CN103539302A - Treatment method of zinc-containing and iron-containing waste acid - Google Patents
Treatment method of zinc-containing and iron-containing waste acid Download PDFInfo
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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 is to form oxyphorase, myohaemoglobin, cytopigment and multiple oxidasic important component, as the carrier of oxygen, guarantees the conveying of oxygen in body tissue, participates in redox processes complicated in body.Utilizing of animal iron deficiency or iron is bad, and by causing, transportation, storage, the dioxy of oxygen are more disorderly than metabolic processes such as the transportation of carbon and redox, affect animal growth the various diseases such as anaemia even occur.
Zinc is the moiety of many metal acids and hormone, and known have the activity of 80 plurality of enzymes relevant with zinc.Zinc participates in protein, carbohydrate and lipid metabolism by enzyme and hormone, participates in the synthetic of thymus nucleic acid and Yeast Nucleic Acid, also with the growth of hair, and the health of skin, the healing of wound, grow on reproductive capability ，Gu road, and the sense of taste and appetite etc. are relevant.Animal lacks zinc and shows as appetite and decline, and decreased growth is given milk, egg drop reduction, and efficiency of feed utilization is low, and severe patient grows and stops, thick disorderly by hair, come off, and skin joy is split, and wound is difficult for healing, and diarrhoea, vomiting are even dead.Breeding stock lacks zinc reproductivity and declines, and produces stillborn foetus, fetal anomaly.Kind of fowl shows as that hatching rate is low, dead germ increase etc.
Ferrous sulfate monohydrate is very stable in air, is not only difficult for being oxidized to absorbing poor ferric salt, nor easy-weathering, be more convenient for storing and use, be a kind of easy absorption, high efficiency benefit iron iron preparation.Meanwhile, Zinc Sulphate Monohydrate is because being difficult for moisture absorption caking and the course of processing without special processing, easy to use, and is 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 on blank surface, generally can be used hydrochloric acid to carry out acid pickling and rust removing to blank.
The steel galvanization part of producing underproof steel galvanization part and scrapping generally all will first pass through withdrawal plating, again to reclaim iron and steel blank.During strip, the steel galvanization part for the treatment of strip need be immersed in acid solution to remove surperficial zinc coating.Thereby, in the spent acid obtaining after strip, containing a large amount of zinc, iron (ferrous iron and ferric iron) ion, in spent acid, zinc content is up to 10～100mg/L, and iron level is up to 100～1000mg/L.
The treatment process of traditional spent acid containing zinc and iron is first ferrous ion to be completely oxidized to ferric ion, add again the pH that alkali regulates spent acid, ferric ion is converted into ferric hydroxide precipitate, due to iron in waste liquid and zinc concentration all very high, part zine ion can become zinc hydroxide precipitation, remove after the ferric hydroxide precipitate and zinc hydroxide precipitation in solution, then reclaim the zine ion in solution.
Because ferric hydroxide precipitate and zinc hydroxide precipitation is all difficult to recycle, while causing processing containing the spent acid of 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 the zinc-iron-containing spent acid that a kind of zinc and iron recovery are higher.
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 after reaction, obtain reduced liquid, described reductive agent is at least one in iron powder and zinc powder;
Described reduced liquid is filtered, collect the first filtrate;
In described the first filtrate, add the vitriol oil, stir and obtain mixed solution;
Described mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of described concentrated solution and described mixed solution is 58～70:100;
By described concentrated solution, 70 ℃～100 ℃ filtrations, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
In an embodiment, the mass ratio of described zinc-iron-containing spent acid and described reductive agent is 1:0.02～0.07 therein.
In an embodiment, in zinc-iron-containing spent acid, add reductive agent therein, fully after reaction, obtain in the operation of reduced liquid, the time of reaction is 12～36 hours.
In an embodiment, the mass ratio of the described vitriol oil and described the first filtrate is 1:0.15～0.3 therein.
Therein in an embodiment, described reduced liquid is filtered, collects in the operation of the first filtrate, described in be filtered into press filtration.
Therein in an embodiment, described by described mixed solution 90 ℃～110 ℃ evaporation concentration, obtain in the operation of concentrated solution, described evaporation concentration is carried out under vacuum condition.
Therein in an embodiment, described by described mixed solution in the operation of 90 ℃～110 ℃ of evaporation concentration, the condensation of gas will evaporation producing, collects phlegma.
In an embodiment, described phlegma is that massfraction is 22.4%～26.9% hydrochloric acid therein.
Therein in an embodiment, described by described concentrated solution in the operation of 70 ℃～100 ℃ of filtrations, described in be filtered into centrifuging.
