CN105481001A - Optimized method for recycling electrogalvanizing waste zinc - Google Patents
Optimized method for recycling electrogalvanizing waste zinc Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01G9/00—Compounds of zinc
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Abstract
The invention discloses an optimized method for recycling electrogalvanizing waste zinc. An appropriate method and an appropriate treating agent are selected according to the chemical property that a solid product of electrogalvanizing wastewater contains a main ingredient zinc-containing mud cake, optimization operation is carried out in the steps of acid leaching, evaporation concentration oxidation, replacement treatment and neutralizing treatment, and finally a zinc product zinc oxide is obtained. Compared with the traditional recycling method, recovery rate of zinc is greatly improved, recycling cost is low, technology is simple, no wastewater is discharged, new pollution is not produced, and environmental and economic values are realized.
Description
Technical field
The present invention relates to a kind of recovery method of metal, especially relate to a kind of optimization method of electro-galvanizing waste zinc recovering.
Background technology
The zinc-plated superior protection coating as ferrous metal, application is quite general, almost accounts for 60% ~ 70% of each plating in the industry such as electromechanics, building, five metals.The use of the passive film of shades of colour, not only increases decorative effect, and also improves erosion resistance.But along with people zincincation constantly developed and promote, creating in a large number to environment, material that human body is harmful.
Three industrial wastes are day by day serious on the impact of environmental quality, especially heavy metal contamination.The heavy metal entered in soil not only affects soil fertility and quality of agricultural product, simultaneously can through delivering path enrichments in animal and plant body such as water, air, crops.Some heavy metal highly toxic substances wherein, have the effect of carcinogenic, teratogenesis and modificator gene sudden change, thus bring health risk to the mankind.So extremely urgent to the recycling work of three industrial wastes, the recycling of three industrial wastes and recycling not only can realize the recycling of Nonrenewable resources, also mitigate the pollution to environment and the harm to human health simultaneously.
The final solid product of waste water from electric galvanization after limestone vegetation-filtration treatment is for containing zinc mud cake, and zinc content about 20%, if it directly to be thrown aside slag field, by osmosis pollution cienega, and can also exist the problem of the wasting of resources.
If a kind of effective zinc recovering method can be provided, it will be a problem having the value of environmental protection and economic worth concurrently.There is certain defect in the acid leaching process of current zinc recovering treatment process, result in zinc recovery general not high.
Summary of the invention
Goal of the invention: in order to solve in prior art existing electro-galvanizing discarded mud cake in the not high problem of the rate of recovery of zinc, the present invention proposes the optimization method carrying out the recycling of zinc for the discarded mud cake containing zinc that a kind of rate of recovery is high, process costs is low.
Technical scheme: to achieve these objectives, the present invention takes following technical scheme:
An optimization method for electro-galvanizing waste zinc recovering, comprises following optimization step:
(1) optimization of step of acid dipping: mud cake is placed in mixed acid solution and carries out stage leaching process, the mixture of the hydrochloric acid of mixing acid to be volume ratio be 3:2:3, acetic acid, sulfuric acid, the pH value of leach liquor is measured every 20min, pH often raises 1, again mixing acid is added to initial pH, do not continue to add mixing acid after leaching process 2h, take out to filter when pH terminal is 5.0-5.5 and preserve filtrate, reject filter residue;
(2) optimization of evaporation concentration oxidation step: the filtrate that step (1) obtains is carried out evaporation concentration, when being heated to 70 DEG C, adds oxygenant a, continues the operation of heating and continuous evaporation concentration after holding temperature continuous heating 50-60min; Obtain crystallization after being heated to constant weight, after filtration, preserve filtrate, reject filter residue;
(3) optimization of replacement Treatment: add reductive agent a in the filtrate that step (2) obtains, dosage is 0.5g/L, temperature of reaction is 70-80 DEG C, reduce temperature after reaction 20-40min and add reductive agent b again to 50-60 DEG C, dosage is 0.2g/L, reaction times is filter after 15-20min to preserve filtrate, reject filter residue;
(4) secondary oxidation: the filtrate that step (3) obtains heated, when being heated to 70 DEG C, adds oxygenant b, is cooled to room temperature after holding temperature continuous heating 50-60min, filters and preserves filtrate, reject filter residue;
(5) optimization of neutralization procedure: add acid in alkali lye He excessive, and add discoloring agent a, reaction 30min post-heating filters after continuing to add discoloring agent b reaction 30min to 50-60 DEG C and abandons filter residue, obtains filtrate;
(6) drying and calcining: drying and calcining is carried out to the filtrate that step (5) obtains, obtains zinc oxide.
