CN106746402A - The method for processing arsenic removal sludge - Google Patents
The method for processing arsenic removal sludge Download PDFInfo
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- CN106746402A CN106746402A CN201611179880.9A CN201611179880A CN106746402A CN 106746402 A CN106746402 A CN 106746402A CN 201611179880 A CN201611179880 A CN 201611179880A CN 106746402 A CN106746402 A CN 106746402A
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- arsenic removal
- calcium
- waste water
- acid solution
- tungsten
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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
- C02F11/00—Treatment of sludge; Devices therefor
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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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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of method for processing arsenic removal sludge, containing at least one in calcium carbonate, calcium hydroxide, iron hydroxide and tungsten oxide in arsenic removal sludge, the method includes：(1) arsenic removal sludge is mixed with water, to obtain pulp liquid；(2) will be filtered after pulp liquid and the first acid solution mixed dissolution, to obtain the filtrate containing calcium ion and iron ion and the filter residue containing tungsten oxide；(3) filtered after being mixed Tungsten smelting waste water and the second acid solution and filtrate containing calcium ion and iron ion, to obtain the first arsenic removal sludge and arsenic removal filtrate；(4) filtered after the filter residue containing tungsten oxide is mixed with alkali lye, to obtain the filtrate containing tungstates and filter residue.The method can not only make the amount of arsenic removal sludge reduce more than 90%, and the consumption of the additional calcium salt of Tungsten smelting waste water arsenic removal and molysite can be made to reduce more than 80%, the rate of recovery of tungsten oxide is reached more than 85%, and low cost, equipment is simple, and operating procedure is easily achieved commercial Application.
Description
Technical field
Field, specifically, the method the present invention relates to process arsenic removal sludge are recycled the invention belongs to resource reclaim.
Background technology
At present, Tungsten smelting Environmental Protection Situation is further severe.In January, 2016, national environmental protection portion is by Tungsten smelting tungsten slag, molybdenum slag and gives up
Removing arsenic from water sludge is classified as dangerous solid waste, thus this " three slags " treatment is slightly improper is possible to touch model law.How to have
Effect treatment " three slags " turns into the thing that current Tungsten smelting enterprise is concerned about the most.If transferring to dangerous waste to process the list of qualification by " three slags "
Position treatment, then because processing cost is sufficiently expensive, cause enterprise to undertake.
The arsenic containing 3~7mg/L is the main sludge factor in Tungsten smelting waste water, and arsenic removal sludge is mainly waste water arsenic removal process
Middle generation.Arsenic removal process mainly includes calcium salt precipitation method, molysite deposition method or calcium salt-molysite co-precipitation method.At present, calcium
Salt precipitation method and molysite deposition method are influenceed larger by pH value of waste water and other foreign ions, so effect of removing arsenic is unstable；And
Calcium salt-molysite co-precipitation method is Tungsten smelting waste water arsenic removal method the most stable, but can produce more arsenic removal sludge.
To dreg containing arsenic, at present mostly using landfill, cement solidification or lime solidification technology is stabilized in industry, that is, allow dangerous useless
All pollution components are presented chemical inertness or are contained in thing, and to reduce subsequent treatment and potential danger, these methods lack
Point is that the valuable metal in arsenic removal sludge can not be recycled, and the solidfied material for being formed is limited using channel.
Therefore, the technology of existing treatment arsenic removal sludge is further improved.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, of the invention
One purpose is to propose a kind of method for processing arsenic removal sludge, and the method can realize the resource such as calcium, iron, tungsten in arsenic removal sludge
Comprehensive cyclic utilization, and the processing equipment of the processing method is simple, and operating procedure is easy, is easy to implement industrialization, small investment,
Be conducive to improving the economic benefit of enterprise.
The application is completed based on the following discovery of inventor：With the tungsten slag of Tungsten smelting, molybdenum slag and waste water arsenic removal sludge
Dangerous solid waste is listed in, the treatment to this " three slags " becomes most important for Tungsten smelting enterprise.For Tungsten smelting
Enterprise, or spending high handling, transfers to dangerous waste to process the processed in units of qualification by " three slags ", otherwise enterprise oneself develops
Respective handling technique, to reach national corresponding environmental emission standard.To waste water arsenic removal sludge, mostly using steady in current industry
Fixedization landfill, cement solidification or lime solidification technology, that is, allow all pollution components in hazardous waste present chemical inertnesses or
Contained, to reduce subsequent treatment and potential danger.The shortcoming of such method be valuable metal in arsenic removal sludge not
Can recycle, and the solidfied material for being formed is limited using channel.In consideration of it, present inventor is by existing treatment
The technology of arsenic removal sludge is tried to explore, it is intended to solve defect of the prior art, and being desirably to obtain can Efficient Cycle utilization
Valuable metal in arsenic removal sludge, and processing equipment is simple, technique is easy, low production cost handling process.
