water
Processing removes arsenic therein, and carries out harmlessness disposing, and for protecting, the ecological environment in China, promoting sustainable development has for this
Significance.
Molysite deposition method is a kind of more common method of current processing arsenic-containing waste water, and the arsenic in solution is synthesized scorodite
It is considered as a kind of matter containing arsenic the most stable.But synthesis scorodite usually requires to carry out at high temperature under high pressure, is processed into
This is high.Although at present can be under normal pressure lower than the acquisition preferable scorodite of crystallinity, the party under the conditions of the temperature of water boiling point
Method requires arsenic concentration (20-50g/L) with higher in waste water and synthesizes under the conditions of lower pH (0.3-1.0), in reality
With regard to needing to be handled again after arsenic-containing waste water is concentrated in production process, the industrial value of this method is reduced.In addition,
It is carried out under the conditions of lower pH, the removal efficiency of arsenic is usually less than 90%, and the removing of arsenic is not thorough.Under normal temperature and pressure, after improving pH
Amorphous ferric arsenate can be obtained, the removal efficiency of arsenic is higher, but the stability of this substance is poor.In order to improve its stabilization
Property, it needs to improve the molar ratio of initial Fe/As in solution, when usual molar ratio is greater than 3, can be good at removing in solution
Arsenic, obtained precipitation slag arsenic fixation effect can greatly improve.But the increase of iron arsenic ratio, the quantity of slag that will lead to generation greatly increase,
It is unfavorable for the stockpiling of slag.
The step of CN 105753209A discloses a kind of processing method of arsenic-containing waste water, this method includes: (1) to containing arsenic
Ferrous salt and oxidant are added in waste water, obtains solution A；(2) molysite is added into solution A, controls the pH value in arsenic-containing waste water
For 8-12, B solution is obtained；(3) organic flocculant and inorganic flocculating agent are added into B solution, stirring carries out solid-liquid point after standing
From by slag phase and liquid phase separation.This method precipitates arsenic from arsenic-containing waste water, but introduces excessive molysite, and arsenic slag is not easy
Processing, solid waste are still very high to the pollution of environment.
107162273 A of CN also discloses a kind of processing method of arsenic-containing waste water, and this method is by being 5- in control pH
A large amount of ferrous sulfate heptahydrate and a large amount of hydrogen peroxide are added in 6 arsenic-containing waste water, iron arsenic is adjusting pH than up to 14-25
To stir when 7-9, obtain largely containing arsenic precipitating, the arsenic concentration in solution can reach discharge standard at this time, but this method produces
Raw a large amount of arsenic slag, is unfavorable for the processing of solid waste.
102674526 A of CN discloses a kind of method of steady arsenic of arsenic heavy from arsenic containing solution, and this method utilizes ferrous salt to make
To sink arsenic meter, in high temperature weak acid and blast large quantity of air under the premise of, generates scorodite crystals.But method is needed at 70-95 DEG C
At a temperature of carry out, be unfavorable for energy conservation and environmental protection.
Therefore, it is few that a kind of co-precipitation of iron arsenic at normal temperatures and pressures, the additive amount of iron are developed, and the few side of yield of arsenic slag
Method has great importance to sustainable development.
Summary of the invention
The purpose of the present invention is to provide a kind of method for innocent treatment of arsenic in arsenic-containing waste water, the additional amounts of this method iron
Few, Leaching is low after treatment for gained arsenic slag, and the gained arsenic removal after treatment of aqueous waste water produce arsenic in water concentration it is low.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention provides a kind of method for innocent treatment of arsenic in arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) ferrous salt is added in arsenic-containing waste water after adjusting the pH to 2-7 of arsenic-containing waste water using pH adjusting agent, is premixed
Liquid；
(2) oxidant is added into premixed liquid obtained by step (1), and is by the pH of addition pH adjusting agent maintenance premixed liquid
2-7 obtains mixed liquor；
(3) mixed liquor obtained by whipping step (2) obtains arsenic slag after separation of solid and liquid and arsenic removal produces water；
(4) mixing inorganic sol and step (3) gained arsenic slag, are separated by solid-liquid separation, filter residue is stablized after drying after stirring
Solid waste.
