CN106007076A - Treatment method of arsenic-containing wastewater in tungsten smelting - Google Patents
Treatment method of arsenic-containing wastewater in tungsten smelting Download PDFInfo
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- CN106007076A CN106007076A CN201610517327.5A CN201610517327A CN106007076A CN 106007076 A CN106007076 A CN 106007076A CN 201610517327 A CN201610517327 A CN 201610517327A CN 106007076 A CN106007076 A CN 106007076A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention discloses a treatment method of arsenic-containing wastewater in tungsten smelting. The treatment method comprises the following steps: step (1) pretreating the arsenic-containing wastewater generated in a tungsten smelting process under normal temperature, and regulating the pH (Potential of Hydrogen) value of the wastewater to be 10.0 to 12.0 after pretreatment; step (2) adding an oxidizing agent in the wastewater obtained in step (1), and then stirring for 15 to 25 minutes; step (3) continuously adding iron salt in the wastewater obtained in step (2), quickly stirring for 10 to 20 seconds, and then slowly stirring for 15 to 25 minutes; step (4) finally carrying out static settlement on the wastewater obtained in step (3), and filtering. According to the treatment method disclosed by the invention, the arsenic-containing wastewater in the tungsten smelting is treated by adopting an oxidizing agent + iron salt method, and the concentration of arsenic in the treated wastewater is up to the national integrated wastewater discharge standard (GB8978-1996); the treatment method is simple in technology and strong in operability, and is suitable for large-scale industrial production and application.
Description
Technical field
The present invention relates to the processing method of a kind of Tungsten smelting arsenic-containing waste water, belong to sewage disposal technology
Field.
Background technology
Tungsten belongs to rare metal, has the feature of high-melting-point, high rigidity, be widely used in metallurgy,
The fields such as machinery, oil, mine, electronics and Aero-Space.Para-tungstic acid in the compound of tungsten
In ammonium (i.e. APT) production process, tungsten concentrate, through soda boiling, prepares sodium tungstate, and remove impurity is also adjusted
After joint pH value and concentration, entering ion exchange column, resin is handed over sodium tungstate solution adverse current
Changing, the arsenic impurities in mineral etc. is in company with entering sodium tungstate solution, when the ion-exchange purification of tungsten
In after handing over, liquid enters waste water.It is said that in general, the concentration that APT produces arsenic in waste water exceedes " dirty
Water comprehensive discharge standard " (GB8978-1996) several times even tens times.
Arsenic is first kind pollutant in water, and arsenic compound can be with the mercapto in human body cell enzyme system
Base (SH-) combines, and makes the enzyme loss of activity containing sulfydryl.Therefore, Tungsten smelting ion is exchanged
The process of the waste water that operation produces is very urgent.The outer arsenic removal technology of Present Domestic mainly has precipitation
Method, ion exchange, membrane separation process, bioanalysis and absorption method etc..
The sedimentation method utilize Soluble Arsenic can be formed with the metal ion such as calcium, magnesium, ferrum, aluminum exactly
The characteristic of insoluble compound, makees precipitant with calcium, ferrum, magnesium, aluminium salt and sulfide etc., through heavy
The arsenic in solution it is filtered to remove behind shallow lake；Mainly include neutralization precipitation method, ferrite process, sulfide
The sedimentation method, Coagulation Method etc., conventional precipitant has Calx, iron chloride, bodied ferric sulfate, sulfur
Acid ferrous iron, Alumen and sodium sulfide etc..Sedimentation method technique is simple, it is little to invest, current or most
The main methods of number enterprises arsenic-containing waste water, shortcoming produces substantial amounts of arsenic-containing waste residue, amount big and
Complicated component, long-term disposal is easily caused secondary pollution.
Ion exchange technique has obtained extensively in terms of the removal of water demineralization and heavy metal ion
Application, this method is entered with the object ion in waste water typically by the ion of ion exchange resin
Row exchanges and reaches to remove the purpose of pollutant, a kind of special absorption.Both at home and abroad
Occurred in that applied activated carbon changed resin, sulfide regenerating resin, chelating resin etc. in recent years
The method of reason arsenic-containing waste water.The great advantage of ion exchange technique is to realize returning of resource
Receiving and utilize, thus turn harm into good, but resin price is higher, disposable input is relatively big, and is set
Fat optionally limits, and the method processes arsenic-containing waste water and requires higher to raw water quality, the suitableeest
Single and to the higher water for industrial use of effluent quality requirement or drink for processing ion component
Water.