Therefore, in one aspect of the invention, the present invention proposes a kind of method for processing arsenic removal sludge, the arsenic removal is dirty
Contain at least one in calcium carbonate, calcium hydroxide, iron hydroxide and tungsten oxide in mud.Embodiments in accordance with the present invention, the party
Method includes：(1) the arsenic removal sludge is mixed with water, to obtain pulp liquid；(2) the pulp liquid is mixed with the first acid solution
Filtered after dissolving, to obtain the filtrate containing calcium ion and iron ion and the filter residue containing tungsten oxide；(3) Tungsten smelting is given up
Water is filtered after being mixed with the second acid solution and the filtrate containing calcium ion and iron ion, to obtain the first arsenic removal sludge
With arsenic removal filtrate, and the first arsenic removal sludge return to step (1) is carried out into the pulp, wherein, in the Tungsten smelting waste water
Contain at least one in NaOH, sodium chloride, natrium arsenicum, sodium metasilicate and tungsten oxide；(4) by the filter containing tungsten oxide
Slag is filtered after mixing with alkali lye, to obtain the filtrate containing tungstates and filter residue.
Thus, the method for the treatment of arsenic removal sludge according to embodiments of the present invention is by by the pulp liquid and acid solution of arsenic removal sludge
Mixed, the calcium carbonate for containing and iron hydroxide in arsenic removal sludge can be converted into soluble calcium salt and molysite, so that
The filtrate containing calcium ion and iron ion and the filter residue containing tungsten oxide can be obtained through filtering, then contain calcium by what is obtained
The filtrate of ion and iron ion is mixed as except arsenic reagent with Tungsten smelting waste water, and the natrium arsenicum in Tungsten smelting waste water can be with
Calcium ion and iron ion in filtrate are combined and are converted into ferric arsenate and calcium arsenate, so that not only can be dirty with effective recycling arsenic removal
Valuable element in mud, and Tungsten smelting cost for wastewater treatment can be significantly reduced, and can substantially reduce Tungsten smelting waste water
In arsenic element content, make its carry out again fluorine removal and adjust pH after by qualified discharge；Simultaneously by Tungsten smelting wastewater treatment process
In separating obtained arsenic removal sludge return to step (1) in be continuing with, can continue the molysite in the part arsenic removal sludge
Utilized with calcium salt, secondly mixed the filter residue containing tungsten oxide isolated in step (2) with alkali lye, can be by
Tungsten oxide is converted into tungstates, it is achieved thereby that in arsenic removal sludge and Tungsten smelting waste water wolfram element recycling, use in addition
The method of present invention treatment arsenic removal sludge, can not only make the amount of arsenic removal sludge reduce more than 90%, and can make Tungsten smelting
The consumption of the additional calcium salt of waste water arsenic removal and molysite reduces more than 80%；Can have by leaching the filter residue containing tungsten oxide with alkali
Effect reclaims tungsten oxide, and the rate of recovery can reach more than 85%.Thus arsenic removal sludge and Tungsten smelting can be realized using the method
The comprehensive cyclic utilization of the resource such as calcium, iron, tungsten in waste water, and the processing equipment of the processing method is simple, operating procedure is easy, just
In realizing industrializing, small investment is conducive to improving the economic benefit of enterprise.
In addition, the method for the treatment of arsenic removal sludge according to the above embodiment of the present invention, can also have following additional skill
Art feature：
In some embodiments of the invention, in step (1), the water is with the mixing quality ratio of the arsenic removal sludge
(20~25)：1.Thus, it is possible to make arsenic removal sludge pulp abundant.
In step (1), the arsenic removal sludge is mixed 0.3~1 hour, preferably 0.5 hour with the water.Thus,
Can further allow arsenic removal sludge pulp abundant.
In some embodiments of the invention, in step (2), first acid solution be selected from hydrochloric acid and nitric acid extremely
Few one kind.Thus, it is possible to significantly improve the dissolution rate of calcium carbonate and iron oxide in arsenic removal sludge.
In some embodiments of the invention, in step (2), the mass concentration of first acid solution is 20~40%,
It is preferred that 31%.Thus, it is possible to further improve the dissolution rate of calcium carbonate and iron oxide in arsenic removal sludge.
In some embodiments of the invention, in step (2), the mixed volume of the pulp liquid and first acid solution
Than being (15~25)：1.Thus, it is possible to further improve the dissolution rate of calcium carbonate and iron oxide in arsenic removal sludge.
In some embodiments of the invention, in step (2), the mixing of the pulp liquid and first acid solution
Time is 0.5~1.5 hour.Thus, it is possible to further improve the dissolution rate of calcium carbonate and iron oxide in arsenic removal sludge.
In some embodiments of the invention, in step (2), the mixing of the pulp liquid and first acid solution
Rotating speed is 30~100r/min, preferably 60r/min.Thus, it is possible to further improve calcium carbonate and iron oxide in arsenic removal sludge
Dissolution rate.
In some embodiments of the invention, in step (3), further include：To containing Tungsten smelting waste water and second
Calcium salt and molysite are added in the mixed liquor of acid solution and the filtrate containing calcium ion and iron ion.Thus, it is possible to significantly improve tungsten smelting
Arsenic removal efficiency in refining waste water.
