CN108706700A - A kind of method and its application of processing waste liquid containing heavy metal ion - Google Patents
A kind of method and its application of processing waste liquid containing heavy metal ion Download PDFInfo
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- CN108706700A CN108706700A CN201810379530.XA CN201810379530A CN108706700A CN 108706700 A CN108706700 A CN 108706700A CN 201810379530 A CN201810379530 A CN 201810379530A CN 108706700 A CN108706700 A CN 108706700A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention relates to technical field of waste water processing, disclose a kind of method and its application of processing waste liquid containing heavy metal ion.The method is directed to the processing of waste liquid in metallurgical off-gas acid-making engineering, including the use of BaS, Na2SO4、H2SO4Solution or BaS, H2SO4Solution mixing generates H2S gases；Again by H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution.Heavy metal in waste liquid ion is eliminated after solid sulfide separation.This method can be applied in smelting process, and the intermediate product of gained can also be utilized in other links of smelting process.Therefore, with BaS, Na2SO4、H2SO4For raw material or BaS, H2SO4For waste H2The problems such as S handles spent acid containing heavy metal ion, and the operation finished product that can not only solve the spent acid processing of smelting industry is high, and sodium ion is enriched in system；And chemical industry BaSO can be solved4Industry consumes the cost problem of big content of starting materials (such as sulfuric acid).
Description
Technical field
The present invention relates to technical field of waste water processing, in particular to a kind of side of processing waste liquid containing heavy metal ion
Method and its application.
Background technology
Since 21 century, the engineer operations such as metallurgical off-gas acid-making, pyrite-based sulfuric acid production and other chemical industry are on the increase.With close
National increasingly strict to environmental requirement over year, the spent acid of the heavy metal ion such as cupric, arsenic for being generated in sulfuric acid production plant is one
Big pollution sources.It includes Na that the country mainly takes vulcanization, vulcanizing agent to metallurgical off-gas acid-making output waste acid processing method2S、
NaHS etc., that there are treatment operating costs is higher for this method, and sodium ion is enriched with the cycle for being unfavorable for follow-up water in system in system,
The problems such as secondary environmental pollution；In order to solve the above problem, in sulfuric acid industry arsenic recycling open circuit, environmental protection while reduces
Operating cost becomes the research hotspot of sulfuric acid industry spent acid process field.
In recent years, in order to realize the recycling of valuable element and the open circuit of harmful element As, Na etc., H2S replaces Na2S is as sulphur
Agent is increasingly widely used, and Na is usually taken2S and sulfuric acid reaction produce H2S or H2H is synthesized with sulphur2S, both
There is prodigious drawback in method, when it is of high cost, second is that H2Dangerous big, the explosive with sulphur synthesis.
Invention content
The purpose of the present invention is to provide a kind of methods of processing waste liquid containing heavy metal ion, can be cost-effective, and
Improve the safety of production.
Another object of the present invention is to provide a kind of methods of processing waste liquid containing heavy metal ion in smelting process
Using, it can be enough cost-effective, and improve the safety of production.
What the embodiment of the present invention was realized in：
A method of processing waste liquid containing heavy metal ion is used for the liquid waste processing of metallurgical off-gas acid-making engineering, including：
By BaS solution and Na2SO4Solution mixing generates Na2S solution；
By Na2S solution and H2SO4Solution mixing generates H2S gases；
By H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution；
Alternatively,
By BaS solution and H2SO4Solution mixing generates H2S gases；
By H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution.
In an embodiment of the present invention：
The mass fraction of BaS is 5%~20% in BaS solution.
In an embodiment of the present invention：
H2SO4H in solution2SO4Mass fraction be 10%~50%.
In an embodiment of the present invention, the method for processing waste liquid containing heavy metal ion further includes：
Prepare BaS solution：The grey black that barite burns is hydrolyzed into leaching in the hot water, then the lime-ash of generation is carried out
Separation.
In an embodiment of the present invention：
The temperature of hot water is 40 DEG C~100 DEG C.
In an embodiment of the present invention, by BaS solution and Na2SO4Solution mixing generates Na2S solution specifically includes：
By BaS solution and Na2SO4Solution mixes；
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.
In an embodiment of the present invention：
Obtain BaSO4By BaSO after filter cake4Filter cake is dried, is packaged.
In an embodiment of the present invention：
Na2S solution and H2SO4Solution mixing generates H2The Na generated while S gases2SO4Solution is reused for and BaS
Solution reaction.