Membrane separation process is the selective penetrated property utilizing film, according to component each in multicomponent fluid at film
The selective difference of middle mass transfer, by higher external pressure, realize the separation to it, classification,
Purify and enrichment, be divided into microfiltration, ultrafiltration, nanofiltration and reverse osmosis according to the big I of membrane aperture.With
The method carries out waste water process, is not related to phase transformation, is not required to add other materials, non-secondary pollution,
Easy to operate, it is possible not only to the purpose reaching to purify, and effluent quality is the highest, can make
For secondary resource, but this technology to equipment, film, operating condition requirement the harshest, mesh
Before be also mainly used in the preparation of high purity water and ultra-pure water, plant-scale application example also compares
Few.
Bioanalysis is due to advantages such as it are efficient, non-secondary pollution, processing cost are low, at sewage
Having clear superiority in reason, arsenic can be by certain micro-organisms enrichment and concentration in water body, it is also possible to
Being aoxidized by these organisms and convert, as methylated, and the arsenic toxicity after methylating is substantially than nothing
The toxicity of machine arsenic reduces.Bioanalysis utilizes this characteristic to come arsenic toxicity reduction, detoxification, to solve exactly
Certainly water body arsenic pollution problem.But the method is presently mainly by cultivating on defined medium
Strain, produces the material of a kind of flocculent structure being similar to activated sludge, abundant with arsenic-containing waste water
Contact, the flocculating sedimentation in conjunction with arsenic therein, it is then peeled off, reaches effect of removing arsenic.
Absorption method is mainly by adsorbent (having big active surface area or adsorption group)
Powerful adsorption arsenic-adsorbing, then reaches the purpose of arsenic removal by filtration, and this method processes containing arsenic
Waste water, can be down to arsenic in waste water concentration floor level and not increase concentration, has process effect
The advantages such as rate is high, adsorptive hindrance is little, but to high concentration waste water containing arsenic process aspect application ratio
Less.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides the place of a kind of Tungsten smelting arsenic-containing waste water
Reason method, the method is to process the arsenic-containing waste water in Tungsten smelting with " oxidant+iron salt " method,
The concentration of the arsenic in waste water after process reaches country's " integrated wastewater discharge standard "
(GB8978-1996), and the method technique is simple, workable, is suitable for extensive
Commercial production is applied.
Realize the purpose of the present invention to reach by adopting the following technical scheme that:
A kind of processing method of Tungsten smelting arsenic-containing waste water, step is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to acid, by the pH regulator of waste water extremely
10.0～12.0；
Step 2) to step 1) in waste water adds oxidant, then stirring 15～25min；
Step 3) continue to step 2) waste water in add iron salt, first quickly stirring 10～20s,
Then low rate mixing 15～25min；
Step 4) finally by step 3) waste water that obtains staticly settles, filters.
As preferably, step 1) in acid be hydrochloric acid, sulphuric acid or nitric acid one therein or two
More than Zhong.
As preferably, step 2) in oxidant be hydrogen peroxide, sodium hypochlorite, SODIUM PERCARBONATE,
Ammonium persulfate., Dexol or potassium permanganate therein one or more.
As preferably, step 2) in the ratio of oxidant and the concentration of arsenic in waste water ion be
(30～40): 1.
As preferably, step 2) in mixing speed be 60～80r/min.Such speed
It is disposed to the ferrous iron in waste water is fully oxidized to ferric iron.
As preferably, step 3) in iron salt be ferric chloride, ferrous sulfate, polyaluminum sulfate
Ferrum, hydrated ferric oxide., ferrous chloride, iron sulfate therein one or more.
As preferably, step 3) in iron salt and step 2) in the ratio of concentration of oxidant be
(0.5～8): 1.