In some embodiments of the invention, in step (3), the mixed liquor containing Tungsten smelting waste water and the second acid solution
PH is 9.5~10.5.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), second acid solution be selected from hydrochloric acid and nitric acid extremely
Few one kind.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), the Tungsten smelting waste water is with described containing calcium ion and iron
The mixed volume ratio of the filtrate of ion is (15~25)：1.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), the Tungsten smelting waste water and second acid solution and described
Filtrate containing calcium ion and iron ion mixed the time for 5~10 minutes.Thus, it is possible to further improve Tungsten smelting waste water
In arsenic removal efficiency.
In some embodiments of the invention, in step (3), continue to stir 5 after adding the calcium salt and the molysite
~10 minutes.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), the calcium salt is calcium chloride, calcium nitrate, calcium carbonate and sulphur
At least one in sour calcium, preferably calcium chloride and calcium nitrate, the molysite are sub- iron chloride, frerrous chloride, ferric sulfate and sulfuric acid
At least one in iron.Thus, it is possible to further remove the arsenic in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), the calcium salt added is mixed with the Tungsten smelting waste water
Composition and division in a proportion is (0.025~0.05)：1.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (3), the molysite added is mixed with the Tungsten smelting waste water
Composition and division in a proportion is (0.025~0.05)：1.Thus, it is possible to further improve the arsenic removal efficiency in Tungsten smelting waste water.
In some embodiments of the invention, in step (4), the alkali lye is selected from NaOH and potassium hydroxide
At least one.Thus, it is possible to improve the rate of recovery of tungsten oxide.
In some embodiments of the invention, in step (4), the weight of the filter residue containing tungsten oxide and the alkali lye
Amount is than being (0.5~1.5)：(1.5~2.5), preferably 1：2.Thus, it is possible to further improve the rate of recovery of tungsten oxide.
In some embodiments of the invention, in step (4), the filter residue containing tungsten oxide mixes with the alkali lye
Temperature is 120~150 degrees Celsius, and the time is 3~6 hours.Thus, it is possible to further improve the rate of recovery of tungsten oxide.
In some embodiments of the invention, in step (2) (3) (4), the filtering is separately inhaled using vacuum
At least one in filter, centrifugal filtration and plate compression.Thus, it is possible to realize the resource such as calcium, iron, tungsten in waste water arsenic removal sludge
Comprehensive cyclic utilization, simplifies handling process, is easy to implement commercial Application.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the schematic flow sheet of the method for the treatment of arsenic removal sludge according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or implying relative importance
Or the implicit quantity for indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or
Implicitly include at least one this feature.In the description of the invention, " multiple " is meant that at least two, such as two, three
It is individual etc., unless otherwise expressly limited specifically.
In one aspect of the invention, the present invention proposes a kind of method for processing arsenic removal sludge, wherein, the arsenic removal is dirty
Contain at least one in calcium carbonate, calcium hydroxide, iron hydroxide and tungsten oxide in mud.Embodiments in accordance with the present invention, the party
Method includes：(1) the arsenic removal sludge is mixed with water, to obtain pulp liquid；(2) the pulp liquid is mixed with the first acid solution
Filtered after dissolving, to obtain the filtrate containing calcium ion and iron ion and the filter residue containing tungsten oxide；(3) Tungsten smelting is given up
Water is filtered after being mixed with the second acid solution and the filtrate containing calcium ion and iron ion, to obtain the first arsenic removal sludge
With arsenic removal filtrate, and the first arsenic removal sludge return to step (1) is carried out into the pulp, wherein, in the Tungsten smelting waste water
Contain at least one in NaOH, sodium chloride, natrium arsenicum, sodium metasilicate and tungsten oxide；(4) by the filter containing tungsten oxide
Slag is filtered after mixing with alkali lye, to obtain the filtrate containing tungstates and filter residue.Inventor has found, enters by by arsenic removal sludge
Row pulp, is then mixed with the first acid solution, can fully be dissolved the calcium salt in arsenic removal sludge and molysite so that after filtering
The filter residue amount of gained only accounts for 5~10wt% of the molten preceding arsenic removal sludge total amount of acid, to significantly reduce and contain 5 in sludge quantity, and filter residue
The tungsten oxide of~15wt%, is conducive to the recovery of subsequent oxidation tungsten；And the filtrate after filtering, because containing substantial amounts of calcium salt and iron
Salt, can be used in Tungsten smelting wastewater treatment process except arsenic reagent is used, can so greatly reduce Tungsten smelting waste water arsenic removal need mend
Plus calcium salt and molysite amount, found according to experiment, both adds consumption and can reduce more than 80%, and through this arsenic removal process,
The content of arsenic greatly reduces in filtrate, less than 0.1mg/L, then carry out fluorine removal and adjust pH after by qualified discharge.By the way that 5 will be contained
The filter residue of~15wt% tungsten oxides carries out alkali and leaches to reclaim tungsten oxide, and the rate of recovery of tungsten oxide can reach more than 85%.It is whole
Individual technical process, the cyclic utilization rate of calcium salt, molysite in arsenic removal sludge is high, and the rate of recovery of tungsten oxide is high, and Tungsten smelting waste water is removed
The effect is significant of arsenic, environmental protection, economy, and handling process is simple, is easy to implement industrialization.