In an embodiment, the treatment process of described zinc-iron-containing spent acid also comprises the steps: therein
Collect the second filtrate that described concentrated solution obtains after 70 ℃～100 ℃ filtrations;
In described the first filtrate, add the vitriol oil and described the second filtrate, stir and obtain mixed solution;
Described mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of described concentrated solution and described mixed solution is 58～70:100;
By described concentrated solution, 70 ℃～100 ℃ filtrations, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
The treatment process of above-mentioned zinc-iron-containing spent acid, by add reductive agent in zinc-iron-containing spent acid, make the iron ion of the trivalent in zinc-iron-containing spent acid 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, after removing by filter the solid impurity in reduced liquid, add the vitriol oil again, after evaporation concentration, filter, the solid obtaining 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 to make contamination precipitation in spent acid by adding the mode of alkali, thereby makes zinc and iron in zinc-iron-containing spent acid 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 above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to 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 obtain reduced liquid zinc-iron-containing spent acid after reaction.
Zinc-iron-containing spent acid can be the spent acid containing zinc and iron obtaining after industrial strip processing.Reductive agent is at least one in iron powder and zinc powder.Particularly, 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, can make the ferric ion in zinc-iron-containing spent acid be converted into ferrous ion on the one hand; Can increase the content of zinc in reduced liquid, iron on the other hand, thereby the zinc of mixture of the ferrous sulfate monohydrate obtaining after regulating zinc-iron-containing spent acid to process and Zinc Sulphate Monohydrate is, the content of iron.
When adding reductive agent to 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 can be also other ratios.
In the present embodiment, in zinc-iron-containing spent acid, add reductive agent, the time of reaction is 12～36 hours, so that the ferric ion in zinc-iron-containing spent acid is converted into ferrous ion completely.Make the heavy metal ion in zinc-iron-containing spent acid be replaced into simple substance simultaneously.
S120: reduced liquid is filtered, collect the first filtrate.
By reduced liquid is filtered, the solid impurity containing in can filtering reduced liquid.
In the present embodiment, filtration can be press filtration.In other embodiments, filtration treatment can be also 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 in mixed solution hydrogen ion and sulfate ion.Introduce hydrogen ion and be for when the evaporation concentration mixed solution, can steam the hydrochloric acid that boiling point is lower than sulfuric acid, introducing sulfate ion is in order 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.The concentration that is appreciated that the vitriol oil adding in the first filtrate is higher, and the water of introducing is fewer, more can effectively save the time of follow-up evaporation concentration, saves cost.
S140: mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of concentrated solution and mixed solution is 58～70:100.
By mixed solution is carried out to evaporation concentration at 90 ℃～110 ℃, the lower hydrochloric acid of mixed solution mid-boiling point can be steamed.Until the mass ratio of concentrated solution and mixed solution while being 58～70:100, stops concentrating, can make ferrous ion in concentrated solution and the concentration of divalent zinc ion reach crystallization concentration.
In the present embodiment, evaporation concentration is carried out under vacuum condition.Evaporation concentration is carried out under vacuum condition, is conducive to collect waste gas on the one hand, contains hydrochloric acid in waste gas, if directly discharge is extraneous, 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.
The condensation of gas that mixed solution is produced 90 ℃～110 ℃ evaporations, collects phlegma.In the present embodiment, phlegma is that massfraction is 22.4%～26.9% hydrochloric acid.
S150: 70 ℃～100 ℃ filtrations, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate by concentrated solution.
In the present embodiment, filtration is operating as centrifuging.In other embodiments, the operation of filtration can also be common filtration.The mode that employing is filtered obtains the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate, simple to operate, does not need to consume too many energy.
Concentrated solution, 70 ℃～100 ℃ filtrations, is conducive to obtain the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.As shown in table 1, when the temperature of filtering is lower, the ferrous sulfate obtaining is FeSO
44H
2o or FeSO
47H
2o.As shown in table 2, when the temperature of filtering is lower, the zinc sulfate obtaining is ZnSO
47H
2o or ZnSO
46H
2o.
Table 1
| Aqueous temperature during FeSO4 crystallization/℃ | <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/℃ | <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 70 ℃～100 ℃ filtrations.
S20: add the vitriol oil and filter rear the second filtrate of collecting in the first filtrate, stir and obtain mixed solution.
Add the vitriol oil can make to introduce in mixed solution hydrogen ion and sulfate ion.Introducing hydrogen ion is that introducing sulfate ion is in order to obtain zinc, iron sulfate in order to steam the hydrochloric acid that boiling point is lower than sulfuric acid when mixed solution is concentrated.In addition, the second filtrate is contained ferrous ion and divalent zinc ion, can make mixed solution 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.The concentration that is appreciated that the vitriol oil adding in the first filtrate is higher, and the water of introducing is fewer, more can effectively save the time of follow-up evaporation concentration, saves cost.
