CN109354288A - The method for handling stainless steel acid cleaning waste water - Google Patents

The method for handling stainless steel acid cleaning waste water Download PDF

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Publication number
CN109354288A
CN109354288A CN201811330306.8A CN201811330306A CN109354288A CN 109354288 A CN109354288 A CN 109354288A CN 201811330306 A CN201811330306 A CN 201811330306A CN 109354288 A CN109354288 A CN 109354288A
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China
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filtrate
filter cake
adjusted
minutes
flocculant
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CN201811330306.8A
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Chinese (zh)
Inventor
薛贤
张晗
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常州润德石墨科技有限公司
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Priority to CN201811330306.8A priority Critical patent/CN109354288A/en
Publication of CN109354288A publication Critical patent/CN109354288A/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The present invention provides a kind of methods for handling stainless steel acid cleaning waste water, are related to environment protection field.It the described method comprises the following steps: flushing water pH is adjusted to 1-2, be added first and fluorine agent and second is gone to go fluorine agent, be then allowed to stand, filter, obtain filter cake and filtrate；Filtrate pH is adjusted to 2-3, is added and removes ferric flocculant, be then allowed to stand, filter, obtain filter cake and filtrate；Filtrate pH is adjusted to 4-5, is added and removes chromium flocculant, be then allowed to stand, filter, obtain filter cake and filtrate；Filtrate pH is adjusted to 6-7, is added and removes nickel flocculant, be then allowed to stand, filter, obtain filter cake and filtrate；Filtrate pH is adjusted to 7-8, then through film process, concentrated water is handled through triple effect evaporation, then dope crystallisation by cooling carries out harmless treatment.Each element in flushing water separation and Extraction one by one is achieved the purpose that comprehensive utilization of resources, environmental protection by the method that please provide itself.

Description

The method for handling stainless steel acid cleaning waste water
Technical field
The present invention relates to environment protection fields, in particular to a kind of method for handling stainless steel acid cleaning waste water.
Background technique
Contain fluorine, iron, chromium, nickel, manganese etc. in the fluorine-containing pickling solution and fluorine-containing acidic flushing water that stainless steel material pickling generates Element, the outward transport of current fluorine-containing pickling solution is by having the processed in units of disposition qualification, usually first at calcium oxide or calcium chloride After managing fluorine, metal ion is disposably precipitated, is filtered out by oxidation plus flocculant, then handles sludge and filtrate.
The prior art can by wastewater treatment to reach can discharge standard, but disposably metal ion is all settled out Come, will lead to following resource and recycle complication, with high costs or even cost is higher than the value for the substance being recovered to, in turn Cause the intention degree for carrying out depth resource reclaim in the market not high, cause the serious wasting of resources, while the stacking of sediment, filling out Bury the generation for also resulting in secondary pollution.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide it is a kind of handle stainless steel acid cleaning waste water method, from waste water recycle calcirm-fluoride, The substances such as iron, chromium, nickel, manganese realize comprehensive utilization of waste materials, reduce environmental pollution.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A method of processing stainless steel acid cleaning waste water the described method comprises the following steps:
A. the pH of the fluorine-containing flushing water of acid-washing stainless steel is adjusted to 1-2, first is sequentially added under stirring and goes fluorine agent and Two go fluorine agent, continue to stir after addition, are then allowed to stand, filter, obtain the first filter cake and the first filtrate；
B. the pH of first filtrate is adjusted to 2-3, is added and removes ferric flocculant, continues to stir, be then allowed to stand, filter, obtain To the second filter cake and the second filtrate；
C. the pH of second filtrate is adjusted to 4-5, polymer is added and removes chromium flocculant, continue to stir, be then allowed to stand, Filtering, obtains third filter cake and third filtrate；
D. the pH of the third filtrate is adjusted to 6-7, the polymer is added and except nickel flocculant, continues to stir, then It stands, filtering, obtains the 4th filter cake and the 4th filtrate；
E. the pH of the 4th filtrate is adjusted to 7-8, then through film process, condensed water is handled through triple effect evaporation, and dope is cold But then crystallization carries out harmless treatment.
Preferably, further include demanganization step F between the step D and E: the pH of the 4th filtrate is adjusted to 7-8, be added The polymer and demanganization flocculant, continue to stir, and are then allowed to stand, filter, and obtain the 5th filter cake and the 5th filtrate；
Then the 4th filtrate is substituted with the 5th filtrate execute the step E.