The method of the treatment arsenic removal sludge of the embodiment of the present invention is described in detail below with reference to Fig. 1.According to the present invention
Embodiment, the method includes：
S100：Arsenic removal sludge is mixed with water
In the step, in arsenic removal sludge can containing calcium carbonate, calcium hydroxide, iron hydroxide and tungsten oxide at least one
Kind, specifically, can the magnesia containing 2wt%, the silica of 7wt%, the calcium carbonate of 70wt%, 11wt% in arsenic removal sludge
Calcium hydroxide, the iron hydroxide of 8wt%, the tungsten oxide of 1.5wt%, the arsenic oxide arsenoxide of 0.5wt% and other.Specifically, will
Arsenic removal sludge mixes with water, obtains pulp liquid.
According to one embodiment of present invention, in the step, water is not particularly restricted with the mixing ratio of arsenic removal sludge, this
Art personnel can be selected according to actual needs, a specific embodiment of the invention, water and arsenic removal sludge
Mixing quality ratio can be (20~25)：1.Inventor has found, when water and arsenic removal sludge mixing quality than it is too high when, can lead
Cause gained pulp liquid product excessive, it is impossible to all to recycle, and because water is on the high side, the efficiency for the treatment of arsenic removal sludge can be reduced；And
When water and arsenic removal sludge mixing quality than it is too low when, the acid too strong of pulp liquid can be caused, so as to waste follow-up added the
One acid solution and the second acid solution, can also cause that the pH value of the first arsenic removal sludge is relatively low.
According to still a further embodiment, in the step, arsenic removal sludge does not receive spy with the mixing time of water
Do not limit, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, arsenic removal
Sludge can be 0.3~1 hour, preferably 0.5 hour with the mixing time of water.Thus, it is possible to further make arsenic removal sludge
Pulp is abundant.
S200：To be filtered after pulp liquid and the first acid solution mixed dissolution
In the step, the pulp liquid that above-mentioned steps are obtained and the first acid solution are mixed, filtering, to obtain containing calcium
The filtrate and the filter residue containing tungsten oxide of ion and iron ion.Inventor's discovery, pulp is added to by by the first acid solution
It is in arsenic removal sludge and stirring while adding, can cause that insoluble calcium salt and molysite in arsenic removal sludge etc. is fully dissolved into filtrate,
So that the filter residue amount of gained only accounts for 5~10wt% of the molten preceding arsenic removal sludge total amount of acid after filtering, so as to significantly reduce sludge quantity,
And the tungsten oxide containing 5~15wt% in separating obtained filter residue, be conducive to the recovery of subsequent oxidation tungsten.The master being related in the step
Want chemical equation as follows：
CaCO3+ HCl=CaCl2+H2O+CO2 (1)
Ca(OH)2+ HCl=CaCl2+H2O (2)
Fe(OH)3+ HCl=FeCl3+H2O (3)
According to one embodiment of present invention, the species of the first acid solution is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, a specific embodiment of the invention, the first acid solution can be selected from hydrochloric acid and nitre
At least one in acid.Inventor has found that such acid solution can fully dissolve calcium salt, molysite in the arsenic removal sludge after pulp etc. and sink
Starch, so as to sludge quantity can be substantially reduced.
According to still a further embodiment, the concentration of the first acid solution is not particularly restricted, those skilled in the art
Can be selected according to actual needs, a specific embodiment of the invention, the mass concentration of the first acid solution can be
20~40%, preferably 31%.Inventor has found that the acid solution of the concentration is substantially better than the arsenic removal after other concentration fully dissolve pulp
The sediments such as calcium salt, molysite in sludge, so as to sludge quantity can be substantially reduced.
According to still another embodiment of the invention, pulp liquid is not particularly restricted with the mixing ratio of the first acid solution, ability
Field technique personnel can be selected according to actual needs, a specific embodiment of the invention, pulp liquid and first acid
The mixed volume ratio of liquid can be (15~25)：1.Inventor has found, when the mixed volume of pulp liquid and the first nitration mixture is than too high
When, gained filtrate volume can be caused excessive, it is impossible to all recycle, the efficiency for the treatment of arsenic removal sludge can be reduced；And work as pulp
The mixed volume of liquid and the first nitration mixture than it is too low when, the acid too strong of pulp liquid can be caused, so as to waste follow-up added second
Acid solution, can also cause that the pH value of the first arsenic removal sludge is relatively low.