S30: mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of concentrated solution and mixed solution is 58～70:100.
By mixed solution is carried out to evaporation concentration at 90 ℃～110 ℃, the lower hydrochloric acid of mixed solution mid-boiling point can be steamed.Until the mass ratio of concentrated solution and mixed solution while being 58～70:100, stops concentrating, can make ferrous ion in concentrated solution and the concentration of divalent zinc ion reach crystallization concentration.
In the present embodiment, evaporation concentration is carried out under vacuum condition.Evaporation concentration is carried out under vacuum condition, is conducive to collect waste gas on the one hand, contains hydrochloric acid in waste gas, if directly discharge is extraneous, 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: 70 ℃～100 ℃ filtrations, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate by concentrated solution.
In the present embodiment, filtration is operating as centrifuging.In other embodiments, the operation of filtration can also be common filtration.
By carrying out the operation of S10～S40, second filtrate of collecting after filtering can be carried out to recycle.In the situation that the content of the reductive agent adding is fixing, can make zinc in the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate and the content of iron 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, zinc 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 zinc content of the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate reaches stationary value.In addition, also make liquid waste treatment system realize zero release.
The treatment process of above-mentioned zinc-iron-containing spent acid, by add reductive agent in zinc-iron-containing spent acid, make the iron ion of the trivalent in zinc-iron-containing spent acid 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, after removing by filter the solid impurity in reduced liquid, add the vitriol oil again, after evaporation concentration, filter, obtain ferrous sulfate monohydrate and Zinc Sulphate Monohydrate mixture.The treatment process of above-mentioned zinc-iron-containing spent acid, does not need to make contamination precipitation in spent acid by adding the mode of alkali, thereby makes zinc and iron in zinc-iron-containing spent acid 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 been difficult for water suction 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, such as adding in animal-feed as nutrition-fortifying agent.
The treatment process of above-mentioned zinc-iron-containing spent acid has been avoided an iron difficult problem separated with zinc, has both avoided the waste of iron or zinc resource, has also avoided adopting 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 to that strip producer is used or for other industrial production.The filtrate obtaining after employing centrifuging is reusable edible also, can not produce pollution.In addition, the technical process of the treatment process of above-mentioned zinc-iron-containing spent acid is short, equipment simple, additional raw material is few, cost is low.
Be specific embodiment part below.
Embodiment 1
In 50kg zinc-iron-containing spent acid, add 1kg iron powder standing, react and within 36 hours, obtain reduced liquid.Zine ion quality percentage composition in reduced liquid is 1.65%, ferrous ion quality percentage composition be 8.13% and hydrochloric acid quality percentage composition be 0.55%.
Reduced liquid is carried out to press filtration processing, collect the first filtrate.
The first filtrate is added in vaporizer, under agitation condition, slowly add the vitriol oil of 7.5kg98%, after stirring, obtain mixed solution.
Vaporizer is vacuumized, and ON cycle water coolant, is warming up to 90 ℃ by vaporizer, and vacuum evaporation 1 hour, obtains concentrated solution.The mass ratio of concentrated solution and mixed solution is 70:100.Concentrated solution is carried out to centrifuging, and the solid obtaining 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 standing, react and within 24 hours, obtain reduced liquid.The quality percentage composition 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 to press filtration processing, collect the first filtrate.The first filtrate is added in vaporizer, under agitation condition, slowly add the vitriol oil of 15kg65%, after stirring, obtain mixed solution.
Vacuumize, make maintain-0.095MPa of evaporator pressure, ON cycle water coolant, is warming up to 95 ℃ by vaporizer, and vacuum evaporation obtains concentration liquid for 1.5 hours.The mass ratio of concentrated solution and mixed solution is 64:100.Concentrated solution is carried out to centrifuging, and the solid obtaining 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 standing, react and within 12 hours, obtain reduced liquid.Reduced liquid is carried out to press filtration processing, collect the first filtrate.The first filtrate is added in vaporizer, under agitation condition, slowly add the vitriol oil of 7.5kg98%, after stirring, obtain mixed solution.
Vacuumize, make maintain-0.095MPa of evaporator pressure, ON cycle water coolant, is warming up to 100 ℃ by vaporizer, and vacuum evaporation obtains concentration liquid for 1.5 hours.The mass ratio of concentrated solution and mixed solution is 64:100.Concentrated solution is sprayed dry, obtain 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:
In step 11, the spent acid containing zinc and iron that obtains after 50kg industry strip is processed, add 3.5kg iron powder standing, react and within 24 hours, obtain reduced liquid.Wherein, containing zine ion quality percentage composition in the spent acid of zinc and iron be 8.13%, ferrous ion quality percentage composition be 8.45% and hydrochloric acid quality percentage composition be 0.25%.