Using the method for controlling each processing step pH value, changing the method for being disposably settled out all metal ions is gradually Fluorine, iron, chromium, nickel are isolated, following resource comprehensive utilization is avoided and complicates, provides space for low cost Resource recovery.PH value Adjustment be from acid to neutrality again to acidity, process is irreversible, and adjustment needs precisely just to can guarantee that each metallic element substep is analysed Out.
It should be noted that " substitute the 4th filtrate with the 5th filtrate and execute the step E " refers to: when useless When containing manganese in water, step F is added between step D and E, the pH of the 5th filtrate is then adjusted to 7-8, then through film process, Concentrated water is handled through triple effect evaporation, then dope crystallisation by cooling carries out harmless treatment.
It is further preferred that the time for continuing stirring is 15-40 minutes, and the time of standing is 25-60 points in the step F Clock；5th filter cake is manganous hydroxide.
Preferably, the sodium hydroxide or potassium hydroxide aqueous solution for the use of mass fraction being 25-35% when adjusting pH.
It is preferred that sodium hydroxide or potassium hydroxide aqueous solution carry out the adjusting of pH value, be conducive to the control of process, Ke Yigeng Good gradually separates each ingredient.
Preferably, it is described except ferric flocculant, it is described except chromium flocculant, it is described except nickel flocculant, the demanganization flocculant are equal For cationic surfactant, the cationic surfactant is polyacrylamide；The polymer is aluminium polychloride.
Preferred flocculant and polymer can preferably realize separation, the precipitating of ingredient.
Preferably, described first go fluorine agent for calcium chloride, described second goes fluorine agent for aluminum aluminum sulfate；In the step A, after The time of continuous stirring is 25-35 minutes, and the time of standing is 50-70 minutes；First filter cake is calcirm-fluoride.
Being applied in combination for calcium chloride and aluminum aluminum sulfate, can convert calcirm-fluoride for fluorine element well, relative to using It individually goes for fluorine agent, has higher efficiency and better effect.
It is further preferred that the time for continuing stirring is 5-15 minutes, and the time of standing is 15-60 points in the step B Clock；Second filter cake is iron hydroxide.
It is further preferred that the time for continuing stirring is 15-35 minutes, and the time of standing is 25-60 in the step C Minute；The third filter cake is chromium hydroxide.
It is further preferred that the time for continuing stirring is 25-35 minutes, and the time of standing is 35- in the step D 60 minutes；4th filter cake is nickel hydroxide.
The control of mixing time and time of repose and the extraction, precipitation, precipitating of each ingredient are closely bound up.
Optionally, film used in the film process is reverse osmosis membrane；In the triple effect evaporation processing, temperature control is 110-140℃。
Using reverse osmosis membrane and triple effect evaporation, the filtrate after separation of metal ions can be further processed, evaporation Discharge after coolant liquid recycles or is up to standard, filtrate is returned triple effect evaporation and is recycled after dope crystallization filtering.It can will be recycled Or the substance separation that can be discharged, the treating capacity of solid waste is reduced, is further reduced the cost.