According to still another embodiment of the invention, the mixing time of pulp liquid and the first acid solution do not limited especially
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, pulp liquid with
The mixing time of the first acid solution can be 0.5~1.5 hour.Thus, it is possible to significantly improve after pulp calcium in arsenic removal sludge
The meltage of the sediments such as salt, molysite, reduces sludge quantity.
According to still another embodiment of the invention, the mixing rotating speed of pulp liquid and the first acid solution is not limited especially
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, pulp liquid with
The mixing rotating speed of the first acid solution can be 30~100r/min, preferably 60r/min.Thus, it is possible to after significantly improving pulp
The meltage of the sediment such as calcium salt, molysite in arsenic removal sludge, reduces sludge quantity.
S300：Filtered after Tungsten smelting waste water and the second acid solution and filtrate containing calcium ion and iron ion are mixed,
And the first arsenic removal sludge return to step S100 is carried out into pulp
In the step, can be containing in NaOH, sodium chloride, natrium arsenicum, sodium metasilicate and tungsten oxide in Tungsten smelting waste water
At least one；Tungsten smelting waste water after being processed by the filtrate containing calcium ion and iron ion obtained by S200 and through the second acid solution
Mixed, to obtain the first arsenic removal sludge and arsenic removal filtrate.Wherein, the first arsenic removal sludge of gained can return to enter in S100
Row pulp.Inventor has found that the filtrate containing calcium ion and iron ion for obtaining step S200 is used as except arsenic reagent and tungsten smelting
Refining waste water is mixed, and the natrium arsenicum in Tungsten smelting waste water can be combined with calcium ion and iron ion in filtrate is converted into arsenic acid
Iron and calcium arsenate, so as to not only with the valuable element in effective recycling arsenic removal sludge, and tungsten smelting can be significantly reduced
Refining cost for wastewater treatment, and can substantially reduce the arsenogen cellulose content in Tungsten smelting waste water, while by Tungsten smelting wastewater treatment
During separating obtained arsenic removal sludge return to step S100 in be continuing with, can continue in the part arsenic removal sludge
Molysite and calcium salt are utilized.Specifically, the content for obtaining arsenic in arsenic removal filtrate is less than 0.1mg/L.The master being related in the step
Want chemical equation as follows：
Na3AsO4+FeCl3=FeAsO4↓+3NaCl (4)
2Na3AsO4+3CaCl2=Ca3(AsO4)2↓+6NaCl (5)
FeCl3+ 3NaOH=Fe (OH)3↓+3NaCl (6)
According to one embodiment of present invention, in the step, can be to containing Tungsten smelting waste water and the second acid solution and containing
Calcium salt and molysite are added in the mixed liquor of the filtrate of calcium ion and iron ion.Inventor has found, if all being obtained using step S200
To the filtrate containing calcium ion and iron ion as except arsenic reagent is used, then will certainly in the Tungsten smelting waste water in the step
Increase the treating capacity in the processing procedure, and in the application using the filtrate containing calcium ion and iron ion and additional calcium salt and
The processing mode of molysite, can not only significantly reduce the cost of material of calcium salt and molysite, and can substantially reduce workload, carry
The economic benefit of enterprise high.
According to still a further embodiment, the pH value of the Tungsten smelting waste water for being processed through the second acid solution is not limited especially
System, those skilled in the art can be selected according to actual needs, and a specific embodiment of the invention contains tungsten smelting
The pH value of the mixed liquor of refining waste water and the second acid solution can be 9.5~10.5.Inventor's discovery, contains Tungsten smelting waste water and second
The pH value of the mixed liquor of acid solution is too high to cause Tungsten smelting waste water arsenic removal not thorough, and it is too low can cause the waste of the second acid solution,
Equally can also cause that Tungsten smelting waste water arsenic removal is not thorough.
According to still another embodiment of the invention, the selection of the second acid solution is not particularly restricted, those skilled in the art
Can be selected according to actual needs, a specific embodiment of the invention, the second acid solution can be selected from hydrochloric acid and
At least one in nitric acid.Thus, it is possible to significantly improve the arsenic removal efficiency in Tungsten smelting waste water.
According to still another embodiment of the invention, through the second acid solution process after Tungsten smelting waste water with contain calcium ion and iron
The mixed volume ratio of the filtrate of ion is not particularly restricted, and those skilled in the art can be selected according to actual needs,
A specific embodiment of the invention, Tungsten smelting waste water after being processed through the second acid solution with containing calcium ion and iron ion
The mixed volume ratio of filtrate can be (15~25)：1.Inventor find, through the second acid solution process after Tungsten smelting waste water with contain
The mixed volume for having the filtrate of calcium ion and iron ion can cause the Tungsten smelting waste water arsenic removal after being processed through the second acid solution than too high
Thoroughly, and the too low pH value that can cause the first arsenic removal sludge is not relatively low, so as to increase the consumption of follow-up alkali lye, while cause containing
The waste of the filtrate of calcium ion and iron ion.