Then the present invention adds oxidation by adding ferrous salt in an acidic solution in the premixed liquid added with ferrous salt
Agent, ferrous salt and arsenic after making oxidation are co-precipitated, and by mixing arsenic slag with inorganic sol, further reduced arsenic slag to environment
Harm.Requirement of the processing method provided by the present invention to process equipment is low, and economic performance is good, and takes off to arsenic in arsenic-containing waste water
Except thorough, since the additive amount of ferrous salt is few, the yield of arsenic slag is few, alleviates the volume of cargo in storage that arsenic slag muck is put, and saves
Space.
Preferably, the concentration of arsenic is 5mg/L or more in step (1) described arsenic-containing waste water, such as can be 5mg/L, 50mg/
L、100mg/L、250mg/L、500mg/L、800mg/L、1000mg/L、1500mg/L、2000mg/L、2500mg/L、3000mg/
L, 5000mg/L, 10000mg/L, 20000mg/L, 30000mg/L, 50000mg/L, 60000mg/L or 80000mg/L, preferably
For 5-1000mg/L.
Preferably, the ferrous salt include ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous phosphate, sulphur hydrogenation it is ferrous,
In iron ammonium sulfate, ferrous acetate, iron iodide or ferrous bromide any one or at least two combination, typical but non-limit
The combination of the combination ferrous sulfate and frerrous chloride of property processed, the combination of frerrous chloride and ferrous nitrate, ferrous nitrate, ferrous phosphate
The ferrous combination with sulphur hydrogenation, iron ammonium sulfate, ferrous acetate, iron iodide, ferrous bromide and frerrous chloride combination or sulphur
Sour ferrous iron, frerrous chloride, ferrous nitrate, ferrous phosphate, sulphur hydrogenation ferrous iron, iron ammonium sulfate, ferrous acetate, iron iodide and bromine
Change ferrous combination.
Preferably, the molar ratio of iron and arsenic in arsenic-containing waste water is (0.5-3) in the ferrous salt: 1, such as can be 0.5:
1,1:1,1.5:1,2:1,2.5:1 or 3:1, preferably (1-2): 1.
Preferably, the pH adjusting agent includes acid or inorganic base.
Preferably, it is described acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid in any one or at least two group
It closes, typical but non-limiting combination includes the combination of sulfuric acid and hydrochloric acid, the combination of hydrochloric acid and phosphoric acid, the combination of acetic acid and nitric acid
The combination of phosphoric acid, sulfuric acid, hydrochloric acid and acetic acid afterwards.
Preferably, the inorganic base includes in sodium hydroxide, calcium oxide, calcium hydroxide, ammonium hydroxide, sodium carbonate or sodium bicarbonate
Any one or at least two combination, it is typical but non-limiting combination include sodium hydroxide and calcium oxide combination, hydrogen
The combination of the combination of sodium oxide molybdena and calcium hydroxide, calcium oxide and ammonium hydroxide, calcium oxide, the combination of ammonium hydroxide and sodium carbonate or hydroxide
The combination of sodium, calcium oxide, ammonium hydroxide and sodium bicarbonate.
Preferably, step (2) described oxidant include ozone, hydrogen peroxide, potassium permanganate, manganese dioxide, bromine water, chlorine,
Any one in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, sodium hypochlorite, sodium chlorate or sodium perchlorate or at least two
Combination, typical but non-limiting combination include the combination of ozone and hydrogen peroxide, the combination of hydrogen peroxide and potassium permanganate, permanganic acid
The combination of potassium, bromine water, chlorine and sodium peroxydisulfate, hydrogen peroxide, titanium dioxides, sodium hypochlorite, sodium chlorate, chlorine and potassium peroxydisulfate
Combination or the combination of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, sodium perchlorate and sodium chlorate.
Preferably, the molar ratio of arsenic is (1-4) in the oxidant and step (1) described arsenic-containing waste water: 1, such as can be with
It is 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1 or 4:1.
Preferably, the time of step (3) described stirring be 1-10h, such as can be 1h, 2h, 3h, 4h, 5h, 6h, 7h,
8h, 9h or 10h, preferably 5-8h.
