CN103539302B - Treatment method of zinc-containing and iron-containing waste acid - Google Patents
Treatment method of zinc-containing and iron-containing waste acid Download PDFInfo
- Publication number
- CN103539302B CN103539302B CN201310530805.2A CN201310530805A CN103539302B CN 103539302 B CN103539302 B CN 103539302B CN 201310530805 A CN201310530805 A CN 201310530805A CN 103539302 B CN103539302 B CN 103539302B
- Authority
- CN
- China
- Prior art keywords
- zinc
- iron
- spent acid
- filtrate
- containing spent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a treatment method of a zinc-containing and iron-containing waste acid. The method comprises the following steps: adding a reducing agent to the zinc-containing and iron-containing waste acid, and fully reacting to obtain a reducing liquid; filtering the reducing liquid to collect a first filtrate; adding concentrated sulfuric acid into the first filtrate, and uniformly stirring to obtain a mixed liquid; evaporating and concentrating the mixed liquid at 90-110 DEG C to obtain a concentrated liquid; filtering the concentrated liquid at 70-100 DEG C to obtain a mixture with solids of FeSO4.H2O and ZnSO4.H2O. A certain amount of zinc-containing and iron-containing waste acid and concentrated sulfuric acid is added into the filtered second filtrate for a concentration and crystallization process in the next cycle. According to the treatment method of the zinc-containing and iron-containing waste acid, heavy metal ions are replaced to single substances, and after solid impurities in the reducing liquid are filtered to remove, the concentrated sulfuric acid is added. The mixture is evaporated, concentrated and filtered to obtain the crystal mixture with solids of FeSO4.H2O and ZnSO4.H2O. The crystal mixture can be used as a mineral additive for feed. According to the treatment method of the zinc-containing and iron-containing waste acid, the recovery rates of zinc and iron are higher, and the product has broad market prospect.
Description
Technical field
The present invention relates to the process field of trade effluent, particularly relate to a kind for the treatment of process of zinc-iron-containing spent acid.
Background technology
Iron forms oxyphorase, myohaemoglobin, cytopigment and multiple oxidasic important component, as the carrier of oxygen, ensures the conveying of oxygen in body tissue, participate in redox processes complicated in body.Utilizing of animal iron deficiency or iron is bad, by causing the transport of oxygen, storage, dioxy than the disturbed metabolic processes such as transport and redox of carbon, affecting animal growth and even the various diseases such as anaemia occurring.
Zinc is the moiety of many metal acids and hormone, and the activity that there will be a known more than 80 kind of enzyme is relevant with zinc.Zinc participates in protein, carbohydrate and lipid metabolism by enzyme and hormone, participates in the synthesis of thymus nucleic acid and Yeast Nucleic Acid, and also with the growth of hair, the health of skin, the healing of wound, reproductive capability, bone road is grown, and the sense of taste and appetite etc. are relevant.Animal lacks zinc and shows as appetite and decline, and decreased growth, gives milk, egg drop reduction, and efficiency of feed utilization is low, and severe patient grows stoppings, thick disorderly by hair, come off, and skin joy is split, and wound not easily heals, the even death of diarrhoea, vomiting.Breeding stock lacks zinc reproductivity and declines, and produces stillborn foetus, fetal anomaly.Kind of fowl then shows as that hatching rate is low, dead germ increase etc.
Ferrous sulfate monohydrate is very stable in atmosphere, is not only not easily oxidized to and absorbs poor ferric salt, nor easy-weathering, be more convenient for storing and use are that one easily absorbs, high efficiency benefit iron iron preparation.Meanwhile, Zinc Sulphate Monohydrate because of not easily moisture absorption caking and the course of processing without the need to special processing, easy to use, and be widely used as zinc supplementation zinc preparation.Ferrous sulfate monohydrate and Zinc Sulphate Monohydrate are suitable iron, zinc feed additives.
In electroplating industry, iron and steel blank, before carrying out surface galvanizing, in order to remove the zone of oxidation of blank surface, generally can use hydrochloric acid to carry out acid pickling and rust removing to blank.
Producing underproof steel galvanization part and the steel galvanization part scrapped generally all will first through withdrawal plating, again to reclaim iron and steel blank.During strip, need will treat that the steel galvanization part of strip immerses in acid solution to remove the zinc coating on surface.Thus, containing a large amount of zinc, iron (ferrous iron and ferric iron) ion in the spent acid obtained after strip, in spent acid, Zn content is up to 10 ~ 100mg/L, and iron level is up to 100 ~ 1000mg/L.