According to still another embodiment of the invention, through the second acid solution process after Tungsten smelting waste water with contain calcium ion and iron
The mixing time of the filtrate of ion is not particularly restricted, and those skilled in the art can be selected according to actual needs
Select, a specific embodiment of the invention, the Tungsten smelting waste water after being processed through the second acid solution with containing calcium ion and iron from
The mixing time of the filtrate of son can be 5~10 minutes.Thus, it is possible to further improve the arsenic removal in Tungsten smelting waste water
Rate.
According to still another embodiment of the invention, add and continue time of stirring after calcium salt and molysite and do not limited especially
System, those skilled in the art can be selected according to actual needs, and a specific embodiment of the invention adds calcium salt
Can it be 5~10 minutes with the time for continuing to stir after molysite.Thus, it is possible to further improve the arsenic removal in Tungsten smelting waste water
Rate.
According to still another embodiment of the invention, the species of the calcium salt added is not particularly restricted, people in the art
Member can be selected according to actual needs, a specific embodiment of the invention, the calcium salt added can for calcium chloride,
At least one in calcium nitrate, calcium carbonate and calcium sulfate, preferably calcium chloride and calcium nitrate.Inventor has found, compared to calcium carbonate
With the calcium salt such as calcium sulfate, calcium ion concentration is higher in the calcium salt in the application, thus, advantageously reduces the consumption of calcium salt, so that
Reduce the cost of material of calcium salt.
According to still another embodiment of the invention, the species of the molysite added is not particularly restricted, people in the art
Member can be selected according to actual needs, a specific embodiment of the invention, the molysite added can for iron chloride,
At least one in frerrous chloride, ferric sulfate and ferrous sulfate.Inventor has found, compared to other molysite, iron chloride, protochloride
Iron concentration in iron, ferric sulfate and ferrous sulfate is higher, thus, advantageously reduces the consumption of molysite, so as to reduce molysite
Cost of material.
According to still another embodiment of the invention, the calcium salt added is not limited especially with the mixing ratio of Tungsten smelting waste water
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, the calcium added
Salt can be (0.025~0.05) with the mixing ratio of Tungsten smelting waste water：1.Inventor's discovery, the calcium salt added and Tungsten smelting waste water
The too high waste that can cause calcium salt of mixing ratio, and too low Tungsten smelting waste water arsenic removal can be caused not thorough.
According to still another embodiment of the invention, the molysite added is not limited especially with the mixing ratio of Tungsten smelting waste water
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, the iron added
Salt can be (0.025~0.05) with the mixing ratio of Tungsten smelting waste water：1.Inventor's discovery, the molysite added and Tungsten smelting waste water
The too high waste that can cause molysite of mixing ratio, and too low Tungsten smelting waste water arsenic removal can be caused not thorough.
S400：Filtered after filter residue containing tungsten oxide is mixed with alkali lye
In the step, the filter residue containing tungsten oxide obtained by S200 is mixed with alkali lye, then filtered, can be contained
The filtrate of tungstates and filter residue.Inventor has found, by the oxidation in the filter residue that contains tungsten oxide with alkali soluble solution in autoclave
Tungsten, chemical equation is：WO3+2OH-=WO4 2-+H2O, so as to reach reclaim tungsten oxide purpose, and generation contain tungsten
Hydrochlorate filtrate, can return to main shop and uses.A specific embodiment of the invention, inventor has found, by using alkali soluble solution
To reclaim tungsten oxide, the exchange rate of tungsten oxide is up to more than 85% to filter residue containing tungsten oxide, not only increases the economic effect of enterprise
Benefit, and equipment is simple, and operating procedure is simple, is advantageously implemented industrial applications.
According to one embodiment of present invention, alkali lye is not particularly restricted, and those skilled in the art can be according to reality
Needs are selected, a specific embodiment of the invention, and alkali lye can be selected from NaOH and potassium hydroxide
It is at least one.
According to still a further embodiment, the filter residue containing tungsten oxide is not limited especially with the weight ratio of alkali lye
System, those skilled in the art can be selected according to actual needs, and a specific embodiment of the invention contains oxidation
The filter residue of tungsten and the weight ratio of alkali lye can be (0.5~1.5)：(1.5~2.5), preferably 1：2.Inventor's discovery, contains oxidation
The filter residue of tungsten is reclaimed not thoroughly with the weight of alkali lye than the too high tungsten oxide that can cause in the filter residue containing tungsten oxide, and too low meeting
Cause the waste of alkali lye.
According to still another embodiment of the invention, the filter residue containing tungsten oxide is not limited especially with the mixing temperature of alkali lye
System, those skilled in the art can be selected according to actual needs, and a specific embodiment of the invention contains oxidation
The filter residue of tungsten can be 120~150 degrees Celsius with the mixing temperature of alkali lye.Thus, it is possible to significantly improve the rate of recovery of tungsten oxide.
According to still another embodiment of the invention, the filter residue containing tungsten oxide is not limited especially with the incorporation time of alkali lye
System, those skilled in the art can be selected according to actual needs, and a specific embodiment of the invention contains oxidation
The filter residue of tungsten can be 3~6 hours with the incorporation time of alkali lye.Thus, it is possible to further improve the rate of recovery of tungsten oxide.