In an embodiment of the present invention, by H2S gases are mixed with the waste liquid containing heavy metal ion, will be generated
Solid sulfide detached with solution, specifically include：
By H2S gases carry out vulcanization reaction with waste liquid in vulcanization reaction slot；
Waste liquid after vulcanization enters concentrator and carries out sedimentation separation；
Thickener underflow containing solid sulfide, which is sent to filter press, to be separated by solid-liquid separation.
The embodiment of the present invention also proposes utilization of the method for above-mentioned processing waste liquid containing heavy metal ion in smelting process.
The advantageous effect of the embodiment of the present invention is：
Method provided in an embodiment of the present invention is directed to the processing of waste liquid in metallurgical off-gas acid-making engineering, including will be molten by BaS
Liquid and Na2SO4Solution mixing generates Na2S solution；The Na that will be obtained2S solution again with H2SO4Solution mixing generates H2S gases；Again
By H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution.Solid-state vulcanizes
Heavy metal in waste liquid ion (such as arsenic, copper etc.) is eliminated after object separation.This method can be applied in smelting process, gained
Intermediate product can also be utilized in other links of smelting process.And smelting process usually has relieving haperacidity process,
Therefore it is also convenient for providing sulfuric acid as raw material.Intermediate product BaSO4Product can be used as to take out again.It is more in entire smelting process
A link complements each other, cost-effective；Also sulphur and H have been prevented2Prepare H2The security risk that S gases may be brought.Therefore, it ties
It closes metallurgical off-gas acid-making industry and chemical industry prepares BaSO4The characteristics of industry, with BaS, Na2SO4、H2SO4For raw material or with BaS,
H2SO4For waste H2S handle spent acid containing heavy metal ion, can not only solve smelting industry spent acid handle operation at
The problems such as product are high, and sodium ion is enriched in system；And chemical industry BaSO can be solved4Industry consumes big content of starting materials (such as sulfuric acid)
Cost problem.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is a kind of process flow chart of the method for processing waste liquid containing heavy metal ion in the embodiment of the present invention；
Fig. 2 is the process flow chart of the method for another processing waste liquid containing heavy metal ion in the embodiment of the present invention；.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Fig. 1 is a kind of process flow chart of the method for processing waste liquid containing heavy metal ion in the embodiment of the present invention.Fig. 1 is shown
Utilize BaS, Na2SO4、H2SO4For waste H2The technique that S handles the spent acid containing heavy metal ion.Fig. 1 is please referred to, the present invention
Embodiment provides a kind of method of processing waste liquid containing heavy metal ion, is directed to the processing of waste water in metallurgical off-gas acid-making engineering,
The equipment being related to includes yellow water preparation system, BaSO4Preparation system, H2S preparation systems, BaSO4Purge drying packaging system gives up
Molten sulfur eliminates heavy metal system, smelting acid making system, smelts smelting system.Processing the waste liquid containing heavy metal ion method include：
One, BaS solution (yellow water) is prepared
This step can be completed in yellow water preparation system.The preparation of BaS solution be by by grey black (barite burn by
At) mix with 40 DEG C~100 DEG C hot water, so that grey black is fully hydrolyzed leaching in the hot water, has obtained in BaS solution and solution
Lime-ash, then the lime-ash of generation is detached.Lime-ash after separation can return to the smelting furnace for smelting smelting system as addition
Agent.The BaS solution (yellow water) that clear liquid obtains concentration (BaS mass fractions) 5%~20% by allotment flows into the storage of yellow water storage tank.
Two, Na is prepared2S solution
Yellow water from elevated dosing vessel from flowing to synthesis tank, while the metabisulfite solution of the addition 10%~50% of equivalent into
Row reaction, reaction equation are as follows：
BaS+Na2SO4=BaSO4↓+Na2S
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.It isolates
Filter cake be sent into BaSO4 purge drying packaging systems, BaSO4 filter cakes are dried, are packaged, for selling outside.