Traditional treatment process containing the spent acid of zinc and iron first ferrous ion is completely oxidized to ferric ion, add the pH that alkali regulates spent acid again, ferric ion is converted into ferric hydroxide precipitate, because iron in waste liquid and zinc concentration are all very high, part zine ion can become zinc hydroxide precipitation, after ferric hydroxide precipitate in removing solution and zinc hydroxide precipitation, then reclaim the zine ion in solution.
Because ferric hydroxide precipitate and zinc hydroxide precipitation are all difficult to recycle, when causing the spent acid process containing zinc and iron, the rate of recovery of zinc and iron is low.
Summary of the invention
Based on this, be necessary to provide the treatment process of a kind of zinc and the higher zinc-iron-containing spent acid of iron recovery.
A treatment process for zinc-iron-containing spent acid, is characterized in that, comprises the steps:
In zinc-iron-containing spent acid, add reductive agent, fully obtain reduced liquid after reaction, described reductive agent is at least one in iron powder and zinc powder;
Described reduced liquid is filtered, collects the first filtrate;
In described first filtrate, add the vitriol oil, stir and obtain mixed solution;
By described mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain concentrated solution, the mass ratio of described concentrated solution and described mixed solution is 58 ~ 70:100;
By described concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
Wherein in an embodiment, the mass ratio of described zinc-iron-containing spent acid and described reductive agent is 1:0.02 ~ 0.07.
Wherein in an embodiment, in zinc-iron-containing spent acid, add reductive agent, fully obtain in the operation of reduced liquid after reaction, the time of reaction is 12 ~ 36 hours.
Wherein in an embodiment, the mass ratio of the described vitriol oil and described first filtrate is 1:0.15 ~ 0.3.
Wherein in an embodiment, described reduced liquid is filtered, collects in the operation of the first filtrate, described in be filtered into press filtration.
Wherein in an embodiment, described by described mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain in the operation of concentrated solution, described evaporation concentration is carried out under vacuum.
Wherein in an embodiment, described by described mixed solution in the operation of 90 DEG C ~ 110 DEG C of evaporation concentration, will evaporation produce condensation of gas, collect phlegma.
Wherein in an embodiment, described phlegma to be massfraction be 22.4% ~ 26.9% hydrochloric acid.
Wherein in an embodiment, described by described concentrated solution 70 DEG C ~ 100 DEG C filter operation in, described in be filtered into centrifuging.
Wherein in an embodiment, the treatment process of described zinc-iron-containing spent acid also comprises the steps:
Collect the second filtrate that described concentrated solution obtains after filtering at 70 DEG C ~ 100 DEG C;
In described first filtrate, add the vitriol oil and described second filtrate, stir and obtain mixed solution;
By described mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain concentrated solution, the mass ratio of described concentrated solution and described mixed solution is 58 ~ 70:100;
By described concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
The treatment process of above-mentioned zinc-iron-containing spent acid, by adding reductive agent in zinc-iron-containing spent acid, the iron ion of the trivalent in zinc-iron-containing spent acid is made to be converted into the iron ion of divalence, make the heavy metal ion in zinc-iron-containing spent acid be replaced into simple substance simultaneously, the vitriol oil was added after passing through to filter the solid impurity in reduced liquid again, filter after evaporation concentration, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.The treatment process of above-mentioned zinc-iron-containing spent acid, does not need the mode by adding alkali to make contamination precipitation in spent acid, thus makes the zinc in zinc-iron-containing spent acid and iron can be converted into vitriol product and recycle, and the organic efficiency of zinc and iron is all higher.
Accompanying drawing explanation
Fig. 1 is the process flow figure of the zinc-iron-containing spent acid of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The treatment process of the zinc-iron-containing spent acid of an embodiment as shown in Figure 1, comprises the steps.
S110: add reductive agent in zinc-iron-containing spent acid, fully obtains reduced liquid zinc-iron-containing spent acid after reaction.
Zinc-iron-containing spent acid can for the spent acid containing zinc and iron obtained after industrial strip process.Reductive agent is at least one in iron powder and zinc powder.Specifically, reductive agent can be the mixture of iron powder, zinc powder or iron powder and zinc powder.