According to still another embodiment of the invention, in step S200, S300 and S400, filter method is not limited especially
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, and filtering can be with
Separately using at least one in vacuum suction filter, centrifugal filtration and plate compression.Thus, it is possible to realize that waste water arsenic removal is dirty
The comprehensive cyclic utilization of the resource such as calcium, iron, tungsten in mud, simplifies handling process, is easy to implement commercial Application.
Below with reference to specific embodiment, present invention is described, it is necessary to explanation, these embodiments are only description
Property, and the present invention is limited never in any form.
Experimental technique described in following embodiments, unless otherwise specified, is conventional method.
Raw material is obtained from commercial channels described in following embodiments.
Embodiment 1
Its step is as follows：
(1) arsenic removal sludge pretreatment：200kg arsenic removal sludge is taken, can the oxidation containing 2wt% wherein in arsenic removal sludge
Magnesium, the silica of 7wt%, the calcium carbonate of 70wt%, the calcium hydroxide of 11wt%, the iron hydroxide of 8wt%, the oxygen of 1.5wt%
Change other of tungsten, the arsenic oxide arsenoxide of 0.5wt% and surplus, add to 10m3Tank diameter in, then toward adding 4000kg in tank diameter
Water, stirs 0.5 hour, obtains pulp liquid.
(2) pulp liquid acid dissolution phase：Add 0.25m toward tank diameter331wt% hydrochloric acid, stirs in acid adding, and stirring is anti-
Answer 0.5 hour, filter, the about 4m for obtaining3Filtrate containing calcium ion and iron ion uses in being left to step (3), obtains
The filter residue that 23kg contains tungsten oxide is used in being left to step (4).The dissolution rate of arsenic removal sludge is up to 88.5%, filter residue in this step
Amount is only the 11.5% of sludge quantity, WO in filter residue3Content is 9%, and arsenic content is 4.5%.
(3) filtrate stage of arsenic removal：Under normal temperature, 100m is taken3Tungsten smelting waste water, arsenic in waste water concentration is 4.8mg/L, by tungsten smelting
The pH value for refining waste water is adjusted to 10.5, adds the 4m of gained in step (2)3Filtrate containing calcium ion and iron ion, stirring
5min, adds 2.5kg iron chloride, is eventually adding 30kg alkalescence calcium chloride, stirs 5min, filters afterwards, obtains arsenic removal filtrate
With arsenic removal sludge, wherein, in arsenic removal filtrate arsenic concentration be 0.21mg/L, then carry out fluorine removal and adjust pH after by qualified discharge；Remove
Then return to step (1) proceeds treatment to arsenic sludge, and the clearance of Tungsten smelting waste water arsenic reaches 95.6% in this step.
(4) alkali is leached and reclaims tungsten：The filter residue that the 23kg produced in step (2) contains tungsten oxide is added closed to 100L
In reactor, 23kg water is added, stir into slurry, add 2.85kg NaOH, be warming up to 140 DEG C, stirring reaction 3 is small
When, after being cooled to 50 DEG C, plate-frame filtering being carried out, the filtrate for obtaining is sodium tungstate solution, can return to main flow and uses；The filter for obtaining
Slag WO3Content is 1.3%, and arsenic content is 5.1%, and filter residue is together recycled with tungsten slag by the unit of tool qualification, this stage pair
WO in filter residue3The rate of recovery reach 85.6%.
Embodiment 2
Its step is as follows：
(1) arsenic removal sludge pretreatment：200kg arsenic removal sludge is taken, can the oxidation containing 2wt% wherein in arsenic removal sludge
Magnesium, the silica of 7wt%, the calcium carbonate of 70wt%, the calcium hydroxide of 11wt%, the iron hydroxide of 8wt%, the oxygen of 1.5wt%
Change other of tungsten, the arsenic oxide arsenoxide of 0.5wt% and surplus, add to 10m3Tank diameter in, then toward adding 5000kg in tank diameter
Water, stirs 0.5 hour, obtains pulp liquid.
(2) pulp liquid acid dissolution phase：Add 0.3m toward tank diameter331% hydrochloric acid, stirs, stirring reaction in acid adding
0.5 hour, filtering, what is obtained about contains the 5m of calcium ion and iron ion3Filtrate uses in being left to step (3), the 15kg for obtaining
Filter residue containing tungsten oxide is used in being left to step (4).Up to 92.5%, filter residue amount is accounted for the dissolution rate of arsenic removal sludge in this step
The 7.5% of sludge quantity, WO in filter residue3Content is 13.5%, and arsenic content is 4.3%.