Step 12, reduced liquid is carried out to press filtration processing, collect the first filtrate.
Step 13, the first filtrate is added in vaporizer, under agitation condition, slowly add the vitriol oil of 13kg98%, after stirring, obtain mixed solution.
Step 14, vacuumize, make maintain-0.095MPa of evaporator pressure, ON cycle water coolant, is warming up to 110 ℃ by vaporizer, vacuum evaporation 1.5 hours, and the mass ratio of concentrated solution and mixed solution is 58:100.
Step 15, by concentrated solution centrifuging, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
The second filtrate for later use that step 16, collection centrifuging obtain.
Circulation 2:
Carry out step 21, the operational condition of step 21 and step 11 is identical.
Carry out step 22, the operational condition of step 22 and step 12 is identical;
Step 23, the first filtrate is added in vaporizer, under agitation condition, slowly add the vitriol oil of 13kg98%, then add the second filtrate that in circulation 1, step 16 obtains, after stirring, obtain mixed solution.
Carry out step 24, the operational condition of step 24 and step 14 is identical.
Carry out step 25, the operational condition of step 25 and step 15 is identical.
Carry out step 26, the operational condition of step 26 and step 16 is identical.
Then circulate 3, circulate 4 and circulate 5, circulate 3, circulate 4 and circulate 5 operation and 2 the operation of circulating basic identical.Different places are, the second filtrate adding in circulation 3 is the second filtrate that in circulation 2, step 26 obtains, circulation 4 the second filtrates that add are circulation 3 the second filtrates that obtain, and the rest may be inferred, second filtrate of the second filtrate that adds in 5 circulated for obtaining in circulation 4.
In the mixture of circulation 1～circulate 5 ferrous sulfate monohydrates that obtain and Zinc Sulphate Monohydrate, the content of zine ion is respectively 3.8%, 9.05%, 12.53%, 12.27%, 12.66%.
Zn in the mixture of circulation 5 ferrous sulfate monohydrates that obtain and Zinc Sulphate Monohydrate
2+and Fe
2+content as shown in table 5.
Table 5
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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 after reaction, obtain reduced liquid, described reductive agent is at least one in iron powder and zinc powder;
Described reduced liquid is filtered, collect the first filtrate;
In described the first filtrate, add the vitriol oil, stir and obtain mixed solution;
Described mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of described concentrated solution and described mixed solution is 58～70:100;
By described concentrated solution, 70 ℃～100 ℃ filtrations, the solid obtaining 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, adds reductive agent, fully after reaction, obtains in the operation of reduced liquid, and 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 the 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, described reduced liquid is filtered, collect 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 ℃～110 ℃ evaporation concentration, obtain in the operation of concentrated solution, described evaporation concentration is carried out under vacuum condition.
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 ℃～110 ℃ of evaporation concentration, the condensation of gas will evaporation producing, collects phlegma.
8. the treatment process of zinc-iron-containing spent acid according to claim 7, is characterized in that, described phlegma is that massfraction is 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 in the operation of 70 ℃～100 ℃ of filtrations, 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 comprises the steps:
Collect the second filtrate that described concentrated solution obtains after 70 ℃～100 ℃ filtrations;
In described the first filtrate, add the vitriol oil and described the second filtrate, stir and obtain mixed solution;
Described mixed solution, 90 ℃～110 ℃ evaporation concentration, is obtained to concentrated solution, and the mass ratio of described concentrated solution and described mixed solution is 58～70:100;
By described concentrated solution, 70 ℃～100 ℃ filtrations, the solid obtaining is the mixture of ferrous sulfate monohydrate and Zinc Sulphate Monohydrate.
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| CN103864254A (en) * | 2014-03-24 | 2014-06-18 | 南通市环境工程设计院有限公司 | Lead and zinc treatment and comprehensive utilization method of pickling and phosphorizing acidic waste liquid of wire cable |
| 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 |
| CN104313320A (en) * | 2014-10-23 | 2015-01-28 | 昆明绩驰环保科技有限公司 | Saturated crystal separation method for zinc and magnesium in zinc electrolyte by using strong acid |
| 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 |
| CN108085489A (en) * | 2017-11-17 | 2018-05-29 | 昆明理工大学 | A kind of method that ferrous sulfate is precipitated in zinc hydrometallurgy solution crystallization |
| 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 |
| CN113772873A (en) * | 2021-10-09 | 2021-12-10 | 北部湾大学 | Method for preparing industrial salt from pickling waste liquid by using waste heat |
| 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 |
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