More preferred, in described step (1), the temperature of acidleach is 40-50 DEG C.
More preferred, in described step (1), the initial liquid-solid ratio of acidleach is 5:1.
More preferred, the middle oxygenant a of described step (2) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:1:1.
More preferred, in described step (3), reductive agent a is zinc powder, and reductive agent b is sodium block.
More preferred, the middle oxygenant b of described step (4) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:2:1.
More preferred, the middle discoloring agent a of described step (5) is anhydrous slufuric acid aluminium, anhydrous magnesium sulfate, wilkinite three mass ratio are the mixture of 3:1:2; Discoloring agent b is anhydrous slufuric acid aluminium, both anhydrous magnesium sulfates mass ratio is the mixture of 1:2.
More preferred, in described step (5), alkali lye selects the one in sodium hydroxide, potassium hydroxide.
Beneficial effect: the optimization method of a kind of electro-galvanizing waste zinc recovering provided by the invention, the chemical property of zinc mud cake main component is contained according to the solid product of waste water from electric galvanization, select suitable treatment process and treatment agent, operation is optimized in acidleach, evaporation concentration oxidation, replacement Treatment, the several step of neutralizing treatment, finally obtain the zinc product of zinc oxide, the rate of recovery of zinc comparatively conventional recovery method is enhanced, cost recovery is low, technique is simple, non-wastewater discharge, do not produce new pollution, have environmental protection and economic worth concurrently.
Embodiment
Embodiment 1:
An optimization method for electro-galvanizing waste zinc recovering, comprises following optimization step:
(1) optimization of step of acid dipping: mud cake is placed in mixed acid solution and carries out stage leaching process, the mixture of the hydrochloric acid of mixing acid to be volume ratio be 3:2:3, acetic acid, sulfuric acid, the pH value of leach liquor is measured every 20min, pH often raises 1, again mixing acid is added to initial pH, do not continue to add mixing acid after leaching process 2h, take out to filter when pH terminal is 5.0 and preserve filtrate, reject filter residue;
(2) optimization of evaporation concentration oxidation step: the filtrate that step (1) obtains is carried out evaporation concentration, when being heated to 70 DEG C, adds oxygenant a, continues the operation of heating and continuous evaporation concentration after holding temperature continuous heating 50min; Obtain crystallization after being heated to constant weight, after filtration, preserve filtrate, reject filter residue;
(3) optimization of replacement Treatment: add reductive agent a in the filtrate that step (2) obtains, dosage is 0.5g/L, temperature of reaction is 70 DEG C, reduce temperature to 50 DEG C after reaction 20min and add reductive agent b again, dosage is 0.2g/L, reaction times is filter after 15min to preserve filtrate, reject filter residue;
(4) secondary oxidation: the filtrate that step (3) obtains heated, when being heated to 70 DEG C, adds oxygenant b, is cooled to room temperature after holding temperature continuous heating 50min, filters and preserves filtrate, reject filter residue;
(5) optimization of neutralization procedure: add acid in alkali lye He excessive, and add discoloring agent a, reaction 30min post-heating to 50 DEG C filters after continuing to add discoloring agent b reaction 30min and abandons filter residue, obtains filtrate;
(6) drying and calcining: drying and calcining is carried out to the filtrate that step (5) obtains, obtains zinc oxide.
Wherein, in described step (1), the temperature of acidleach is 40 DEG C; The initial liquid-solid ratio of acidleach is 5:1; The middle oxygenant a of described step (2) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:1:1; In step (3), reductive agent a is zinc powder, and reductive agent b is sodium block; The middle oxygenant b of step (4) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:2:1; The middle discoloring agent a of step (5) is anhydrous slufuric acid aluminium, anhydrous magnesium sulfate, wilkinite three mass ratio are the mixture of 3:1:2; Discoloring agent b is anhydrous slufuric acid aluminium, both anhydrous magnesium sulfates mass ratio is the mixture of 1:2; In step (5), alkali lye selects sodium hydroxide.