(3) filtrate stage of arsenic removal：Under normal temperature, 100m is taken3Tungsten smelting waste water, arsenic in waste water concentration is 5.4mg/L, by tungsten smelting
The pH value for refining waste water is adjusted to 10.0, adds the 5m obtained by step (2)3Filtrate containing calcium ion and iron ion, stirs 5min,
2.0kg iron chloride is added, 24kg alkalescence calcium chloride is eventually adding, 5min is stirred, filtered afterwards, obtain arsenic removal filtrate and arsenic removal
Sludge.Wherein, in arsenic removal filtrate arsenic concentration be 0.08mg/L, then carry out fluorine removal and adjust pH after by qualified discharge；Arsenic removal sludge
Then return to step (1) proceeds treatment, and the clearance of Tungsten smelting waste water arsenic reaches 98.5% in this step.
(4) alkali is leached and reclaims tungsten：The filter residue that the 15kg produced in step (2) contains tungsten oxide is added closed to 100L
In reactor, 15kg water is added, stir into slurry, add 3.5kg NaOH, be warming up to 160 DEG C, stirring reaction 4 hours,
After being cooled to 50 DEG C, plate-frame filtering is carried out, the filtrate for obtaining is sodium tungstate solution, can return to main flow and uses；The filter residue for obtaining
WO3Content is 0.9%, and arsenic content is 5.7%, and filter residue is together recycled with tungsten slag by the unit of tool qualification, and this stage is to filter
WO in slag3The rate of recovery reach 93.3%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of method for processing arsenic removal sludge, contains calcium carbonate, calcium hydroxide, iron hydroxide and oxidation in the arsenic removal sludge
At least one in tungsten, it is characterised in that methods described includes：
(1) the arsenic removal sludge is mixed with water, to obtain pulp liquid；
(2) will be filtered after the pulp liquid and the first acid solution mixed dissolution, to obtain the filtrate containing calcium ion and iron ion
And the filter residue containing tungsten oxide；
(3) filtered after Tungsten smelting waste water is mixed with the second acid solution and the filtrate containing calcium ion and iron ion, with
Just the first arsenic removal sludge and arsenic removal filtrate are obtained, and the first arsenic removal sludge return to step (1) is carried out into the pulp, its
In, contain at least one in NaOH, sodium chloride, natrium arsenicum, sodium metasilicate and tungsten oxide in the Tungsten smelting waste water；
(4) filtered after the filter residue containing tungsten oxide is mixed with alkali lye, to obtain the filtrate containing tungstates and filter residue.
2. method according to claim 1, it is characterised in that in step (1), the water is mixed with the arsenic removal sludge
It is (20~25) to close mass ratio：1；
Optional, the arsenic removal sludge is mixed 0.3~1 hour, preferably 0.5 hour with the water.
3. method according to claim 1, it is characterised in that in step (2), first acid solution be selected from hydrochloric acid and
At least one in nitric acid；
Optional, the mass concentration of first acid solution is 20~40%, preferably 31%.
4. method according to claim 3, it is characterised in that in step (2), the pulp liquid and first acid solution
Mixed volume ratio be (15~25)：1；
Optional, the pulp liquid is 0.5~1.5 hour with the mixing time of first acid solution；
Optional, the pulp liquid is 30~100r/min, preferably 60r/min with the mixing rotating speed of first acid solution.
5. method according to claim 1, it is characterised in that step (3) is further included：To containing Tungsten smelting waste water with
Calcium salt and molysite are added in the mixed liquor of the second acid solution and the filtrate containing calcium ion and iron ion.
6. method according to claim 5, it is characterised in that the pH of the mixed liquor containing Tungsten smelting waste water and the second acid solution
It is 9.5~10.5；
Optional, second acid solution is selected from least one in hydrochloric acid and nitric acid.
7. the method according to claim 5 or 6, it is characterised in that the Tungsten smelting waste water with it is described containing calcium ion and
The mixed volume ratio of the filtrate of iron ion is (15~25)：1；
Optional, the Tungsten smelting waste water is mixed with second acid solution and the filtrate containing calcium ion and iron ion
Time is 5~10 minutes.
8. method according to claim 7, it is characterised in that add continue after the calcium salt and the molysite stir 5~
10 minutes；
Optional, the calcium salt is at least one in calcium chloride, calcium nitrate, calcium carbonate and calcium sulfate, preferably calcium chloride and nitre
Sour calcium, the molysite is at least one in iron chloride, frerrous chloride, ferric sulfate and ferrous sulfate.
Optional, the calcium salt added is (0.025~0.05) with the mixing ratio of the Tungsten smelting waste water：1；
Optional, the molysite added is (0.025~0.05) with the mixing ratio of the Tungsten smelting waste water：1.
9. method according to claim 1, it is characterised in that in step (4), the alkali lye be selected from NaOH and
At least one in potassium hydroxide；
Optional, the filter residue containing tungsten oxide is (0.5~1.5) with the weight ratio of the alkali lye：(1.5~2.5), preferably
1：2.
Optional, the filter residue containing tungsten oxide is 120~150 degrees Celsius with the alkali lye mixing temperature, and the time is 3~6
Hour.
10. method according to claim 1, it is characterised in that in step (2) (3) (4), the filtering is independently
Ground is using at least one in vacuum suction filter, centrifugal filtration and plate compression.
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