Three, H is prepared2S gases
This step utilizes H2S preparation systems are completed.Filtrate Na2S solution and 10%~50%H2SO4It is sent into H together2It is prepared by S
Vulcanization reaction slot in system is reacted, and reaction equation is as follows：
Na2S+H2SO4=H2S↑+Na2SO4
Wherein, 10%~50%H2SO4It is that the concentrated sulfuric acid of smelting acid making system output is diluted with water and obtains.It obtains
Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent to waste liquid vulcanization except a huge sum of money
Category system vulcanization reaction slot.BaSO is prepared with traditional mirabilite method is used alone4It compares, the Na generated due to this step2SO4It is molten
Liquid can re-apply the reaction in step 2, therefore save cost.Also, BaSO is prepared separately in tradition4Technique in,
The a large amount of lime-ash generated when BaS are prepared to be difficult to handle；But since the method for the embodiment of the present invention can be applied in smelting process,
Therefore a large amount of lime-ash can be used as the furnace charge for smelting engineering, solved the problems, such as that lime-ash is reluctant, also saved simultaneously
Cost.
Four, H is utilized2S gases remove the heavy metal ion in waste liquid
This step is completed using waste liquid vulcanization removing heavy metals system.The waste liquid that smelting acid making system generates is sent by pumping to sulphur
The hydrogen sulfide reactive tank for eliminating heavy metal system carries out vulcanization reaction, the H obtained in waste liquid and previous step2S gas mixings connect
It touches, the reaction solid sulfide of generating portion (such as sulfide of copper, arsenic), vulcanization concentrator is sent into after waste liquid vulcanization and is sunk
Drop detaches, and the supernatant in concentrator flows into vulcanization filtrate receiver, then is pumped to wastewater treatment process, carries out at further waste water
Reason.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
Five, the superfluous H of processing2S gases
The H of the equipment discharges such as hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S are used by pipeline
Wind turbine, which is concentrated, to be pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, and the gas after reaction is logical
Piping chimney qualified discharge.
The method of processing waste liquid containing heavy metal ion provided in an embodiment of the present invention can be applied in smelting process.
Fig. 2 is the process flow chart of the method for another processing waste liquid containing heavy metal ion in the embodiment of the present invention, and Fig. 2 shows
Go out and has utilized BaS, H2SO4For waste H2The technique that S handles the spent acid containing heavy metal ion.Fig. 2 is please referred to, the present invention's
In other embodiments, the step two in Fig. 1 technological processes prepares Na2The process of S gases can be omitted, and step 3 is changed to directly
It connects and utilizes BaS solution and 10%~50%H2SO4It is sent into H together2S、BaSO4It is reacted in preparation system, reaction equation is such as
Under：
BaS+H2SO4=H2S↑+BaSO4
The method of processing waste liquid containing heavy metal ion provided in an embodiment of the present invention is applied in smelting acid making engineering
Advantage is：
1, using H2S is instead of conventional Na2S handles vulcanizing agent as spent acid in metallurgical off-gas acid-making.It can effectively solve
Certainly sodium ion is to the pollution of arsenic filter cake and the problem of bring liquid after processing into.
2, using BaS, Na2SO4、H2SO4For raw material or use BaS, H2SO4For waste H2The mode of S, for smelting
The removing of the heavy metals such as copper, arsenic in the waste liquid generated in refining flue gas acid preparing, pyrite-based sulfuric acid production and other chemical processes.It produces simultaneously
Go out BaSO4Product, improves income, the high problem of the operation finished product of the effective solution spent acid processing of smelting industry.
3, using BaS, Na2SO4、H2SO4For waste H2The technique of S, output BaSO4While product, Na2SO4Cycle
It uses, does not consume, solve chemical industry mirabilite method well and prepare BaSO4When, it needs to purchase a large amount of Na2SO4Raw material is asked
Topic.
4, using BaS, Na2SO4、H2SO4For raw material or use BaS, H2SO4For waste H2The technique of S, raw material H2SO4
It is derived from metallurgical gas sulphuric acid system, solves preparation H well2When S gases, a large amount of H of outsourcing are needed2SO4The problem of raw material.
5, using BaS, Na2SO4、H2SO4For raw material or use BaS, H2SO4For waste H2The technique of S prepares BaS
The a large amount of waste residue Returning smelting stoves generated when solution solve chemical industry BaSO well as additive4Industry prepares BaS solution
When generate a large amount of Solid state fermentations the problem of.
6, using BaS, H2SO4For the H of waste2S is used for liquid waste processing containing heavy metal ion, solves biography well
Chemical industry sulfuric acid process of uniting prepares BaSO4When the H that generates2The problem of S exhaust-gas treatments.
It describes in detail to the method for handling the waste liquid containing heavy metal ion with reference to specific embodiment：
Embodiment 1
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 40 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 5% by allotment flows into the storage of yellow water storage tank.