Preferably, the revolving speed of step (3) described stirring is 100-2000r/min, such as can be 100r/min, 200r/
min、500r/min、800r/min、1000r/min、1100r/min、1200r/min、1300r/min、1400r/min、
1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min or 2000r/min, preferably 1200-
1500r/min。
Preferably, the method for step (3) described separation of solid and liquid includes centrifuge separation, vacuum filter, plate compression or whirlwind
Any one in separation.
Preferably, step (4) inorganic sol includes that preferably magnesium aluminum hydroxide sol solution, silicate sol is molten
Any one in liquid, phosphate sol solution, hydroxide sol solution, montmorillonite sol solution or bentonite sol solution
Or at least two combination, preferably magnesium aluminum hydroxide sol solution.
Preferably, the molar ratio of Mg and Al is (1-2): (2-1) in the magnesium aluminum hydroxide sol solution, such as can be with
It is 1:1,1:2 or 2:1, preferably 1:2.
Preferably, the liquid-solid ratio of step (4) inorganic sol and arsenic slag is 0.1-5, preferably 1-2.
Preferably, the time of step (4) described stirring be 1-12h, such as can be 1h, 2h, 3h, 4h, 5h, 6h, 7h,
8h, 9h, 10h, 11h or 12h, preferably 5-10h.
Preferably, the speed of step (4) described stirring is 100-2000r/min, such as can be 100r/min, 200r/
min、500r/min、800r/min、1000r/min、1100r/min、1200r/min、1300r/min、1400r/min、
1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min or 2000r/min, preferably 1200-
1500r/min。
Preferably, the method for step (4) described separation of solid and liquid includes centrifuge separation, vacuum filter, plate compression or whirlwind
Any one in separation.
The optimal technical scheme of processing method is provided as the present invention, the treating method comprises following steps:
(1) ferrous salt, ferrous salt are added in arsenic-containing waste water after adjusting the pH to 2-7 of arsenic-containing waste water using acid or inorganic base
The molar ratio of arsenic is (0.5-3) in middle iron and arsenic-containing waste water: 1, obtain premixed liquid, in arsenic-containing waste water the concentration of arsenic be 5mg/L with
On；
(2) oxidant is added into premixed liquid obtained by step (1), arsenic in oxidant and step (1) described arsenic-containing waste water
Molar ratio is (1-4): 1, and maintaining the pH of premixed liquid by addition acid or inorganic base is 2-7, obtains mixed liquor；
(3) with mixed liquor 1-10h obtained by the revolving speed whipping step (2) of 100-2000r/min, arsenic slag is obtained after separation of solid and liquid
Water is produced with arsenic removal；
(4) mixing inorganic sol and step (3) gained arsenic slag, with solid-liquid after the revolving speed stirring 1-12h of 100-2000r/min
Separation, filter residue obtain stablizing solid waste after drying.
Compared with the existing technology, the invention has the following advantages:
Then the present invention adds oxidation by adding ferrous salt in an acidic solution in the premixed liquid added with ferrous salt
Agent, ferrous salt and arsenic after making oxidation are co-precipitated, and by mixing arsenic slag with inorganic sol, further reduced arsenic slag to environment
Harm.Requirement of the processing method provided by the present invention to process equipment is low, and economic performance is good, and takes off to arsenic in arsenic-containing waste water
Except thorough, since the additive amount of ferrous salt is few, the yield of arsenic slag is few, alleviates the volume of cargo in storage that arsenic slag muck is put, and saves
Space, and the Leaching of finally obtained stable solid waste, down to 0.2mg/L, arsenic removal after treatment produces the content of arsenic in water
Down to 0.2mg/L.
Detailed description of the invention
Fig. 1 is the process flow chart for the processing method that embodiment 1 provides.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Present embodiments provide a kind of method for innocent treatment of arsenic in arsenic-containing waste water, the process flow of the processing method
Figure is as shown in Figure 1, the treating method comprises following steps:
(1) pH to 4 of arsenic-containing waste water is adjusted using sulfuric acid or sodium hydroxide, and is added in arsenic-containing waste water after adjustment of ph
Ferrous sulfate, the concentration of arsenic is 500mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 1.5 in iron and arsenic-containing waste water in ferrous sulfate:
1, obtain premixed liquid；
(2) hydrogen peroxide is added into premixed liquid obtained by step (1), and premixed liquid is maintained by addition sulfuric acid or sodium hydroxide
PH be 4, the molar ratio of arsenic is 2.5:1 in hydrogen peroxide and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 6h obtained by the revolving speed whipping step (2) of 1300r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) mixing magnalium sodium hydroxide sol solution and step (3) gained arsenic slag, stir 6h with the revolving speed of 1300r/min
After be separated by solid-liquid separation, filter residue obtains stablizing solid waste after drying, the molar ratio of Mg and Al in the magnalium sodium hydroxide sol solution
For 1:2, the liquid-solid ratio of the magnalium sodium hydroxide sol solution and arsenic slag is 1.5.