In zinc-iron-containing spent acid, add at least one in iron powder and zinc powder, the ferric ion in zinc-iron-containing spent acid can be made to be converted into ferrous ion on the one hand; The content of zinc in reduced liquid, iron can be increased on the other hand, thus the zinc of mixture, the content of iron of the ferrous sulfate monohydrate obtained after regulating the process of zinc-iron-containing spent acid and Zinc Sulphate Monohydrate.
When adding reductive agent and process in zinc-iron-containing spent acid, the mass ratio of zinc-iron-containing spent acid and reductive agent can be 1:0.02 ~ 0.07.Be appreciated that in actual applications, the mass ratio of zinc-iron-containing spent acid and reductive agent also can be other ratios.
In the present embodiment, in zinc-iron-containing spent acid, add reductive agent, the time of reaction is 12 ~ 36 hours, is converted into ferrous ion completely to make the ferric ion in zinc-iron-containing spent acid.Make the heavy metal ion in zinc-iron-containing spent acid be replaced into simple substance simultaneously.
S120: reduced liquid is filtered, collects the first filtrate.
By reduced liquid is filtered, the solid impurity that can contain in filtering reduced liquid.
In the present embodiment, filtration can be press filtration.In other embodiments, filtration treatment also can be other common filtration treatment.
S130: add the vitriol oil in the first filtrate, stir and obtain mixed solution.
Add the vitriol oil toward the first filtrate, can make to introduce hydrogen ion and sulfate ion in mixed solution.Introducing hydrogen ion is in order to when evaporation concentration mixed solution, can steam the hydrochloric acid that boiling point is lower than sulfuric acid, and introducing sulfate ion is to obtain zinc, iron sulfate.
In the present embodiment, the mass ratio of the vitriol oil and the first filtrate can be 1:0.15 ~ 0.3.Be appreciated that the concentration of the vitriol oil added in the first filtrate is higher, the water of introducing is fewer, more effectively can save the time of follow-up evaporation concentration, saves cost.
S140: by mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain concentrated solution, the mass ratio of concentrated solution and mixed solution is 58 ~ 70:100.
By mixed solution is carried out evaporation concentration at 90 DEG C ~ 110 DEG C, hydrochloric acid lower for mixed solution mid-boiling point can be steamed.Until when the mass ratio of concentrated solution and mixed solution is 58 ~ 70:100, stops concentrated, the concentration of the ferrous ion in concentrated solution and divalent zinc ion can be made to reach crystallisation concentration.
In the present embodiment, evaporation concentration is carried out under vacuum.Evaporation concentration is carried out under vacuum, is conducive on the one hand collecting waste gas, containing hydrochloric acid in waste gas, if directly discharge the external world, pollutes the environment; On the other hand, under vacuum condition, the air pressure in reactor is lower, and the boiling point of mixed solution is also lower, can improve vaporization efficiency.
By the condensation of gas that mixed solution produces 90 DEG C ~ 110 DEG C evaporations, collect phlegma.In the present embodiment, phlegma to be massfraction be 22.4% ~ 26.9% hydrochloric acid.
S150: by concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
In the present embodiment, filtration be operating as centrifuging.In other embodiments, the operation of filtration can also be common filtration.The mode of filtering is adopted to obtain the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, simple to operate, do not need to consume too many energy.
By concentrated solution 70 DEG C ~ 100 DEG C filtrations, be conducive to the mixture obtaining ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.As shown in table 1, when the temperature of filtering is lower, the ferrous sulfate obtained is FeSO
44H
2o or FeSO
47H
2o.As shown in table 2, when the temperature of filtering is lower, the zinc sulfate obtained is ZnSO
47H
2o or ZnSO
46H
2o.
Table 1
| Aqueous temperature during FeSO4 crystallization/DEG C | <56.6 | 56.6～64.4 | >64.4 |
| FeSO4 crystal habit | FeSO 4·7H 2O | FeSO 4·4H 2O | FeSO 4·H 2O |
Table 2
| Aqueous temperature during ZnSO4 crystallization/DEG C | <39 | 39～60 | >60 |
| ZnSO4 crystal habit | ZnSO 4·7H 2O | ZnSO 4·6H 2O | ZnSO 4·H 2O |
The treatment process of above-mentioned zinc-iron-containing spent acid can also comprise the steps:
S10: collect the second filtrate that concentrated solution obtains after filtering at 70 DEG C ~ 100 DEG C.
S20: the second filtrate adding the vitriol oil and collect after filtering in the first filtrate, stirs and obtain the second mixed solution.