As preferably, step 3) in the speed of quick stirring be 300～500r/min, stirring
Time is 10～20s；The speed of low rate mixing is 20～50r/min, mixing time be 15～
25min.Quickly mixing speed is fast, the time is short, and this is to enable ferrous iron to absorb air
In oxygen, or react with oxidant, Quick Oxidation becomes ferric iron, low rate mixing speed is slow,
Time is long, and this is to make hydrated ferric oxide. fully react with the arsenic in waste water, precipitate.
As preferably, step 4) in time of staticly settling be 1～3min.Staticly settle and be
In order to make the precipitation in waste water fully separate out, it is sink to container bottom, it is simple to filter.
" oxidant+iron salt " method of the present invention processes the processing method of Tungsten smelting arsenic-containing waste water
Principle is as follows:
First, the ferrous ion in waste water is combined generation ferrous iron hydroxide with hydroxyl
Ferrum, Fe2++2OH-=Fe (OH)2, after then passing to oxidant, ferrous hydroxide is oxidized to hydrogen
Ferrum oxide, as a example by hydrogen peroxide, 2Fe (OH)2+2H2O2+=2Fe (OH)3+H2O, when quickly stirring,
Oxygen in air enters in waste water, and ferrous hydroxide also generates hydroxide as oxygen reaction
Ferrum, 4Fe (OH)2+O2+2H2O=4Fe (OH)3, then add iron salt, wherein two in iron salt
Valency iron ion occurs as above reaction regeneration to become hydrated ferric oxide., and ferric ion is directly and hydrogen-oxygen root knot
Symphysis becomes hydrated ferric oxide., hydrated ferric oxide. to react with the arsenic in waste water, Fe (OH)3+AsO4 3-
→FeAsO4↓+3H20, generate precipitated ferric arsenate, finally precipitate filtration, will arsenic in waste water
Remove, the waste residue produced is carried out harmlessness disposing so that it is do not produce secondary pollution.
Compared to existing technology, the beneficial effects of the present invention is:
1, the processing method of the present invention is to process containing in Tungsten smelting with " oxidant+iron salt " method
Arsenic waste water, the concentration ＜ 0.1mg/L of the arsenic in waste water after process, reach country's " integrated wastewater
Discharge standard " (GB8978-1996) (arsenic≤0.5mg/L), and also the method technique is simple,
Workable, it is suitable for large-scale industrial production application；
2, the processing method of the present invention is initially charged after oxidant and adds iron salt, be possible not only to by
Ferrous oxidising one-tenth ferric iron in waste water, it is also possible to by the ferrous oxidising one-tenth trivalent in iron salt
Ferrum, and do not affect the reaction process of ferric iron and arsenic, make in the ferric iron after oxidation and waste water
Arsenic fully react；
When 3, the processing method of the present invention adding iron salt, the most quickly stirring, rear low rate mixing,
Quickly stirring is to be passed through in waste water by the oxygen in air, makes ferrous iron by oxygen or oxidation
Agent fully oxidized one-tenth ferric iron, low rate mixing is in order to ferric iron fully reacts with arsenic, and it is heavy to generate
Form sediment.
Accompanying drawing explanation
Fig. 1 is the flow chart of the processing method of the present invention.
Detailed description of the invention
Below, in conjunction with accompanying drawing and detailed description of the invention, the present invention is described further:
Embodiment 1:
The selected arsenic-containing waste water of certain tungsten mines (total arsenic mass concentration is 10.0mg/L), contains this
The process step of arsenic waste water is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to sulphuric acid, by the pH regulator of waste water
To 10.0～12.0；
Step 2) to step 1) in waste water adds 3.0% hydrogen peroxide, the concentration of hydrogen peroxide is
0.4g/L, then stirs 15min, and mixing speed is 60r/min；
Step 3) continue to step 2) waste water in add 3.3% ferric chloride, ferric chloride
Concentration be 3.2g/L, add ferric chloride, while quickly stir, stirring is fast
Degree is 300r/min, and mixing time is 10s；Carrying out low rate mixing again, the speed of stirring is
20r/min, mixing time is 15min；
Step 4) finally by step 3) waste water that obtains staticly settles 1min, filter.
Detecting the supernatant after filtering, arsenic removal rate reaches 90.4%, and arsenic mass concentration is
0.48mg/L, (the most total less than country " integrated wastewater discharge standard " (GB8978-1996)
Arsenic≤0.5mg/L).