Embodiment 2
The method for innocent treatment for present embodiments providing arsenic in a kind of arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 3 of arsenic-containing waste water is adjusted using nitric acid or calcium oxide, and adds sulphur in arsenic-containing waste water after adjustment of ph
Sour ferrous, the concentration of arsenic is 1000mg/L in arsenic-containing waste water, and the molar ratio of iron and arsenic in arsenic-containing waste water is 2:1 in ferrous sulfate,
Obtain premixed liquid；
(2) potassium permanganate is added into premixed liquid obtained by step (1), and premixed liquid is maintained by addition hydrochloric acid or sodium carbonate
PH be 3, the molar ratio of arsenic is 3:1 in potassium permanganate and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 5h obtained by the revolving speed whipping step (2) of 1500r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) mixing magnalium sodium hydroxide sol solution and step (3) gained arsenic slag, stir 5h with the revolving speed of 1500r/min
After be separated by solid-liquid separation, filter residue obtains stablizing solid waste after drying, the molar ratio of Mg and Al in the magnalium potassium hydroxide sol solution
For 1:1, the liquid-solid ratio of the magnalium potassium hydroxide sol solution and arsenic slag is 2.
Embodiment 3
The method for innocent treatment for present embodiments providing arsenic in a kind of arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 5 of arsenic-containing waste water is adjusted using acetic acid or sodium bicarbonate, and is added in arsenic-containing waste water after adjustment of ph
Ferrous sulfate, the concentration of arsenic is 100mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 1:1 in iron and arsenic-containing waste water in ferrous sulfate,
Obtain premixed liquid；
(2) sodium peroxydisulfate is added into premixed liquid obtained by step (1), and premix is maintained by addition phosphoric acid or calcium hydroxide
The pH of liquid is 5, and the molar ratio of arsenic is 2:1 in sodium peroxydisulfate and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 8h obtained by the revolving speed whipping step (2) of 1200r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) mixing magnalium sodium hydroxide sol solution and step (3) gained arsenic slag, stir 8h with the revolving speed of 1200r/min
After be separated by solid-liquid separation, filter residue obtains stablizing solid waste after drying, the molar ratio of Mg and Al in the magnalium sodium hydroxide sol solution
For 2:1, the liquid-solid ratio of the magnalium sodium hydroxide sol solution and arsenic slag is 1.
Embodiment 4
The method for innocent treatment for present embodiments providing arsenic in a kind of arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 2 of arsenic-containing waste water is adjusted using sulfuric acid or ammonium hydroxide, and adds sulfuric acid in arsenic-containing waste water after adjustment of ph
Ferrous iron, the concentration of arsenic is 5mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 0.5:1 in iron and arsenic-containing waste water in ferrous sulfate, is obtained
Premixed liquid；
(2) sodium hypochlorite is added into premixed liquid obtained by step (1), and premixed liquid is maintained by addition sulfuric acid or ammonium hydroxide
PH is 2, and the molar ratio of arsenic is 1:1 in sodium hypochlorite and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 10h obtained by the revolving speed whipping step (2) of 100r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) mixing sodium metasilicate sol solution and step (3) gained arsenic slag, with solid-liquid after the revolving speed stirring 10h of 100r/min
Separation, filter residue obtain stablizing after drying solid waste, and the liquid-solid ratio of the sodium metasilicate sol solution and arsenic slag is 0.1.