Add the vitriol oil can make to introduce hydrogen ion and sulfate ion in the second mixed solution.Introducing hydrogen ion is to can steam the boiling point hydrochloric acid lower than sulfuric acid when the second mixed solution concentrates, and introducing sulfate ion is to obtain zinc, iron sulfate.In addition, the second filtrate contains ferrous ion and divalent zinc ion, and the second mixed solution can be made to introduce more ferrous ion and divalent zinc ion.
In the present embodiment, the mass ratio of the vitriol oil and the first filtrate can be 1:0.15 ~ 0.3.Be appreciated that the concentration of the vitriol oil added in the first filtrate is higher, the water of introducing is fewer, more effectively can save the time of follow-up evaporation concentration, saves cost.
S30: by the second mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain concentrated solution, the mass ratio of concentrated solution and the second mixed solution is 58 ~ 70:100.
By the second mixed solution is carried out evaporation concentration at 90 DEG C ~ 110 DEG C, hydrochloric acid lower for the second mixed solution mid-boiling point can be steamed.Until when the mass ratio of concentrated solution and the second mixed solution is 58 ~ 70:100, stops concentrated, the concentration of the ferrous ion in the second mixed solution and divalent zinc ion can be made to reach crystallisation concentration.
In the present embodiment, evaporation concentration is carried out under vacuum.Evaporation concentration is carried out under vacuum, is conducive on the one hand collecting waste gas, containing hydrochloric acid in waste gas, if directly discharge the external world, pollutes the environment; On the other hand, under vacuum condition, the air pressure in reactor is lower, and the boiling point of mixed solution is also lower, can improve vaporization efficiency.
S40: by concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
In the present embodiment, filtration be operating as centrifuging.In other embodiments, the operation of filtration can also be common filtration.
By carrying out the operation of S10 ~ S40, recycle can be carried out by filtering rear second filtrate of collecting.When the content of the reductive agent added is fixing, the content of the zinc in the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate and iron can be made to reach stationary value.Be appreciated that zinc sulfate solubleness is less, when recycle number of times is less, the zinc ion concentration in the filtrate of collecting after centrifuging does not reach capacity, and in the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, Zn content is lower.When recycle number of times reaches certain number of times, the zinc ion concentration in the filtrate of collecting after filtering reaches capacity, and the Zn content of the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate reaches stationary value.In addition, liquid waste treatment system is also made to realize zero release.
The treatment process of above-mentioned zinc-iron-containing spent acid, by adding reductive agent in zinc-iron-containing spent acid, the iron ion of the trivalent in zinc-iron-containing spent acid is made to be converted into the iron ion of divalence, make the heavy metal ion in zinc-iron-containing spent acid be replaced into simple substance simultaneously, the vitriol oil was added after passing through to filter the solid impurity in reduced liquid again, filter after evaporation concentration, obtain ferrous sulfate monohydrate and Zinc Sulphate Monohydrate mixture.The treatment process of above-mentioned zinc-iron-containing spent acid, does not need the mode by adding alkali to make contamination precipitation in spent acid, thus makes the zinc in zinc-iron-containing spent acid and iron can be converted into vitriol product and recycle, and the organic efficiency of zinc and iron is all higher.
The product that treatment process obtains of above-mentioned zinc-iron-containing spent acid is FeSO
4h
2o and ZnSO
4h
2the mixture of O, stability is high, has both not easily absorbed water also not oxidizable.In addition, FeSO
4h
2o and ZnSO
4h
2the mixture of O is rich in zinc, ferro element, and purity is higher, can directly use, and is such as used as nutrition-fortifying agent and adds in animal-feed.
The treatment process of above-mentioned zinc-iron-containing spent acid avoids the difficult problem that iron is separated with zinc, has both avoided the waste of iron or zinc resource, it also avoid and adopts complicated extraction and separation technology.Simultaneously the method environmental protection, can not produce " three wastes " problem, and the hydrochloric acid purity that condensation is reclaimed is higher, can return strip producer and to use or for other industrial production.The filtrate also reusable edible obtained after adopting centrifuging, can not produce pollution.In addition, the technical process of the treatment process of above-mentioned zinc-iron-containing spent acid is short, equipment is simple, additional materials is few, cost is low.
Be specific embodiment part below.