Embodiment 2:
An optimization method for electro-galvanizing waste zinc recovering, comprises following optimization step:
(1) optimization of step of acid dipping: mud cake is placed in mixed acid solution and carries out stage leaching process, the mixture of the hydrochloric acid of mixing acid to be volume ratio be 3:2:3, acetic acid, sulfuric acid, the pH value of leach liquor is measured every 20min, pH often raises 1, again mixing acid is added to initial pH, do not continue to add mixing acid after leaching process 2h, take out to filter when pH terminal is 5.5 and preserve filtrate, reject filter residue;
(2) optimization of evaporation concentration oxidation step: the filtrate that step (1) obtains is carried out evaporation concentration, when being heated to 70 DEG C, adds oxygenant a, continues the operation of heating and continuous evaporation concentration after holding temperature continuous heating 60min; Obtain crystallization after being heated to constant weight, after filtration, preserve filtrate, reject filter residue;
(3) optimization of replacement Treatment: add reductive agent a in the filtrate that step (2) obtains, dosage is 0.5g/L, temperature of reaction is 80 DEG C, reduce temperature to 60 DEG C after reaction 40min and add reductive agent b again, dosage is 0.2g/L, reaction times is filter after 20min to preserve filtrate, reject filter residue;
(4) secondary oxidation: the filtrate that step (3) obtains heated, when being heated to 70 DEG C, adds oxygenant b, is cooled to room temperature after holding temperature continuous heating 60min, filters and preserves filtrate, reject filter residue;
(5) optimization of neutralization procedure: add acid in alkali lye He excessive, and add discoloring agent a, reaction 30min post-heating to 60 DEG C filters after continuing to add discoloring agent b reaction 30min and abandons filter residue, obtains filtrate;
(6) drying and calcining: drying and calcining is carried out to the filtrate that step (5) obtains, obtains zinc oxide.
Wherein, in described step (1), the temperature of acidleach is 50 DEG C; The initial liquid-solid ratio of acidleach is 5:1; The middle oxygenant a of described step (2) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:1:1; In step (3), reductive agent a is zinc powder, and reductive agent b is sodium block; The middle oxygenant b of step (4) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:2:1; The middle discoloring agent a of step (5) is anhydrous slufuric acid aluminium, anhydrous magnesium sulfate, wilkinite three mass ratio are the mixture of 3:1:2; Discoloring agent b is anhydrous slufuric acid aluminium, both anhydrous magnesium sulfates mass ratio is the mixture of 1:2; Alkali lye selects potassium hydroxide.
Embodiment 3:
An optimization method for electro-galvanizing waste zinc recovering, comprises following optimization step:
(1) optimization of step of acid dipping: mud cake is placed in mixed acid solution and carries out stage leaching process, the mixture of the hydrochloric acid of mixing acid to be volume ratio be 3:2:3, acetic acid, sulfuric acid, the pH value of leach liquor is measured every 20min, pH often raises 1, again mixing acid is added to initial pH, do not continue to add mixing acid after leaching process 2h, take out to filter when pH terminal is 5.2 and preserve filtrate, reject filter residue;
(2) optimization of evaporation concentration oxidation step: the filtrate that step (1) obtains is carried out evaporation concentration, when being heated to 70 DEG C, adds oxygenant a, continues the operation of heating and continuous evaporation concentration after holding temperature continuous heating 55min; Obtain crystallization after being heated to constant weight, after filtration, preserve filtrate, reject filter residue;
(3) optimization of replacement Treatment: add reductive agent a in the filtrate that step (2) obtains, dosage is 0.5g/L, temperature of reaction is 75 DEG C, reduce temperature to 55 DEG C after reaction 30min and add reductive agent b again, dosage is 0.2g/L, reaction times is filter after 17min to preserve filtrate, reject filter residue;
(4) secondary oxidation: the filtrate that step (3) obtains heated, when being heated to 70 DEG C, adds oxygenant b, is cooled to room temperature after holding temperature continuous heating 55min, filters and preserves filtrate, reject filter residue;
(5) optimization of neutralization procedure: add acid in alkali lye He excessive, and add discoloring agent a, reaction 30min post-heating to 55 DEG C filters after continuing to add discoloring agent b reaction 30min and abandons filter residue, obtains filtrate;
(6) drying and calcining: drying and calcining is carried out to the filtrate that step (5) obtains, obtains zinc oxide.
Wherein, in described step (1), the temperature of acidleach is 45 DEG C; The initial liquid-solid ratio of acidleach is 5:1; The middle oxygenant a of described step (2) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:1:1; In step (3), reductive agent a is zinc powder, and reductive agent b is sodium block; The middle oxygenant b of step (4) is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio are the mixture of 3:2:1; The middle discoloring agent a of step (5) is anhydrous slufuric acid aluminium, anhydrous magnesium sulfate, wilkinite three mass ratio are the mixture of 3:1:2; Discoloring agent b is anhydrous slufuric acid aluminium, both anhydrous magnesium sulfates mass ratio is the mixture of 1:2; Alkali lye selects sodium hydroxide.
Adopt the method for the recovery zinc of embodiment of the present invention 1-3 to recycle its discarded zinc mud cake that contains in Suzhou City of Jiangsu Province company electro-galvanizing workshop, arrange simultaneously and adopt conventional recovery method to carry out the control group processed, concrete test-results is as shown in the table:
| Zinc recovery | Produce the cost of 1t zinc oxide | |
| Embodiment 1 | 88.6％ | 3734 yuan |
| Embodiment 2 | 89.8％ | 3647 yuan |
| Embodiment 3 | 87.9％ | 3834 yuan |
| Control group | 60.5％ | 6542 yuan |
Can draw from upper table data, the more traditional recovery process of optimization method of a kind of electro-galvanizing of the present invention waste zinc recovering, zinc recovery has had the raising of about 27%, the cost producing 1t zinc oxide also reduces about 2500 yuan, economic worth is remarkable, and technique is simple, non-wastewater discharge, do not produce new pollution, have environmental protection and economic worth concurrently.
It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (8)
1. an optimization method for electro-galvanizing waste zinc recovering, is characterized in that being to comprise following optimization step:
(1) optimization of step of acid dipping: mud cake is placed in mixed acid solution and carries out stage leaching process, the mixture of the hydrochloric acid of mixing acid to be volume ratio be 3:2:3, acetic acid, sulfuric acid, the pH value of leach liquor is measured every 20min, pH often raises 1, again mixing acid is added to initial pH, do not continue to add mixing acid after leaching process 2h, take out to filter when pH terminal is 5.0-5.5 and preserve filtrate, reject filter residue;
(2) optimization of evaporation concentration oxidation step: the filtrate that step (1) obtains is carried out evaporation concentration, when being heated to 70 DEG C, adds oxygenant a, continues the operation of heating and continuous evaporation concentration after holding temperature continuous heating 50-60min; Obtain crystallization after being heated to constant weight, after filtration, preserve filtrate, reject filter residue;
(3) optimization of replacement Treatment: add reductive agent a in the filtrate that step (2) obtains, dosage is 0.5g/L, temperature of reaction is 70-80 DEG C, reduce temperature after reaction 20-40min and add reductive agent b again to 50-60 DEG C, dosage is 0.2g/L, reaction times is filter after 15-20min to preserve filtrate, reject filter residue;
(4) secondary oxidation: the filtrate that step (3) obtains heated, when being heated to 70 DEG C, adds oxygenant b, is cooled to room temperature after holding temperature continuous heating 50-60min, filters and preserves filtrate, reject filter residue;
(5) optimization of neutralization procedure: add acid in alkali lye He excessive, and add discoloring agent a, reaction 30min post-heating filters after continuing to add discoloring agent b reaction 30min to 50-60 DEG C and abandons filter residue, obtains filtrate;
(6) drying and calcining: drying and calcining is carried out to the filtrate that step (5) obtains, obtains zinc oxide.
2. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (1), the temperature of acidleach is 40-50 DEG C.
3. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (1), the initial liquid-solid ratio of acidleach is 5:1.
4. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (2), oxygenant a is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio be the mixture of 3:1:1.
5. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (3), reductive agent a is zinc powder, and reductive agent b is sodium block.
6. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (4), oxygenant b is potassium permanganate, Potassium Persulphate, potassium hypochlorite mass ratio be the mixture of 3:2:1.
7. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (5), discoloring agent a is anhydrous slufuric acid aluminium, anhydrous magnesium sulfate, wilkinite three mass ratio be the mixture of 3:1:2; Discoloring agent b is anhydrous slufuric acid aluminium, both anhydrous magnesium sulfates mass ratio is the mixture of 1:2.
8. the optimization method of a kind of electro-galvanizing waste zinc recovering according to claim 1, is characterized in that: in described step (5), alkali lye selects the one in sodium hydroxide, potassium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109183013A (en) * | 2018-10-25 | 2019-01-11 | 济南实达紧固件有限公司 | A kind of method that use mud cake containing zinc replaces zinc oxide to prepare phosphating solution |
| CN110683572A (en) * | 2019-09-23 | 2020-01-14 | 海西华汇化工机械有限公司 | Method for preparing nano zinc oxide from hot-dip galvanizing slag |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109183013A (en) * | 2018-10-25 | 2019-01-11 | 济南实达紧固件有限公司 | A kind of method that use mud cake containing zinc replaces zinc oxide to prepare phosphating solution |
| CN110683572A (en) * | 2019-09-23 | 2020-01-14 | 海西华汇化工机械有限公司 | Method for preparing nano zinc oxide from hot-dip galvanizing slag |
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