S2, BaS solution flow to synthesis tank, and the metabisulfite solution of the addition 10% of simultaneous equal (isometric) is reacted.
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.The filter cake isolated is sent
Enter BaSO4Purge drying packaging system, by BaSO4Filter cake is dried, is packaged, for selling outside.
S3, filtrate Na2The H of S solution and mass fraction 10%2SO4It is sent into H together2Vulcanization reaction slot in S preparation systems
It is reacted.Obtained Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent
Vulcanize removing heavy metals system vulcanization reaction slot to waste liquid.
The hydrogen sulfide reactive tank that the waste liquid that S4, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S5, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 2
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 60 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 10% by allotment flows into the storage of yellow water storage tank.
S2, BaS solution flow to synthesis tank, and the metabisulfite solution of the addition 35% of simultaneous equal (isometric) is reacted.
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.The filter cake isolated is sent
Enter BaSO4Purge drying packaging system, by BaSO4Filter cake is dried, is packaged, for selling outside.
S3, filtrate Na2The H of S solution and mass fraction 35%2SO4It is sent into H together2Vulcanization reaction slot in S preparation systems
It is reacted.Obtained Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent
Vulcanize removing heavy metals system vulcanization reaction slot to waste liquid.
The hydrogen sulfide reactive tank that the waste liquid that S4, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S5, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 3
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 80 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 15% by allotment flows into the storage of yellow water storage tank.
S2, BaS solution flow to synthesis tank, and the metabisulfite solution of the addition 50% of simultaneous equal (isometric) is reacted.
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.The filter cake isolated is sent
Enter BaSO4Purge drying packaging system, by BaSO4Filter cake is dried, is packaged, for selling outside.
S3, filtrate Na2The H of S solution and mass fraction 50%2SO4It is sent into H together2Vulcanization reaction slot in S preparation systems
It is reacted.Obtained Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent
Vulcanize removing heavy metals system vulcanization reaction slot to waste liquid.
The hydrogen sulfide reactive tank that the waste liquid that S4, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S5, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 4
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 100 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 20% by allotment flows into the storage of yellow water storage tank.
S2, BaS solution flow to synthesis tank, and the metabisulfite solution of the addition 50% of simultaneous equal (isometric) is reacted.
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.The filter cake isolated is sent
Enter BaSO4Purge drying packaging system, by BaSO4Filter cake is dried, is packaged, for selling outside.
S3, filtrate Na2The H of S solution and mass fraction 50%2SO4It is sent into H together2Vulcanization reaction slot in S preparation systems
It is reacted.Obtained Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent
Vulcanize removing heavy metals system vulcanization reaction slot to waste liquid.
The hydrogen sulfide reactive tank that the waste liquid that S4, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S5, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 5
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 90 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 15% by allotment flows into the storage of yellow water storage tank.
S2, BaS solution flow to synthesis tank, and the metabisulfite solution of the addition 50% of simultaneous equal (isometric) is reacted.
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains Na2S solution and BaSO4Filter cake.The filter cake isolated is sent
Enter BaSO4Purge drying packaging system, by BaSO4Filter cake is dried, is packaged, for selling outside.
S3, filtrate Na2The H of S solution and mass fraction 50%2SO4It is sent into H together2Vulcanization reaction slot in S preparation systems
It is reacted.Obtained Na2SO4Solution returns to synthesis tank after evaporation and concentration and recycles；React the H generated2S gases are sent
Vulcanize removing heavy metals system vulcanization reaction slot to waste liquid.
The hydrogen sulfide reactive tank that the waste liquid that S4, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S5, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 6
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 40 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 5% by allotment flows into the storage of yellow water storage tank.
The H of S2, BaS solution and mass fraction 10%2SO4Solution is sent into H together2S、BaSO4Vulcanization in preparation system is anti-
Slot is answered to be reacted.The BaSO isolated4It is pressed into filter cake and is sent into BaSO4Purge drying packaging system, by BaSO4Filter cake carries out
Dry, packing, for selling outside.React the H generated2S gases send to waste liquid the vulcanization reaction slot for vulcanizing removing heavy metals system.
The hydrogen sulfide reactive tank that the waste liquid that S3, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S4, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 7
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 60 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 10% by allotment flows into the storage of yellow water storage tank.