Embodiment 5
The method for innocent treatment for present embodiments providing arsenic in a kind of arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 7 of arsenic-containing waste water is adjusted using phosphoric acid or sodium hydroxide, and is added in arsenic-containing waste water after adjustment of ph
Ferrous sulfate, the concentration of arsenic is 2000mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 3 in iron and arsenic-containing waste water in ferrous sulfate:
1, obtain premixed liquid；
(2) sodium perchlorate is added into premixed liquid obtained by step (1), and premix is maintained by addition phosphoric acid or sodium hydroxide
The pH of liquid is 7, and the molar ratio of arsenic is 4:1 in sodium perchlorate and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 1h obtained by the revolving speed whipping step (2) of 2000r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) mixing montmorillonite sol solution and step (3) gained arsenic slag, with solid-liquid after the revolving speed stirring 1h of 2000r/min
Separation, filter residue obtain stablizing after drying solid waste, and the liquid-solid ratio of the montmorillonite sol solution and arsenic slag is 5.
Embodiment 6
A kind of method for innocent treatment of arsenic in arsenic-containing waste water is present embodiments provided, the processing method removes step (4)
Inorganic sol used is outside potassium phosphate sol solution, remaining is same as Example 1.
Embodiment 7
A kind of method for innocent treatment of arsenic in arsenic-containing waste water is present embodiments provided, the processing method removes step (4)
Inorganic sol used is outside aluminum hydroxide sol solution, remaining is same as Example 1.
Embodiment 8
A kind of method for innocent treatment of arsenic in arsenic-containing waste water is present embodiments provided, the processing method removes step (4)
Inorganic sol used is outside bentonite sol solution, remaining is same as Example 1.
Comparative example 1
This comparative example provides a kind of method for innocent treatment of arsenic in arsenic-containing waste water, and the processing method removes step (1)
The pH that arsenic-containing waste water is adjusted using sulfuric acid or sodium hydroxide is outside 1.5, remaining is same as Example 1.
Comparative example 2
This comparative example provides a kind of method for innocent treatment of arsenic in arsenic-containing waste water, and the processing method removes step step
(1) adjusting the pH of arsenic-containing waste water using sulfuric acid or sodium hydroxide is outside 7.5, remaining is same as Example 1.
Comparative example 3
This comparative example provides a kind of method for innocent treatment of arsenic in arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 4 of arsenic-containing waste water is adjusted using sulfuric acid or sodium hydroxide, and is added in arsenic-containing waste water after adjustment of ph
Ferrous sulfate, the concentration of arsenic is 500mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 1.5 in iron and arsenic-containing waste water in ferrous sulfate:
1, obtain premixed liquid；
(2) hydrogen peroxide is added into premixed liquid obtained by step (1), and premixed liquid is maintained by addition sulfuric acid or sodium hydroxide
PH be 4, the molar ratio of arsenic is 2.5:1 in hydrogen peroxide and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 6h obtained by the revolving speed whipping step (2) of 1300r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) arsenic slag obtained by method processing step (3) disclosed in the embodiment 1 according to CN 108774024A, is stablized
Solid waste.
Comparative example 4
This comparative example provides a kind of method for innocent treatment of arsenic in arsenic-containing waste water, the treating method comprises following step
It is rapid:
(1) pH to 4 of arsenic-containing waste water is adjusted using sulfuric acid or sodium hydroxide, and is added in arsenic-containing waste water after adjustment of ph
Ferrous sulfate, the concentration of arsenic is 500mg/L in arsenic-containing waste water, and the molar ratio of arsenic is 1.5 in iron and arsenic-containing waste water in ferrous sulfate:
1, obtain premixed liquid；
(2) hydrogen peroxide is added into premixed liquid obtained by step (1), and premixed liquid is maintained by addition sulfuric acid or sodium hydroxide
PH be 4, the molar ratio of arsenic is 2.5:1 in hydrogen peroxide and step (1) described arsenic-containing waste water, obtains mixed liquor；
(3) with mixed liquor 6h obtained by the revolving speed whipping step (2) of 1300r/min, arsenic slag and arsenic removal are obtained after separation of solid and liquid
Produce water；
(4) arsenic slag obtained by method processing step (3) disclosed in the embodiment 1 according to CN 102218428A, is stablized
Solid waste.
Using " solid waste Leaching leaching method horizontal vibration method " (HJ557-2010) to embodiment 1-8 and right
Stablize solid waste obtained by ratio 1-4 and do Leaching experiment, and measure the arsenic content in arsenic removal production water, gained Leaching data are such as
Shown in table 1.