Embodiment 1
In 50kg zinc-iron-containing spent acid, add 1kg iron powder leave standstill, react and obtain reduced liquid in 36 hours.Zine ion mass percentage in reduced liquid is 1.65%, ferrous ion mass percentage be 8.13% and hydrochloric acid mass percentage be 0.55%.
Reduced liquid is carried out press filtration process, collects the first filtrate.
First filtrate is added in vaporizer, slowly adds the vitriol oil of 7.5kg 98% under agitation, after stirring, obtain mixed solution.
Vacuumized by vaporizer, ON cycle water coolant, vaporizer is warming up to 90 DEG C, vacuum evaporation 1 hour, obtains concentrated solution.The mass ratio of concentrated solution and mixed solution is 70:100.Concentrated solution is carried out centrifuging, and the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, and wherein, the mass percent of iron is 28.11%, and the mass percent of zinc is 2.02%.
Embodiment 2
In 50kg zinc-iron-containing spent acid, add 2.5kg iron powder leave standstill, react and obtain reduced liquid in 24 hours.The mass percentage of zine ion, ferrous ion and hydrochloric acid etc. in untreated zinc-iron-containing spent acid and reduced liquid is as shown in table 3.
Table 3
Reduced liquid is carried out press filtration process, collects the first filtrate.First filtrate is added in vaporizer, slowly adds the vitriol oil of 15kg 65% under agitation, after stirring, obtain mixed solution.
Vacuumize, make evaporator pressure maintain-0.095MPa, ON cycle water coolant, vaporizer is warming up to 95 DEG C, vacuum evaporation obtains concentration liquid in 1.5 hours.The mass ratio of concentrated solution and mixed solution is 64:100.Concentrated solution is carried out centrifuging, and the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, and Mixture component analysis is in table 4, and wherein, the mass percent of ferrous ion is 28.12%, and the mass percent of zine ion is 2.19%.
Table 4
Embodiment 3
In 50kg zinc-iron-containing spent acid, add 2.5kg zinc powder leave standstill, react and obtain reduced liquid in 12 hours.Reduced liquid is carried out press filtration process, collects the first filtrate.First filtrate is added in vaporizer, slowly adds the vitriol oil of 7.5kg 98% under agitation, after stirring, obtain mixed solution.
Vacuumize, make evaporator pressure maintain-0.095MPa, ON cycle water coolant, vaporizer is warming up to 100 DEG C, vacuum evaporation obtains concentration liquid in 1.5 hours.The mass ratio of concentrated solution and mixed solution is 64:100.Concentrated solution is carried out spraying dry, obtains the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, wherein, the mass percent of ferrous ion is 23.5%, and the mass percent of zine ion is 7.05%.
Embodiment 4
Circulation 1:
Step 11, leaving standstill containing adding 3.5kg iron powder in the spent acid of zinc and iron of obtaining after 50kg industry strip process, react and obtain reduced liquid in 24 hours.Wherein, containing zine ion mass percentage in the spent acid of zinc and iron be 8.13%, ferrous ion mass percentage be 8.45% and hydrochloric acid mass percentage be 0.25%.
Step 12, reduced liquid is carried out press filtration process, collect the first filtrate.
Step 13, the first filtrate is added in vaporizer, slowly add the vitriol oil of 13kg 98% under agitation, after stirring, obtain mixed solution.
Step 14, vacuumize, make evaporator pressure maintain-0.095MPa, ON cycle water coolant, vaporizer is warming up to 110 DEG C, vacuum evaporation 1.5 hours, the mass ratio of concentrated solution and mixed solution is 58:100.
Step 15, by concentrated solution centrifuging, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
The second filtrate that step 16, collection centrifuging obtain is for subsequent use.
Circulation 2:
Carry out step 21, step 21 is identical with the operational condition of step 11.
Carry out step 22, step 22 is identical with the operational condition of step 12;
Step 23, the first filtrate is added in vaporizer, slowly add the vitriol oil of 13kg 98% under agitation, then add the second filtrate that step 16 in circulation 1 obtains, after stirring, obtain mixed solution.
Carry out step 24, step 24 is identical with the operational condition of step 14.
Carry out step 25, step 25 is identical with the operational condition of step 15.
Carry out step 26, step 26 is identical with the operational condition of step 16.
Then carry out circulation 3, circulation 4 and circulation 5, circulation 3, circulation 4 and circulation 5 operation with circulation 2 operation substantially identical.Different places is, the second filtrate added in circulation 3 is the second filtrate that in circulation 2, step 26 obtains, the second filtrate that circulation 4 adds is the second filtrate that circulation 3 obtains, and the rest may be inferred, and the second filtrate added in circulation 5 is the second filtrate obtained in circulation 4.