The H of S2, BaS solution and mass fraction 35%2SO4Solution is sent into H together2S、BaSO4Vulcanization in preparation system is anti-
Slot is answered to be reacted.The BaSO isolated4It is pressed into filter cake and is sent into BaSO4Purge drying packaging system, by BaSO4Filter cake carries out
Dry, packing, for selling outside.React the H generated2S gases, which are sent to waste liquid, vulcanizes removing heavy metals system vulcanization reaction slot.
The hydrogen sulfide reactive tank that the waste liquid that S3, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S4, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 8
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 80 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 15% by allotment flows into the storage of yellow water storage tank.
The H of S2, BaS solution and mass fraction 50%2SO4Solution is sent into H together2S、BaSO4Vulcanization in preparation system is anti-
Slot is answered to be reacted.The BaSO isolated4It is pressed into filter cake and is sent into BaSO4Purge drying packaging system, by BaSO4Filter cake carries out
Dry, packing, for selling outside.React the H generated2S gases, which are sent to waste liquid, vulcanizes removing heavy metals system vulcanization reaction slot.
The hydrogen sulfide reactive tank that the waste liquid that S3, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S4, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 9
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 100 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 20% by allotment flows into the storage of yellow water storage tank.
The H of S2, BaS solution and mass fraction 50%2SO4Solution is sent into H together2S、BaSO4Vulcanization in preparation system is anti-
Slot is answered to be reacted.The BaSO isolated4It is pressed into filter cake and is sent into BaSO4Purge drying packaging system, by BaSO4Filter cake carries out
Dry, packing, for selling outside.React the H generated2S gases, which are sent to waste liquid, vulcanizes removing heavy metals system vulcanization reaction slot.
The hydrogen sulfide reactive tank that the waste liquid that S3, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S4, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 10
The present embodiment provides a kind of methods of processing waste liquid containing heavy metal ion comprising：
S1, grey black is mixed with 100 DEG C of hot water in leaching tanks, so that grey black is fully hydrolyzed leaching in the hot water, obtains
Lime-ash in BaS solution and solution, then the lime-ash of generation is detached.Lime-ash after separation, which returns, smelts smelting system
Smelting furnace is as additive.The BaS solution that clear liquid obtains mass fraction 15% by allotment flows into the storage of yellow water storage tank.
The H of S2, BaS solution and mass fraction 50%2SO4Solution is sent into H together2S、BaSO4Vulcanization in preparation system is anti-
Slot is answered to be reacted.The BaSO isolated4It is pressed into filter cake and is sent into BaSO4Purge drying packaging system, by BaSO4Filter cake carries out
Dry, packing, for selling outside.React the H generated2S gases, which are sent to waste liquid, vulcanizes removing heavy metals system vulcanization reaction slot.
The hydrogen sulfide reactive tank that the waste liquid that S3, smelting acid making system generate is sent by pumping to vulcanization removing heavy metals system carries out
The H obtained in vulcanization reaction, waste liquid and previous step2S gas mixings contact, the solid sulfide of reaction generating portion (such as
The sulfide of copper, arsenic), it is sent into vulcanization concentrator after waste liquid vulcanization and carries out sedimentation separation, the supernatant in concentrator flows into vulcanization
Filtrate receiver, then it is pumped to wastewater treatment process, carry out further wastewater treatment.
Contain CuS and As2S3The thickener underflow of sulfides is squeezed into vulcanization filter press by pump and is separated by solid-liquid separation, filtered
Liquid returns to vulcanization concentrator, and vulcanization filter cake collects in case selling outside.
The H of the equipment discharges such as S4, hydrogen sulfide reactive tank, vulcanization concentrator, vulcanization filtrate receiver2The pernicious gases such as S pass through pipe
Road is concentrated with wind turbine and is pumped into harmful waste removing tower, and flowing from lower to upper is reacted with the NaOH solution sprayed from top to bottom, the gas after reaction
Body passes through pipeline chimney qualified discharge.
Embodiment 1 to 5 can refer to the process flow chart of Fig. 1, and embodiment 6 to 10 can refer to the process flow chart of Fig. 2.It should
Understand, each step link of embodiment 1 to embodiment 10 both can be applied in smelting process, using in the smelting process of part
Equipment, product, to its smelting process generate spent acid synchronize the processing (relative to smelting process other processes link)；
It can also individually be handled for other waste liquids containing heavy metal, and not depend on the equipment in smelting process and product.