Table 1
| Leaching (mg/L) | Arsenic removal produces Water jet cleaning (mg/L) | |
| Embodiment 1 | 0.3 | 0.2 |
| Embodiment 2 | 0.8 | 0.4 |
| Embodiment 3 | 0.3 | 0.2 |
| Embodiment 4 | 0.2 | 0.2 |
| Embodiment 5 | 1.3 | 0.5 |
| Embodiment 6 | 0.7 | 0.2 |
| Embodiment 7 | 0.6 | 0.2 |
| Embodiment 8 | 0.9 | 0.2 |
| Comparative example 1 | 0.3 | 1.7 |
| Comparative example 2 | 0.3 | 1.4 |
| Comparative example 3 | 1.8 | 0.2 |
| Comparative example 4 | 2.1 | 0.2 |
As shown in Table 1, gained is stablized in the method for innocent treatment of arsenic in the arsenic-containing waste water that 1-8 of the embodiment of the present invention is provided
The Leaching of solid waste is 0.2-0.9mg/L, and it is 0.2- that arsenic-containing waste water gained arsenic removal after treatment, which produces arsenic content in water,
0.5mg/L。
In the arsenic-containing waste water that comparative example 1 provides in the method for innocent treatment of arsenic, except step (1) uses sulfuric acid or hydroxide
The pH that sodium adjusts arsenic-containing waste water is outside 1.5, remaining is same as Example 1.Although the stabilization solid waste that comparative example 1 finally obtains
Leaching is 0.3mg/L, same as Example 1, but it is 1.7mg/L that arsenic removal, which produces the concentration of arsenic in water, higher than in embodiment 1
0.2mg/L。
In the arsenic-containing waste water that comparative example 2 provides in the method for innocent treatment of arsenic, except step (1) uses sulfuric acid or hydroxide
The pH that sodium adjusts arsenic-containing waste water is outside 7.5, remaining is same as Example 1.Although the stabilization solid waste that comparative example 2 finally obtains
Leaching is 0.3mg/L, same as Example 1, but it is 1.4mg/L that arsenic removal, which produces the concentration of arsenic in water, higher than in embodiment 1
0.2mg/L。
In the arsenic-containing waste water that comparative example 3 provides in the method for innocent treatment of arsenic, except the reality using 108774024 A of CN
It applies outside arsenic slag obtained by method processing step (3) disclosed in example 1, remaining is same as Example 1, and gained stablizes the leaching poison of solid waste
Property is 1.8mg/L, higher than the 0.3mg/L in embodiment 1.
In the arsenic-containing waste water that comparative example 4 provides in the method for innocent treatment of arsenic, except the reality using 102218428 A of CN
It applies outside arsenic slag obtained by method processing step (3) disclosed in example 1, remaining is same as Example 1, and gained stablizes the leaching poison of solid waste
Property is 2.1mg/L, higher than the 0.3mg/L in embodiment 1.
To sum up, then the present invention is added by adding ferrous salt in an acidic solution in the premixed liquid added with ferrous salt
Oxidizer, ferrous salt and arsenic after making oxidation are co-precipitated, and by mixing arsenic slag with inorganic sol, further reduced arsenic slag
Harm to environment.Requirement of the processing method provided by the present invention to process equipment is low, and economic performance is good, and in arsenic-containing waste water
The removing of arsenic is thorough, and since the additive amount of ferrous salt is few, the yield of arsenic slag is few, alleviates the volume of cargo in storage that arsenic slag muck is put,
Space is saved, and the Leaching of finally obtained stable solid waste, down to 0.2mg/L, arsenic removal after treatment produces arsenic in water
Content down to 0.2mg/L.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the method for innocent treatment of arsenic in a kind of arsenic-containing waste water, which is characterized in that the treating method comprises following steps:
(1) ferrous salt is added in arsenic-containing waste water after adjusting the pH to 2-7 of arsenic-containing waste water using pH adjusting agent, obtains premixed liquid；
(2) oxidant is added into premixed liquid obtained by step (1), and maintaining the pH of premixed liquid by addition pH adjusting agent is 2-7,
Obtain mixed liquor；
(3) mixed liquor obtained by whipping step (2) obtains arsenic slag after separation of solid and liquid and arsenic removal produces water；
(4) mixing inorganic sol and step (3) gained arsenic slag, are separated by solid-liquid separation, filter residue obtains stablizing solid waste after drying after stirring.