Compared with prior art, the invention has the benefit that
(1) gradually each ingredient in stainless steel acid cleaning waste water is separated, is convenient for subsequent comprehensive utilization, reduce secondary use Basic cost；
(2) processing method environmental protection, to the greatest extent pollution of the reduction waste water to environment；
(3) comprehensive utilization ratio is promoted, the wasting of resources is reduced.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The pickling flush water 600g for taking A stainless steel enterprises, it is fluorine-containing through detecting: 2.1 × 103Mg/L, iron content: 5.83 × 103Mg/L, containing chromium: 1.094 × 103Mg/L, it is nickeliferous: 6.344 × 102mg/L；The pH of flushing water is adjusted to 1, under stirring according to Secondary addition calcium chloride 8g and aluminum aluminum sulfate 4g continues stirring 25 minutes after addition, be then allowed to stand 70 minutes, filtering, obtain First filtrate, filter cake obtain calcirm-fluoride 2.4g in dry 1 hour through 110 DEG C；
The pH of first filtrate is adjusted to 2 with the sodium hydrate aqueous solution that mass fraction is 25%, polyacrylamide is added 0.2g continues stirring 15 minutes, is then allowed to stand 15 minutes, filtering, obtains the second filtrate；Filter cake is iron hydroxide, dry through 110 DEG C It is dry, turn crystalline substance and obtain di-iron trioxide 5.1g；
The pH of second filtrate is adjusted to 4 with the sodium hydrate aqueous solution that mass fraction is 25%, polyacrylamide is added 0.1g, aluminium polychloride 0.9g continue stirring 15 minutes, are then allowed to stand 60 minutes, filtering, obtain third filtrate；Filter cake is through 110 DEG C obtain chromium hydroxide 1.3g within dry 1 hour；
The pH of third filtrate is adjusted to 6 with the sodium hydrate aqueous solution that mass fraction is 25%, polyacrylamide is added 0.1g, aluminium polychloride 0.9g continue stirring 35 minutes, are then allowed to stand 35 minutes, filtering, obtain the 4th filtrate；Filter cake is through 110 DEG C obtain nickel hydroxide 0.6g within dry 1 hour；
Through detecting, fluorine is not detected in the 4th filtrate, iron content 5mg/L, 0.16mg/L containing chromium (are free of high valence chrome), nickeliferous 0.3mg/L；
The 4th filtrate 10Kg is collected, the pH of the 4th filtrate is adjusted to 7 with the sodium hydrate aqueous solution that mass fraction is 25%, Then it is handled through reverse osmosis membrane (RO film), obtains clear water 8.5Kg, condensed water 1.5Kg；Clear water discharge, condensed water through triple effect evaporation at Reason, it is 110-140 DEG C that triple effect evaporation, which controls temperature range, evaporative cooling liquid qualified discharge, and dope is concentrated under reduced pressure, after crystallisation by cooling It filters, be dried to obtain inorganic salts 730g, then carry out harmless treatment, filtrate returns to triple effect evaporation or discharge.
The mode of harmless treatment are as follows: take quartz sand that suitable sodium carbonate is added, be heated to quartz sand fusing, then slowly Above-mentioned inorganic salts are added, finish maintenance 10-20 minutes, then cooling crush is used to prepare concrete.
Embodiment 2
The pickling flush water 600g for taking B stainless steel enterprises, it is fluorine-containing through detecting: 1.15 × 103Mg/L, iron content: 5.483 × 104Mg/L, containing chromium: 1.515 × 103Mg/L, it is nickeliferous: 6.979 × 103Mg/L contains manganese 4.119 × 102mg/L；By flushing water PH is adjusted to 2, and calcium chloride 4g and aluminum aluminum sulfate 2g are sequentially added under stirring, continues stirring 30 minutes after addition, then 60 minutes, filtering are stood, the first filtrate is obtained, filter cake obtains calcirm-fluoride 1.3g in dry 1 hour through 110 DEG C；
The pH of first filtrate is adjusted to 3 with the potassium hydroxide aqueous solution that mass fraction is 30%, polyacrylamide is added 0.3g continues stirring 10 minutes, is then allowed to stand 50 minutes, filtering, obtains the second filtrate；Filter cake is iron hydroxide, dry through 110 DEG C It is dry, turn crystalline substance and obtain di-iron trioxide 47g；
The pH of second filtrate is adjusted to 5 with the potassium hydroxide aqueous solution that mass fraction is 30%, polyacrylamide is added 0.1g, aluminium polychloride 1.8g continue stirring 30 minutes, are then allowed to stand 40 minutes, filtering, obtain third filtrate；Filter cake is through 110 DEG C obtain chromium hydroxide 1.8g within dry 1 hour；
The pH of third filtrate is adjusted to 7 with the potassium hydroxide aqueous solution that mass fraction is 30%, polyacrylamide is added 0.1g, aluminium polychloride 1.8g continue stirring 30 minutes, are then allowed to stand 40 minutes, filtering, obtain the 4th filtrate；Filter cake is through 110 DEG C obtain nickel hydroxide 6.62g within dry 1 hour；
The pH of 4th filtrate is adjusted to 7 with the potassium hydroxide aqueous solution that mass fraction is 30%, polyacrylamide is added 0.1g, aluminium polychloride 1.8g continue stirring 30 minutes, are then allowed to stand 40 minutes, filtering, obtain the 5th filtrate and the 5th filter Cake, filter cake obtain manganous hydroxide 0.4g in dry 1 hour through 110 DEG C.
Through detecting, fluorine-containing 4.2mg/L in the 5th filtrate, iron content 3mg/L, 0.18mg/L containing chromium (are free of high valence chrome), nickeliferous 0.25mg/L does not detect manganese.
The 5th filtrate 10Kg is collected, the pH of the 5th filtrate is adjusted to 8 with the potassium hydroxide aqueous solution that mass fraction is 30%, Then it is handled through reverse osmosis membrane (RO film), obtains clear water 8.7Kg, condensed water 1.3Kg；Clear water discharge, condensed water through triple effect evaporation at Reason, it is 110-140 DEG C that triple effect evaporation, which controls temperature range, evaporative cooling liquid qualified discharge, and dope is concentrated under reduced pressure, after crystallisation by cooling It filters, be dried to obtain inorganic salts 750g, then carry out harmless treatment, filtrate returns to triple effect evaporation or discharge.
The mode of harmless treatment are as follows: take quartz sand that suitable sodium carbonate is added, be heated to quartz sand fusing, then slowly Above-mentioned inorganic salts are added, finish maintenance 10-20 minutes, then cooling crush is used to prepare concrete.
Embodiment 3
The pickling flush water 600g for taking B stainless steel enterprises, it is fluorine-containing through detecting: 1.15 × 103Mg/L, iron content: 5.483 × 104Mg/L, containing chromium: 1.515 × 103Mg/L, it is nickeliferous: 6.979 × 103Mg/L contains manganese 4.119 × 102mg/L；By flushing water PH is adjusted to 2, and calcium chloride 3.8g and aluminum aluminum sulfate 2.1g are sequentially added under stirring, continues stirring 35 minutes after addition, It is then allowed to stand 50 minutes, filtering, obtains the first filtrate, filter cake obtains calcirm-fluoride 1.25g in dry 1 hour through 110 DEG C；
The pH of first filtrate is adjusted to 3 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.3g continues stirring 5 minutes, is then allowed to stand 60 minutes, filtering, obtains the second filtrate；Filter cake is iron hydroxide, dry through 110 DEG C It is dry, turn crystalline substance and obtain di-iron trioxide 46.8g；
The pH of second filtrate is adjusted to 4 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.5g continue stirring 35 minutes, are then allowed to stand 25 minutes, filtering, obtain third filtrate；Filter cake is through 110 DEG C obtain chromium hydroxide 1.7g within dry 1 hour；
The pH of third filtrate is adjusted to 6 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.6g continue stirring 25 minutes, are then allowed to stand 60 minutes, filtering, obtain the 4th filtrate；Filter cake is through 110 DEG C obtain nickel hydroxide 6.58g within dry 1 hour；
The pH of 4th filtrate is adjusted to 8 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.7g continue stirring 15 minutes, are then allowed to stand 60 minutes, filtering, obtain the 5th filtrate and the 5th filter Cake, filter cake obtain manganous hydroxide 0.38g in dry 1 hour through 110 DEG C.
Through detecting, fluorine-containing 4.3mg/L in the 5th filtrate, iron content 3.1mg/L, 0.19mg/L containing chromium (are free of high valence chrome), contain Nickel 0.26mg/L, does not detect manganese.
The 5th filtrate 10Kg is collected, the pH of the 5th filtrate is adjusted to 7 with the potassium hydroxide aqueous solution that mass fraction is 35%, Then it is handled through reverse osmosis membrane (RO film), obtains clear water 8.6Kg, condensed water 1.4Kg；Clear water discharge, condensed water through triple effect evaporation at Reason, it is 110-140 DEG C that triple effect evaporation, which controls temperature range, evaporative cooling liquid qualified discharge, and dope is concentrated under reduced pressure, after crystallisation by cooling It filters, be dried to obtain inorganic salts 748g, then carry out harmless treatment, filtrate returns to triple effect evaporation or discharge.
The mode of harmless treatment are as follows: take quartz sand that suitable sodium carbonate is added, be heated to quartz sand fusing, then slowly Above-mentioned inorganic salts are added, finish maintenance 10-20 minutes, then cooling crush is used to prepare concrete.
Embodiment 4
The pickling flush water 600g for taking B stainless steel enterprises, it is fluorine-containing through detecting: 1.15 × 103Mg/L, iron content: 5.483 × 104Mg/L, containing chromium: 1.515 × 103Mg/L, it is nickeliferous: 6.979 × 103Mg/L contains manganese 4.119 × 102mg/L；By flushing water PH is adjusted to 1, and calcium chloride 4.1g and aluminum aluminum sulfate 2.2g are sequentially added under stirring, continues stirring 32 minutes after addition, It is then allowed to stand 55 minutes, filtering, obtains the first filtrate, filter cake obtains calcirm-fluoride 1.32g in dry 1 hour through 110 DEG C；
The pH of first filtrate is adjusted to 2 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.35g continues stirring 5 minutes, is then allowed to stand 60 minutes, filtering, obtains the second filtrate；Filter cake is iron hydroxide, dry through 110 DEG C It is dry, turn crystalline substance and obtain di-iron trioxide 47.1g；
The pH of second filtrate is adjusted to 5 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.9g continue stirring 32 minutes, are then allowed to stand 50 minutes, filtering, obtain third filtrate；Filter cake is through 110 DEG C obtain chromium hydroxide 1.81g within dry 1 hour；
The pH of third filtrate is adjusted to 7 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.9g continue stirring 28 minutes, are then allowed to stand 50 minutes, filtering, obtain the 4th filtrate；Filter cake is through 110 DEG C obtain nickel hydroxide 6.6g within dry 1 hour；
The pH of 4th filtrate is adjusted to 8 with the potassium hydroxide aqueous solution that mass fraction is 35%, polyacrylamide is added 0.1g, aluminium polychloride 1.85g continue stirring 40 minutes, are then allowed to stand 25 minutes, filtering, obtain the 5th filtrate and the 5th filter Cake, filter cake obtain manganous hydroxide 0.41g in dry 1 hour through 110 DEG C.
Through detecting, fluorine-containing 4.0mg/L in the 5th filtrate, iron content 2.9mg/L, 0.17mg/L containing chromium (are free of high valence chrome), contain Nickel 0.25mg/L, does not detect manganese.
The 5th filtrate 10Kg is collected, the pH of the 5th filtrate is adjusted to 7 with the potassium hydroxide aqueous solution that mass fraction is 35%, Then it is handled through reverse osmosis membrane (RO film), obtains clear water 8.5Kg, condensed water 1.5Kg；Clear water discharge, condensed water through triple effect evaporation at Reason, it is 110-140 DEG C that triple effect evaporation, which controls temperature range, evaporative cooling liquid qualified discharge, and dope is concentrated under reduced pressure, after crystallisation by cooling It filters, be dried to obtain inorganic salts 750g, then carry out harmless treatment, filtrate returns to triple effect evaporation or discharge.
The mode of harmless treatment are as follows: take quartz sand that suitable sodium carbonate is added, be heated to quartz sand fusing, then slowly Above-mentioned inorganic salts are added, finish maintenance 10-20 minutes, then cooling crush is used to prepare concrete.
Comparative example
Pickling flush water same as Example 4 is taken, fluorine is removed according to the identical method of embodiment 4, then directly by it PH is adjusted to 7, and polyacrylamide 2g and aluminium polychloride 5g is added, and continues stirring 40 minutes, is then allowed to stand 25 minutes, filtering, point Analyse filter cake.
Contain iron hydroxide, nickel hydroxide, chromium hydroxide and manganous hydroxide in filter cake.In filtrate, fluorine-containing 4.0mg/L contains Iron 200mg/L, 186mg/L containing chromium (contain high valence chrome), nickeliferous 97mg/L, 128mg/L containing manganese.
Embodiment 4 and comparative example 1 are compared it is found that directly adjusting pH to neutrality, addition flocculant removes metal ion Method suffers from the drawback that 1. can not separate one by one, makes troubles to subsequent comprehensive utilization；2. removing efficient lower, filtrate In still still need to continue to post-process to reach discharge standard containing a large amount of metal ions.
The calcirm-fluoride that method provided by the present application obtains after processing can be used for making steel, and iron hydroxide is by turning crystalline substance Obtaining di-iron trioxide can be used for smelting iron, and nickel hydroxide, chromium hydroxide and manganous hydroxide are for manufacturing stainless steel material.
Each element in acid-washing stainless steel flushing water separation and Extraction one by one is reduced subsequent synthesis by the method that please provide itself The cost utilized, technological innovation drive market to carry out comprehensive utilization of resources, reach energy-saving and environment-friendly purpose.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

1. a kind of method for handling stainless steel acid cleaning waste water, which is characterized in that the described method comprises the following steps:
A. the pH of the fluorine-containing flushing water of acid-washing stainless steel is adjusted to 1-2, first is sequentially added under stirring, fluorine agent and second is gone to go Fluorine agent continues to stir after addition, is then allowed to stand, filters, and obtains the first filter cake and the first filtrate；
B. the pH of first filtrate is adjusted to 2-3, is added and removes ferric flocculant, continues to stir, be then allowed to stand, filter, obtain the Two filter cakes and the second filtrate；
C. the pH of second filtrate is adjusted to 4-5, polymer is added and removes chromium flocculant, continued to stir, be then allowed to stand, mistake Filter, obtains third filter cake and third filtrate；
D. the pH of the third filtrate is adjusted to 6-7, the polymer is added and except nickel flocculant, continues to stir, be then allowed to stand, Filtering, obtains the 4th filter cake and the 4th filtrate；
E. the pH of the 4th filtrate is adjusted to 7-8, then through film process, condensed water is handled through triple effect evaporation, the cooling knot of dope It is brilliant then to carry out harmless treatment.
2. the method according to claim 1, wherein further including demanganization step F between the step D and E: by institute The pH for stating the 4th filtrate is adjusted to 7-8, and the polymer and demanganization flocculant is added, and continues to stir, and is then allowed to stand, filters, obtains 5th filter cake and the 5th filtrate；
Then the 4th filtrate is substituted with the 5th filtrate execute the step E.
3. according to the method described in claim 2, it is characterized in that, continuing the time of stirring in the step F as 15-40 points Clock, the time of standing are 25-60 minutes；5th filter cake is manganous hydroxide.
4. according to the method described in claim 2, using mass fraction when it is characterized in that, adjusting pH is the hydrogen of 25-35% Sodium oxide molybdena or potassium hydroxide aqueous solution.
5. according to the method described in claim 2, it is characterized in that, it is described except ferric flocculant, it is described except chromium flocculant, described remove Nickel flocculant, the demanganization flocculant are cationic surfactant, and the cationic surfactant is polyacrylamide； The polymer is aluminium polychloride.
6. described second removes fluorine the method according to claim 1, wherein described first goes fluorine agent for calcium chloride Agent is aluminum aluminum sulfate；In the step A, the time for continuing stirring is 25-35 minutes, and the time of standing is 50-70 minutes；It is described First filter cake is calcirm-fluoride.
7. according to the method described in claim 6, it is characterized in that, continuing the time of stirring in the step B as 5-15 points Clock, the time of standing are 15-60 minutes；Second filter cake is iron hydroxide.
8. the method according to the description of claim 7 is characterized in that continuing the time of stirring in the step C as 15-35 points Clock, the time of standing are 25-60 minutes；The third filter cake is chromium hydroxide.
9. according to the method described in claim 8, it is characterized in that, continuing the time of stirring in the step D as 25-35 points Clock, the time of standing are 35-60 minutes；4th filter cake is nickel hydroxide.
10. -9 described in any item methods according to claim 1, which is characterized in that film used in the film process is reverse osmosis Permeable membrane；In the triple effect evaporation processing, temperature control is 110-140 DEG C.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002322581A (en) * 2001-04-25 2002-11-08 Kawasaki Steel Corp Method for regenerating waste solution of nitric- hydrofluoric acid and method for pickling stainless steel
CN101096276A (en) * 2007-06-22 2008-01-02 陈启松 Method for abstracting chromium and nickel salt for stainless steel acid-washing wastewater
CN102757142A (en) * 2012-08-06 2012-10-31 浙江海拓环境技术有限公司 Method for recycling and processing nickel in stainless steel pickling waste acid
CN104805291A (en) * 2015-04-16 2015-07-29 南阳师范学院 Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002322581A (en) * 2001-04-25 2002-11-08 Kawasaki Steel Corp Method for regenerating waste solution of nitric- hydrofluoric acid and method for pickling stainless steel
CN101096276A (en) * 2007-06-22 2008-01-02 陈启松 Method for abstracting chromium and nickel salt for stainless steel acid-washing wastewater
CN102757142A (en) * 2012-08-06 2012-10-31 浙江海拓环境技术有限公司 Method for recycling and processing nickel in stainless steel pickling waste acid
CN104805291A (en) * 2015-04-16 2015-07-29 南阳师范学院 Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel

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