Embodiment 2:
Certain Tungsten smelting arsenic-containing waste water (total arsenic mass concentration is 10.5mg/L), gives up containing arsenic to this
The process step of water is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to hydrochloric acid, by the pH regulator of waste water
To 10.0～12.0；
Step 2) to step 1) in waste water adds SODIUM PERCARBONATE, the concentration of SODIUM PERCARBONATE is
0.38g/L, then stirs 18min, and mixing speed is 75r/min；
Step 3) continue to step 2) waste water in add ferrous chloride, ferrous chloride dense
Degree is 0.2g/L, adds ferrous chloride, while quickly stirring, mixing speed is
400r/min, mixing time is 15s；Carrying out low rate mixing again, the speed of stirring is 30r/min,
Mixing time is 20min；
Step 4) finally by step 3) waste water that obtains staticly settles 1.5min, filter.
Detecting the supernatant after filtering, arsenic removal rate reaches 99.5%, and arsenic mass concentration is
0.05mg/L, (the most total less than country " integrated wastewater discharge standard " (GB8978-1996)
Arsenic≤0.5mg/L).
Embodiment 3:
Certain Tungsten smelting arsenic-containing waste water (total arsenic mass concentration is 46.95mg/L), gives up containing arsenic to this
The process step of water is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to nitric acid, by the pH regulator of waste water
To 10.0～12.0；
Step 2) to step 1) in waste water adds sodium hypochlorite, the concentration of sodium hypochlorite is
1.64g/L, then stirs 25min, and mixing speed is 80r/min；
Step 3) continue to step 2) waste water in add ferrous sulfate, ferrous sulfate dense
Degree is 0.83g/L, adds ferrous sulfate, while quickly stirring, mixing speed is
500r/min, mixing time is 20s；Carrying out low rate mixing again, the speed of stirring is 50r/min,
Mixing time is 25min；
Step 4) finally by step 3) waste water that obtains staticly settles 3min, filter.
Detecting the supernatant after filtering, arsenic removal rate reaches 99.8%, and arsenic mass concentration is
0.09mg/L, (the most total less than country " integrated wastewater discharge standard " (GB8978-1996)
Arsenic≤0.5mg/L).
Embodiment 4:
Certain Tungsten smelting arsenic-containing waste water (total arsenic mass concentration is 19.36mg/L), gives up containing arsenic to this
The process step of water is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to sulphuric acid, by the pH regulator of waste water
To 10.0～12.0；
Step 2) to step 1) in waste water adds Ammonium persulfate., the concentration of Ammonium persulfate. is
0.61g/L, then stirs 25min, and mixing speed is 80r/min；
Step 3) continue to step 2) waste water in add hydrated ferric oxide., the mixing of iron sulfate
Iron salt, the concentration of mixed molysite is 1.3g/L, hydrated ferric oxide. in mixed molysite, iron sulfate
The ratio of concentration is 1:5, adds mixed molysite, while quickly stirring, mixing speed
For 500r/min, mixing time is 18s；Carrying out low rate mixing again, the speed of stirring is
40r/min, mixing time is 25min；
Step 4) finally by step 3) waste water that obtains staticly settles 3min, filter.
Detecting the supernatant after filtering, arsenic removal rate reaches 99.4%, and arsenic mass concentration is
0.03mg/L, (the most total less than country " integrated wastewater discharge standard " (GB8978-1996)
Arsenic≤0.5mg/L).
Embodiment 5:
Certain Tungsten smelting arsenic-containing waste water (total arsenic mass concentration is 34.52mg/L), gives up containing arsenic to this
The process step of water is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to nitric acid, by the pH regulator of waste water
To 10.0～12.0；
Step 2) to step 1) in waste water adds hydrogen peroxide, the mixed oxidization of sodium hypochlorite
Agent, the concentration of hybrid oxidant is 1.11g/L, hydrogen peroxide, sodium hypochlorite in hybrid oxidant
Concentration than for 1:2, then stir 25min, mixing speed is 80r/min；
Step 3) continue to step 2) waste water in add iron sulfate, the concentration of iron sulfate is
3.14g/L, adds iron sulfate, while quickly stirring, mixing speed is 400r/min,
Mixing time is 20s；Carrying out low rate mixing again, the speed of stirring is 40r/min, during stirring
Between be 25min；
Step 4) finally by step 3) waste water that obtains staticly settles 3min, filter.
Detecting the supernatant after filtering, arsenic removal rate reaches 97.8%, and arsenic mass concentration is
0.32mg/L, (the most total less than country " integrated wastewater discharge standard " (GB8978-1996)
Arsenic≤0.5mg/L).
For a person skilled in the art, can technical scheme as described above and structure
Think, make other various corresponding changes and deformation, and all these changes and deformation
Within all should belonging to the protection domain of the claims in the present invention.
Claims (9)
1. the processing method of a Tungsten smelting arsenic-containing waste water, it is characterised in that step is as follows:
Step 1) under room temperature, the arsenic-containing waste water produced in tungsten smelting process is carried out pretreatment,
Regulate the pH of waste water after pretreatment, in waste water, be slowly added to acid, by the pH regulator of waste water extremely
10.0～12.0；
Step 2) to step 1) in waste water adds oxidant, then stirring 15～25min；
Step 3) continue to step 2) waste water in add iron salt, first quickly stirring 10～20s,
Then low rate mixing 15～25min；
Step 4) finally by step 3) waste water that obtains staticly settles, filters.
The processing method of a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1, it is special
Levy and be: step 1) in acid be hydrochloric acid, sulphuric acid or nitric acid therein one or more.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 2) in oxidant be hydrogen peroxide, sodium hypochlorite, percarbonic acid
Sodium, Ammonium persulfate., Dexol or potassium permanganate therein one or more.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 2) in the ratio of oxidant and the concentration of arsenic in waste water ion be
(30～40): 1.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 2) in mixing speed be 60～80r/min.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 3) in iron salt be ferric chloride, ferrous sulfate, polymerised sulphur
Acid ferrum, hydrated ferric oxide., ferrous chloride, iron sulfate therein one or more.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 3) in iron salt and step 2) in the ratio of concentration of oxidant
For (0.5～8): 1.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 3) in the speed of quick stirring be 300～500r/min, slowly
The speed of speed stirring is 20～50r/min.
The process side of described a kind of Tungsten smelting arsenic-containing waste water the most according to claim 1
Method, it is characterised in that: step 4) in time of staticly settling be 1～3min.
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| CN106396199A (en) * | 2016-12-06 | 2017-02-15 | 河北工业大学 | Method for removing arsenic in wastewater with combination of compound medicine and sludge adsorption material |
| CN106477768A (en) * | 2016-10-31 | 2017-03-08 | 江西稀有金属钨业控股集团有限公司 | A kind of processing method of tungsten mineral material baking flue gas spent shower water |
| CN108862720A (en) * | 2018-07-11 | 2018-11-23 | 郴州市金贵银业股份有限公司 | A kind of processing method of arsenic-containing waste water |
| CN109574319A (en) * | 2019-01-07 | 2019-04-05 | 紫金矿业集团股份有限公司 | The solid arsenic technique of the high arsenic waste acid of non-ferrous metal metallurgy |
| CN109607872A (en) * | 2019-01-07 | 2019-04-12 | 紫金矿业集团股份有限公司 | A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic |
| CN110255615A (en) * | 2019-07-05 | 2019-09-20 | 长沙紫宸科技开发有限公司 | A method of using arsenic alkaline slag as waste antimony oxide, arsenate and soda ash |
| CN110510665A (en) * | 2019-09-29 | 2019-11-29 | 攀钢集团攀枝花钢铁研究院有限公司 | Purification is accelerated to remove the reagent and its application method of vanadium mud sinking speed |
| CN113562891A (en) * | 2021-06-30 | 2021-10-29 | 长沙华时捷环保科技发展股份有限公司 | Method for treating ammonium paratungstate production wastewater |
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| CN110255615A (en) * | 2019-07-05 | 2019-09-20 | 长沙紫宸科技开发有限公司 | A method of using arsenic alkaline slag as waste antimony oxide, arsenate and soda ash |
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