2. processing method according to claim 1, which is characterized in that the concentration of arsenic is in step (1) described arsenic-containing waste water
5mg/L or more, preferably 5-1000mg/L；
Preferably, the ferrous salt includes ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous phosphate, sulphur hydrogenation ferrous iron, sulfuric acid
In ferrous ammonium, ferrous acetate, iron iodide or ferrous bromide any one or at least two combination；
Preferably, the molar ratio of iron and arsenic in arsenic-containing waste water is (0.5-3): 1, preferably (1-2): 1 in the ferrous salt.
3. processing method according to claim 1 or 2, which is characterized in that the pH adjusting agent includes acid or inorganic base；
Preferably, it is described acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetic acid in any one or at least two combination；
Preferably, the inorganic base includes appointing in sodium hydroxide, calcium oxide, calcium hydroxide, ammonium hydroxide, sodium carbonate or sodium bicarbonate
It anticipates a kind of or at least two combinations.
4. processing method according to claim 1-3, which is characterized in that step (2) described oxidant includes smelly
Oxygen, hydrogen peroxide, potassium permanganate, manganese dioxide, bromine water, chlorine, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, sodium hypochlorite, chlorine
In sour sodium or sodium perchlorate any one or at least two combination；
Preferably, the molar ratio of the oxidant and arsenic in step (1) described arsenic-containing waste water is (1-4): 1.
5. processing method according to claim 1-4, which is characterized in that the time of step (3) described stirring is
1-10h, preferably 5-8h；
Preferably, the revolving speed of step (3) described stirring is 100-2000r/min, preferably 1200-1500r/min；
Preferably, the method for step (3) described separation of solid and liquid includes centrifuge separation, vacuum filter, plate compression or cyclonic separation
In any one.
6. processing method according to claim 1-5, which is characterized in that step (4) described inorganic sol includes
Magnesium aluminum hydroxide sol solution, silicate sol solution, phosphate sol solution, hydroxide sol solution, montmorillonite are molten
In sol solution or bentonite sol solution any one or at least two combination, preferably magnesium aluminum hydroxide colloidal sol is molten
Liquid；
Preferably, the molar ratio of Mg and Al is (1-2): (2-1) in the magnesium aluminum hydroxide sol solution.
7. processing method according to claim 1-6, which is characterized in that step (4) inorganic sol and arsenic
The liquid-solid ratio of slag is 0.1-5, preferably 1-2.
8. processing method according to claim 1-7, which is characterized in that the time of step (4) described stirring is
1-12h, preferably 5-10h；
Preferably, the speed of step (4) described stirring is 100-2000r/min, preferably 1200-1500r/min.
9. processing method according to claim 1-8, which is characterized in that the side of step (4) described separation of solid and liquid
Method includes any one in centrifuge separation, vacuum filter, plate compression or cyclonic separation.
10. -9 described in any item processing methods according to claim 1, which is characterized in that the treating method comprises following step
It is rapid:
(1) ferrous salt, iron in ferrous salt are added in arsenic-containing waste water after adjusting the pH to 2-7 of arsenic-containing waste water using acid or inorganic base
Molar ratio with arsenic in arsenic-containing waste water is (0.5-3): 1, premixed liquid is obtained, the concentration of arsenic is 5mg/L or more in arsenic-containing waste water；
(2) oxidant is added into premixed liquid obtained by step (1), and maintaining the pH of premixed liquid by addition acid or inorganic base is 2-
7, the molar ratio of arsenic is (1-4) in oxidant and step (1) described arsenic-containing waste water: 1, obtain mixed liquor；
(3) it with mixed liquor 1-10h obtained by the revolving speed whipping step (2) of 100-2000r/min, obtains arsenic slag after separation of solid and liquid and removes
Arsenic produces water；
(4) mixing inorganic sol and step (3) gained arsenic slag, solid-liquid divides after stirring 1-12h with the revolving speed of 100-2000r/min
From filter residue obtains stablizing solid waste after drying.
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Application publication date: 20190412 |