In conclusion processing of the method provided in an embodiment of the present invention for waste liquid in metallurgical off-gas acid-making engineering, including
By BaS solution and Na2SO4Solution mixing generates Na2S solution；The Na that will be obtained2S solution again with H2SO4Solution mixing generates H2S
Gas；Or by BaS solution and H2SO4Solution mixing generates H2S gases.Again by H2S gases and the waste liquid containing heavy metal ion
It is mixed, the solid sulfide of generation is detached with solution.Solid sulfide separation after i.e. eliminate heavy metal in waste liquid from
Sub (such as arsenic, copper etc.).This method can be applied in smelting process, the intermediate product of gained can also smelting process its
It is utilized in his link.And smelting process usually has relieving haperacidity process, therefore is also convenient for providing sulfuric acid as raw material.It is intermediate
Product BaSO4Product can be used as to take out again.Multiple links in entire smelting process complement each other, cost-effective；Also prevent
Sulphur and H2Prepare H2The security risk that S gases may be brought.Therefore, it is prepared in conjunction with metallurgical off-gas acid-making industry and chemical industry
BaSO4The characteristics of industry, with BaS, Na2SO4、H2SO4For raw material or with BaS, H2SO4For waste H2S processing contains heavy metal
The problems such as ion spent acid, the operation finished product that can not only solve the spent acid processing of smelting industry is high, and sodium ion is enriched in system；
And chemical industry BaSO can be solved4Industry consumes the cost problem of big content of starting materials (such as sulfuric acid).
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of processing waste liquid containing heavy metal ion, is used for the liquid waste processing of metallurgical off-gas acid-making engineering, feature exists
In, including：
By BaS solution and Na2SO4Solution mixing generates Na2S solution；
By the Na2S solution and H2SO4Solution mixing generates H2S gases；
By the H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution；
Alternatively,
By BaS solution and H2SO4Solution mixing generates H2S gases；
By the H2S gases are mixed with the waste liquid containing heavy metal ion, and the solid sulfide of generation is detached with solution.
2. the method for processing waste liquid containing heavy metal ion according to claim 1, it is characterised in that：
The mass fraction of BaS is 5%~20% in the BaS solution.
3. the method for processing waste liquid containing heavy metal ion according to claim 1, it is characterised in that：
The H2SO4H in solution2SO4Mass fraction be 10%~50%.
4. the method for processing waste liquid containing heavy metal ion according to claim 1, which is characterized in that the processing is containing a huge sum of money
Belong to ion waste liquid method further include：
Prepare the BaS solution：The grey black that barite burns is hydrolyzed into leaching in the hot water, then the lime-ash of generation is carried out
Separation.
5. the method for processing waste liquid containing heavy metal ion according to claim 4, it is characterised in that：
The temperature of the hot water is 40 DEG C~100 DEG C.
6. it is according to claim 1 processing the waste liquid containing heavy metal ion method, which is characterized in that by BaS solution with
Na2SO4Solution mixing generates Na2S solution specifically includes：
By the BaS solution and the Na2SO4Solution mixes；
Mixed liquor after reaction is sent into filter press to be separated by solid-liquid separation, obtains the Na2S solution and BaSO4Filter cake.
7. the method for processing waste liquid containing heavy metal ion according to claim 6, it is characterised in that：
Obtain the BaSO4By the BaSO after filter cake4Filter cake is dried, is packaged.
8. the method for processing waste liquid containing heavy metal ion according to claim 1, it is characterised in that：
The Na2S solution and the H2SO4Solution mixing generates the H2The Na generated while S gases2SO4Solution is by again
For with the BaS solution reactions.
9. the method for processing waste liquid containing heavy metal ion according to claim 1, which is characterized in that by the H2S gases with
Waste liquid containing heavy metal ion is mixed, and the solid sulfide of generation is detached with solution, is specifically included：
By the H2S gases carry out vulcanization reaction with the waste liquid in vulcanization reaction slot；
The waste liquid after vulcanization enters concentrator and carries out sedimentation separation；
Thickener underflow containing the solid sulfide, which is sent to filter press, to be separated by solid-liquid separation.
10. utilization of the method for processing waste liquid containing heavy metal ion described in any one of claim 1-9 in smelting process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110116991A (en) * | 2019-05-21 | 2019-08-13 | 长沙有色冶金设计研究院有限公司 | A kind of recovery process of metallurgical off-gas acid-making purification waste acid |
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