In the mixture of the ferrous sulfate monohydrate that circulation 1 ~ circulation 5 obtains and Zinc Sulphate Monohydrate, the content of zine ion is respectively 3.8%, 9.05%, 12.53%, 12.27%, 12.66%.
In the mixture of the ferrous sulfate monohydrate that circulation 5 obtains and Zinc Sulphate Monohydrate, the content of Zn2+ and Fe2+ is as shown in table 5.
Table 5
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a treatment process for zinc-iron-containing spent acid, is characterized in that, comprises the steps:
In zinc-iron-containing spent acid, add reductive agent, fully obtain reduced liquid after reaction, described reductive agent is at least one in iron powder and zinc powder;
Described reduced liquid is filtered, collects the first filtrate;
In described first filtrate, add the vitriol oil, stir and obtain mixed solution;
By described mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain concentrated solution, the mass ratio of described concentrated solution and described mixed solution is 58 ~ 70:100;
By described concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
2. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, the mass ratio of described zinc-iron-containing spent acid and described reductive agent is 1:0.02 ~ 0.07.
3. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, in zinc-iron-containing spent acid, add reductive agent, and fully obtain in the operation of reduced liquid after reaction, the time of reaction is 12 ~ 36 hours.
4. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, the mass ratio of the described vitriol oil and described first filtrate is 1:0.15 ~ 0.3.
5. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, is filtered by described reduced liquid, collects in the operation of the first filtrate, described in be filtered into press filtration.
6. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, described by described mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain in the operation of concentrated solution, described evaporation concentration is carried out under vacuum.
7. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, described by described mixed solution in the operation of 90 DEG C ~ 110 DEG C of evaporation concentration, will evaporation produce condensation of gas, collect phlegma.
8. the treatment process of zinc-iron-containing spent acid according to claim 7, is characterized in that, described phlegma to be massfraction be 22.4% ~ 26.9% hydrochloric acid.
9. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, described by described concentrated solution 70 DEG C ~ 100 DEG C filter operation in, described in be filtered into centrifuging.
10. the treatment process of zinc-iron-containing spent acid according to claim 1, is characterized in that, also comprise the steps:
Collect the second filtrate that described concentrated solution obtains after filtering at 70 DEG C ~ 100 DEG C;
In described first filtrate, add the vitriol oil and described second filtrate, stir and obtain the second mixed solution;
By described second mixed solution 90 DEG C ~ 110 DEG C evaporation concentration, obtain the second concentrated solution, the mass ratio of described second concentrated solution and described second mixed solution is 58 ~ 70:100;
By described second concentrated solution 70 DEG C ~ 100 DEG C filtrations, the solid obtained is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310530805.2A CN103539302B (en) | 2013-10-31 | 2013-10-31 | Treatment method of zinc-containing and iron-containing waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310530805.2A CN103539302B (en) | 2013-10-31 | 2013-10-31 | Treatment method of zinc-containing and iron-containing waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103539302A CN103539302A (en) | 2014-01-29 |
| CN103539302B true CN103539302B (en) | 2015-04-22 |
Family
ID=49963223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310530805.2A Active CN103539302B (en) | 2013-10-31 | 2013-10-31 | Treatment method of zinc-containing and iron-containing waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539302B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864254B (en) * | 2014-03-24 | 2015-08-12 | 南通市环境工程设计院有限公司 | The method of the deleading zinc process of steel cable acid washing phosphorization acid waste liquid and comprehensive utilization |
| CN104313320B (en) * | 2014-10-23 | 2017-04-05 | 云南煜锜环保科技有限公司 | The strong acid saturated crystallization separation method of zinc-magnesium in a kind of zinc electrolyte |
| CN107117992A (en) * | 2017-06-12 | 2017-09-01 | 贵州诺威施生物工程有限公司 | Calcium chloride preparation system and calcium chloride preparation method |
| CN108085489B (en) * | 2017-11-17 | 2019-06-07 | 昆明理工大学 | A kind of method that ferrous sulfate is precipitated in the crystallization of zinc hydrometallurgy solution |
| CN107954480A (en) * | 2017-12-18 | 2018-04-24 | 东北大学 | A kind of sludge extraction iron of iron content containing zinc and the method for preparing iron oxide |
| CN108751263A (en) * | 2018-06-08 | 2018-11-06 | 常州清流环保科技有限公司 | A kind of recovery and treatment method of iron content zinc pickle liquor and its application |
| CN112499668A (en) * | 2020-12-16 | 2021-03-16 | 中国船舶重工集团公司第七一八研究所 | Method and device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder |
| CN113476885A (en) * | 2021-07-08 | 2021-10-08 | 斯瑞尔环境科技股份有限公司 | Method for continuously producing iron salt crystals |
| CN113772873B (en) * | 2021-10-09 | 2023-08-25 | 北部湾大学 | Method for preparing industrial salt from pickling waste liquid by utilizing waste heat |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973574A (en) * | 2010-10-25 | 2011-02-16 | 汪晋强 | Method for preparing sulfates from waste residues in lithopone production |
| CN102689932A (en) * | 2011-03-24 | 2012-09-26 | 镇江市丹徒区江南热镀锌有限公司 | Separation and refining process for ferrous sulphate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3273901B2 (en) * | 1997-04-24 | 2002-04-15 | 日鉄鉱業株式会社 | Treatment method of hydrochloric acid waste liquid in which iron and zinc are dissolved |
| JP2002284509A (en) * | 2001-03-28 | 2002-10-03 | Osaka Gas Co Ltd | Treatment method of spent sulfuric acid and the treatment equipment |
-
2013
- 2013-10-31 CN CN201310530805.2A patent/CN103539302B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973574A (en) * | 2010-10-25 | 2011-02-16 | 汪晋强 | Method for preparing sulfates from waste residues in lithopone production |
| CN102689932A (en) * | 2011-03-24 | 2012-09-26 | 镇江市丹徒区江南热镀锌有限公司 | Separation and refining process for ferrous sulphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103539302A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539302B (en) | Treatment method of zinc-containing and iron-containing waste acid | |
| CN105696010B (en) | A kind of recoverying and utilizing method of iron content abraum salt containing zinc acid solution | |
| CN102107978B (en) | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry | |
| CN106495404B (en) | A kind of processing method of the high salinity cupric organic wastewater of highly acidity | |
| CN102276060A (en) | Method for treating acidic heavy-metal-containing sulfate wastewater by sulfate reducing bacteria | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN110510648A (en) | A method of separating and recovering aluminium, potassium and ammonium from the mixed solution of sulfur acid aluminium, potassium sulfate and ammonium sulfate | |
| CN105129838A (en) | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant | |
| CN104355497A (en) | Method for treating electroplating wastewater | |
| CN102910760A (en) | Treatment process of contaminated acid containing heavy metals | |
| CN1308897A (en) | Micronutrient additive | |
| CN102963921A (en) | Preparation method of electroplating-grade copper sulfate | |
| CN114702075A (en) | Purification preparation method of manganese sulfate | |
| CN101759315B (en) | Method for recycling waste diluted sulfuric acid from acid washing solution of steel | |
| CN103303964A (en) | Method for producing food-grade copper sulfate by smelting byproduct-copper sulfate | |
| CN103265083B (en) | Method for producing feed-grade manganese sulfate monohydrate | |
| US8911611B2 (en) | Method of obtaining electrolytic manganese from ferroalloy production waste | |
| CN111717930A (en) | Method for producing basic copper carbonate based on copper-containing etching waste liquid | |
| CN108675498B (en) | Method for resource utilization of stone coal acidic wastewater | |
| CN116462347A (en) | Treatment method of iron phosphate production wastewater | |
| CN113402096B (en) | Stripping and hanging waste liquid treatment method for PCB factory | |
| CN212864145U (en) | Phosphoric acid dearsenification system | |
| CN102718259B (en) | Method for depositing and converting arsenic wastewater into arsenic trioxide | |
| CN112357947A (en) | Preparation method for producing high-purity anhydrous copper sulfate by dynamic drying method | |
| CN102021338A (en) | Method for separating and enriching tellurium and nickel from electrolyte waste acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 516267 Laowuixia Village, Yonghu Town, Huiyang District, Huizhou City, Guangdong Province Patentee after: SRIEL ENVIRONMENTAL SCIENCE AND TECHNOLOGY CO., LTD. Address before: 516267 Laowuixia Village, Yonghu Town, Huiyang District, Huizhou City, Guangdong Province Patentee before: Huizhou Siruier Environment Chemical Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |