CN107555469A - A kind of technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia - Google Patents
A kind of technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia Download PDFInfo
- Publication number
- CN107555469A CN107555469A CN201710745323.7A CN201710745323A CN107555469A CN 107555469 A CN107555469 A CN 107555469A CN 201710745323 A CN201710745323 A CN 201710745323A CN 107555469 A CN107555469 A CN 107555469A
- Authority
- CN
- China
- Prior art keywords
- zinc
- liquid
- chlorine
- cadmia
- chloride
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of technique that zinc sulfate combined producting ammonium chloride is prepared with high chlorine cadmia, the technique comprises the following steps：（1）Wash two sections of chlorine leached in high chlorine cadmia of ammonification；（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue；（3）The purification of chloride liquid；（4）The preparation of ammonium chloride；（5）The purification of zincate solution.The present invention is using washing ammonia leaching → acidleach substep separating technology, solve the problems, such as high chlorine cadmia application conventional wet smelting process technology recovery zinc and abandon the technical bottleneck of chlorine resource, so as to provide a kind of technique that zinc and chlorine are reclaimed from high chlorine cadmia, realize low cost recovery zinc and chlorine, ammonium chloride and sulfuric acid zinc product are produced, and realizes the environmentally friendly technology technology of zero emission.The valuable metal lead in high chlorine cadmia, cadmium, copper etc. is set to be enriched with and make its recycling again simultaneously.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, and in particular to valuable element synthetical recovery side in a kind of high chlorine cadmia
Method.
Background technology
High chlorine cadmia is the cigarette ash discharged during coloured and iron and steel industry through wet scrubber, sack cleaner, electrostatic
The blast furnace dust that the collections such as deduster obtain, and rich in metallic lead, cadmium, copper, zinc, tin etc., while also containing silicon, arsenic, chlorine, fluorine etc.
Nonmetalloid.At present, when being reclaimed to the valuable element in smelting ash, the metal member in reclaiming smelting cigarette ash is only considered
Element, and the elements such as chlorine therein, fluorine are directly discharged, environmental pollution is caused, and operating cost is high.
In Publication No. CN102534228《A kind of method of the synthetical recovery valuable element from high-arsenic-containing copper smelting soot》
In, using pyrogenic process-wet method combined technique, pass through（It is oxygen-enriched）Roasting → leaching → extraction → displacement → Crystallization Procedure is integrated
Reclaim the valuable element in high-arsenic-containing copper smelting soot.Although make time of the zinc in smelting ash, copper, lead, tin by this technology
Yield is more than 95%, but complex procedures, and equipment investment is big, and high energy consumption sulfuric acid consumption is big, and produces substantial amounts of sulfuric acid and give up
Liquid.
Li Xiaoling of Guangxi University et al.（Li Xiao reclaim research [D] the Guangxi University of copper zinc from high chlorine smelting ash,
2014）Copper zinc is reclaimed from high chlorine smelting ash using Whote-wet method technology.Be washed with water first → sodium carbonate liquor washing
Two sections of pre- dechlorination process carry out dechlorination to smelting ash, then to dechlorination slag soak the experiment of copper and zinc with sulfuric acid, then use oxygen
The impurity element such as As and Fe in change → neutralization → coprecipitation method removing pickle liquor.Electrodeposition finally is carried out to the leachate after removal of impurities
Reclaim copper and evaporative crystallization recovery zinc.By the technique, obtain good apparent mass and tough cathode of the purity more than 98.16% and
Monohydrate zinc sulphate.But this method has the following disadvantages：（1）Due to first neutralizing treatment sulfuric acid leaching again so that sulfuric acid consumption is big；
（2）Caused chloride liquid is expelled directly out in technique, pollution environment and waste of resource；（3）The impurity sodium carbonate increased newly in technique gives up
Liquid needs otherwise processed, so as to increase operating cost.
The content of the invention
It is an object of the invention to use washing-ammonia leaching → acidleach substep separating technology technology, solves high chlorine cadmia application
Conventional wet smelting process technology reclaims zinc and abandons the technical bottleneck problem of chlorine resource, so as to provide one kind from high chlorine cadmia
The technique for reclaiming zinc and chlorine, realize in low cost recovery zinc and chlorine, produce ammonium chloride and sulfuric acid zinc product, and realize the three wastes
The environmentally friendly technology technology of zero-emission.The valuable metal lead in high chlorine cadmia, cadmium, copper etc. is set to be enriched with and make it simultaneously
Recycling again.
The object of the invention and the technical problem underlying of solution are realized using following technical scheme：A kind of high chlorine zinc
Slag prepares the technique of zinc sulfate combined producting ammonium chloride, comprises the following steps：
（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 20~90 DEG C in washing temperature when washing high chlorine cadmia, liquid
Gu weight ratio is 2~8:1 and ball milling average grain diameter be 40~200 μm under conditions of, wash 0.5~3h after, separation of solid and liquid, obtain
Water lotion and washing slag；It is 7.0 in Leaching Systems pH value using ammoniacal liquor as pH adjuster when the chlorine in washing slag is leached in ammonification
~9.5, solvent and solute weight ratio is 2~8:1 and extraction temperature be 20~70 DEG C, leach 0.5~3h after, separation of solid and liquid, obtain ammonia leaching
Liquid and ammonia leaching residue；
（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：It it is 30~90 DEG C in reaction temperature, liquid is solid when leaching the zinc in ammonia leaching residue
Weight ratio is 2~6:1, hydrogen peroxide addition is the weight of hydrogen peroxide and solid than 0.1~0.6:1 and the addition of sulfuric acid be sulphur
Acid and zinc mol ratio 1.1~3 in ammonia leaching residue:Under conditions of 1, extraction time separation of solid and liquid, obtains soaking zinc up to after 20~200min
Liquid and zinc leaching residue；
（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and it is molten with 10~28% ammoniacal liquor
The pH value of liquid or ammonia regulation mixed liquor filtering, obtains purification slag and filtrate to 7.5~9.5, is added to filtrate in terms of sulfate radical
Coefficient of discharge is 0.2~1 calcium chloride solution, and filtering, most backward filtrate adds counts excess coefficient as 0.01~0.1 using calcium ion
Ammonium bicarbonate soln, filtering, the chloride liquid after being purified；
（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 4.5~7.5 with hydrochloric acid, then ions screen is added into solution
Agent, most obtain arrival ammonium chloride product through being evaporated under reduced pressure, condensing, crystallizing afterwards；Wherein, ion sequestering agent is added by every cube of chloride liquid
Enter 0.5~3 L；
（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve
Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 5.0~6.5, filtered,
Obtain filter residue and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, most obtained afterwards through being evaporated under reduced pressure, condensing, crystallizing
Sulfuric acid zinc product；Wherein, ion sequestering agent adds 0.5~4 L by every cube of chloride liquid.
A kind of foregoing technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia, it is characterised in that：Step（4）With
（5）Described in ion sequestering agent for ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, citric acid, sodium citrate, citric acid
In ammonium, tren, maleopimaric acid, dimercaprol dimercaptopropanol, DMPS, Succimer, double hydrogen phenylglycines
One or more.
Advantages of the present invention：
1）Using washing-ammonification extract technology, improve the wash-off rate of chlorine in high chlorine cadmia, greatly reduce follow-up dechlorination into
This；
2）Using oxidation acid leaching technology, the leaching rate of zinc in slag is substantially increased, the metallic element of other high added values is such as
Copper, nickel, the leaching rate of cobalt and tin also improve；
3）By substep impurity removal process, the separation and concentration of metallic element in high chlorine cadmia is realized, is enriched with lead, cadmium, copper etc.
And make its recycling again；
4）In ammonium chloride and zinc sulfate Product Process is prepared, add ion sequestering agent masking harmful element and improve the pure of product
Degree；And caused condensed water can realize the zero-emission of the three wastes as the leaching water of high chlorine cadmia in the process.
Embodiment
Below in conjunction with preferred embodiment, to preparing zinc sulfate coproduction chlorination with high chlorine cadmia according to one kind proposed by the present invention
Technique embodiment, feature and its effect of ammonium, describe in detail as after.
A kind of technique that zinc sulfate combined producting ammonium chloride is prepared with high chlorine cadmia, comprises the following steps：
（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 20~90 DEG C in washing temperature when washing high chlorine cadmia, liquid
Gu weight ratio is 2~8:1 and ball milling average grain diameter be 40~200 μm under conditions of, wash 0.5~3h after, separation of solid and liquid, obtain
Water lotion and washing slag；It is 7.0 in Leaching Systems pH value using ammoniacal liquor as pH adjuster when the chlorine in washing slag is leached in ammonification
~9.5, solvent and solute weight ratio is 2~8:1 and extraction temperature be 20~70 DEG C, leach 0.5~3h after, separation of solid and liquid, obtain ammonia leaching
Liquid and ammonia leaching residue；
（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：It it is 30~90 DEG C in reaction temperature, liquid is solid when leaching the zinc in ammonia leaching residue
Weight ratio is 2~6:1, hydrogen peroxide addition is the weight of hydrogen peroxide and solid than 0.1~0.6:1 and the addition of sulfuric acid be sulphur
Acid and zinc mol ratio 1.1~3 in ammonia leaching residue:Under conditions of 1, extraction time separation of solid and liquid, obtains soaking zinc up to after 20~200min
Liquid and zinc leaching residue；
（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and it is molten with 10~28% ammoniacal liquor
The pH value of liquid or ammonia regulation mixed liquor filtering, obtains purification slag and filtrate to 7.5~9.5, is added to filtrate in terms of sulfate radical
Coefficient of discharge is 0.2~1 calcium chloride solution, and filtering, most backward filtrate adds counts excess coefficient as 0.01~0.1 using calcium ion
Ammonium bicarbonate soln, filtering, the chloride liquid after being purified；
（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 4.5~7.5 with hydrochloric acid, then ions screen is added into solution
Agent, most obtain arrival ammonium chloride product through being evaporated under reduced pressure, condensing, crystallizing afterwards；Wherein, ion sequestering agent is added by every cube of chloride liquid
Enter 0.5~3 L；
（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve
Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 5.0~6.5, filtered,
Obtain filter residue and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, most obtained afterwards through being evaporated under reduced pressure, condensing, crystallizing
Sulfuric acid zinc product；Wherein, ion sequestering agent adds 0.5~4 L by every cube of chloride liquid.
A kind of foregoing technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia, it is characterised in that：Step（4）With
（5）Described in ion sequestering agent for ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, citric acid, sodium citrate, citric acid
In ammonium, tren, maleopimaric acid, dimercaprol dimercaptopropanol, DMPS, Succimer, double hydrogen phenylglycines
One or more.
Embodiment 1, comprises the following steps：
（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 2 by solvent and solute weight ratio in the case where washing temperature is 90 DEG C:1
The high chlorine cadmia that average grain diameter is 200 μm is added to the water by ratio, after washing 3h, filtering, obtains water lotion and washing slag, its
In, about 85% chlorine and about 15% zinc enter water lotion in high chlorine cadmia；It is 2 by solvent and solute weight ratio at 70 DEG C:1 ratio
Washing slag is added to the water, then passes to ammonia, after pH value of reaction system is adjusted into 9.5, reaction 3h, filtering, obtains ammonia leaching solution
And ammonia leaching residue, wherein, the leaching rate about 89% of chlorine, the leaching rate of zinc is 0；
Then after two sections of extract technologies of washing-ammonification, for the leaching rate of chlorine up to more than 98%, zinc leaching rate is about 15%.
（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：Reaction temperature be 90 DEG C, solvent and solute weight ratio 2:1, hydrogen peroxide adds
It is the weight of hydrogen peroxide and solid than 0.1 to enter amount:1 and the addition of sulfuric acid be zinc mol ratio 3 in sulfuric acid and ammonia leaching residue:1 bar
Under part, after extraction time reaches 20min, filtering, zincate solution and zinc leaching residue are obtained, wherein, zinc, copper, nickel, the leaching rate point of cobalt and tin
Not up to 98%, 99%, 94%, 96% and more than 85%；
Then total leaching rate of zinc and copper is respectively up to 98% and more than 99%.
（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and adjusted and mixed with ammonia
The pH value of liquid is closed to 9.5, filtering, purification slag and filtrate containing zinc and copper is obtained, is added to filtrate and excess coefficient is counted as 1 using sulfate radical
Calcium chloride solution, filtering, most backward filtrate add counts excess coefficient as 0.1 ammonium bicarbonate soln using calcium ion, filtering, obtains
Chloride liquid after to purification, wherein, more than 99% zinc and copper generation precipitation enter in purification slag in mixed liquor；
（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 7.5 with hydrochloric acid, then ion sequestering agent is added into solution, most
By being evaporated under reduced pressure, condensing, crystallization, arrival ammonium chloride product is obtained；Wherein, ion sequestering agent is maleopimaric acid, dimercapto third
Alcohol, DMPS by volume 3：2：3 ratio mixing, addition add 3 L by every cube of chloride liquid；
（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve
Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 6.5, filtering, filtered
Slag and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, through being evaporated under reduced pressure, condensing, crystallizing, obtain zinc sulfate production
Product；Wherein, ion sequestering agent is the disodium ethylene diamine tetra-acetic acid solution that concentration is 10%, adds 4 L by every cube of chloride liquid, contains
More than 99% copper, nickel, cobalt and tin enter in filter residue in zinc liquid, realize purification and valuable metal copper, nickel, the cobalt of the liquid containing zinc
With the enrichment of tin.
Embodiment 2, comprises the following steps：
（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 8 by solvent and solute weight ratio in the case where washing temperature is 20 DEG C:1
The high chlorine cadmia that average grain diameter is 40 μm is added to the water by ratio, after washing 0.5h, filtering, obtains water lotion and washing slag, its
In, about 85% chlorine and about 15% zinc enter water lotion in high chlorine cadmia；It is 8 by solvent and solute weight ratio at 20 DEG C:1 ratio
Washing slag is added to the water, then passes to ammonia, after pH value of reaction system is adjusted into 8.5, reaction 2h, filtering, obtains ammonia leaching solution
And ammonia leaching residue, wherein, the leaching rate about 89% of chlorine, the leaching rate of zinc is 0；
Then after two sections of extract technologies of washing-ammonification, for the leaching rate of chlorine up to more than 98%, zinc leaching rate is about 15%.
（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：Reaction temperature be 30 DEG C, solvent and solute weight ratio 2:1, hydrogen peroxide adds
It is the weight of hydrogen peroxide and solid than 0.6 to enter amount:1 and the addition of sulfuric acid be zinc mol ratio 3 in sulfuric acid and ammonia leaching residue:1 bar
Under part, after extraction time reaches 200min, filtering, zincate solution and zinc leaching residue are obtained, wherein, zinc, copper, nickel, the leaching rate of cobalt and tin
Respectively up to 98%, 99%, 94%, 96% and more than 85%；
Then total leaching rate of zinc and copper is respectively up to 98% and more than 99%.
（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and adjusted and mixed with ammonia
The pH value of liquid is closed to 7.5, filtering, purification slag and filtrate containing zinc and copper is obtained, is added to filtrate and excess coefficient is counted as 1 using sulfate radical
Calcium chloride solution, filtering, most backward filtrate add counts excess coefficient as 0.01 ammonium bicarbonate soln using calcium ion, filtering,
Chloride liquid after being purified, wherein, more than 99% zinc and copper generation precipitation enter in purification slag in mixed liquor；
（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 4.5 with hydrochloric acid, then ion sequestering agent is added into solution, most
By being evaporated under reduced pressure, condensing, crystallization, arrival ammonium chloride product is obtained, wherein, ion sequestering agent is dimercaprol dimercaptopropanol, and addition is pressed
Every cube of chloride liquid adds 0.5 L；
（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve
Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 5.5, filtering, filtered
Slag and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, through being evaporated under reduced pressure, condensing, crystallizing, obtain zinc sulfate production
Product；Wherein, ion sequestering agent is the edta solution that concentration is 10%, and 0.5L, liquid containing zinc are added by every cube of chloride liquid
In more than 99% copper, nickel, cobalt and tin enter in filter residue, realize purification and valuable metal copper, nickel, cobalt and the tin of the liquid containing zinc
Enrichment.
Embodiment 3, comprises the following steps：
（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 5 by solvent and solute weight ratio in the case where washing temperature is 70 DEG C:1
The high chlorine cadmia that average grain diameter is 100 μm is added to the water by ratio, after washing 2h, filtering, obtains water lotion and washing slag, its
In, about 85% chlorine and about 15% zinc enter water lotion in high chlorine cadmia；It is 5 by solvent and solute weight ratio at 50 DEG C:1 ratio
Washing slag is added to the water, then passes to ammonia, after pH value of reaction system is adjusted into 8.5, reaction 2h, filtering, obtains ammonia leaching solution
And ammonia leaching residue, wherein, the leaching rate about 89% of chlorine, the leaching rate of zinc is 0；
Then after two sections of extract technologies of washing-ammonification, for the leaching rate of chlorine up to more than 98%, zinc leaching rate is about 15%.
（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：Reaction temperature be 70 DEG C, solvent and solute weight ratio 4:1, hydrogen peroxide adds
It is the weight of hydrogen peroxide and solid than 0.3 to enter amount:1 and the addition of sulfuric acid be zinc mol ratio 1.1 in sulfuric acid and ammonia leaching residue:1
Under the conditions of, after extraction time reaches 100min, filtering, zincate solution and zinc leaching residue are obtained, wherein, the leaching of zinc, copper, nickel, cobalt and tin
Rate is respectively up to 98%, 99%, 94%, 96% and more than 85%；
Then total leaching rate of zinc and copper is respectively up to 98% and more than 99%.
（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and it is molten with 28% ammoniacal liquor
The pH value of liquid regulation mixed liquor filtering, obtains purification slag and filtrate containing zinc and copper to 7.5, is added to filtrate in terms of sulfate radical
Coefficient of discharge is 1 calcium chloride solution, and filtering, most backward filtrate add that to count excess coefficient using calcium ion molten as 0.05 ammonium hydrogen carbonate
Liquid, filtering, the chloride liquid after being purified, wherein, more than 99% zinc and copper generation precipitation enter in purification slag in mixed liquor；
（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 4.5 with hydrochloric acid, then ion sequestering agent is added into solution, most
By being evaporated under reduced pressure, condensing, crystallization, arrival ammonium chloride product is obtained, wherein, ion sequestering agent is the dimercapto third that concentration is 15%
Sodium sulfonate solution, addition add 2.5 L by every cube of chloride liquid；
（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve
Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 6.0, filtering, filtered
Slag and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, through being evaporated under reduced pressure, condensing, crystallizing, obtain zinc sulfate production
Product；Wherein, ion sequestering agent is the edta solution that concentration is 10%, and 3 L, liquid containing zinc are added by every cube of chloride liquid
In more than 99% copper, nickel, cobalt and tin enter in filter residue, realize purification and valuable metal copper, nickel, cobalt and the tin of the liquid containing zinc
Enrichment.
To sum up, advantages of the present invention：
1）Using washing-ammonification extract technology, the wash-off rate of chlorine in high chlorine cadmia is set to greatly reduce follow-up dechlorination up to more than 98%
Cost；
2）Using oxidation acid leaching technology, the leaching rate of zinc in slag is substantially increased, makes the leaching rate of zinc up to more than 98%, its
The metallic element such as copper of his high added value, nickel, the leaching rate of cobalt and tin are also respectively up to 99%, 94%, 96% and more than 85%.
3）By substep impurity removal process, the separation and concentration of metallic element in high chlorine cadmia is realized, obtains lead, cadmium, copper etc.
It is enriched with and makes its recycling again；
4）In ammonium chloride and zinc sulfate Product Process is prepared, add ion sequestering agent masking harmful element and improve the pure of product
Degree；And caused condensed water can realize the zero-emission of the three wastes as the leaching water of high chlorine cadmia in the process.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint
Without departing from technical solution of the present invention content, what the technical spirit according to the present invention was made to above example any simply repaiies for what
Change, convert material, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (2)
- A kind of 1. technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia, it is characterised in that：Comprise the following steps：（1）Two sections of chlorine leached in high chlorine cadmia of washing-ammonification：It is 20~90 DEG C in washing temperature when washing high chlorine cadmia, liquid Gu weight ratio is 2~8:1 and ball milling average grain diameter be 40~200 μm under conditions of, wash 0.5~3h after, separation of solid and liquid, obtain Water lotion and washing slag；When the chlorine in washing slag is leached in ammonification, using ammoniacal liquor or ammonia as pH adjuster, in Leaching Systems pH value It is 2~8 for 7.0~9.5, solvent and solute weight ratio:1 and extraction temperature be 20~70 DEG C, leach 0.5~3h after, separation of solid and liquid, obtain Ammonia leaching solution and ammonia leaching residue；（2）Aoxidize the zinc in vitriol lixiviation ammonia leaching residue：It it is 30~90 DEG C in reaction temperature, liquid is solid when leaching the zinc in ammonia leaching residue Weight ratio is 2~6:1, hydrogen peroxide addition is the weight of hydrogen peroxide and solid than 0.1~0.6:1 and the addition of sulfuric acid be sulphur Acid and zinc mol ratio 1.1~3 in ammonia leaching residue:Under conditions of 1, extraction time separation of solid and liquid, obtains soaking zinc up to after 20~200min Liquid and zinc leaching residue；（3）The purification of chloride liquid：Chloride water lotion is added in chloride ammonia leaching solution, obtains mixed liquor, and it is molten with 10~28% ammoniacal liquor The pH value of liquid or ammonia regulation mixed liquor filtering, obtains purification slag and filtrate to 7.5~9.5, is added to filtrate in terms of sulfate radical Coefficient of discharge is 0.2~1 calcium chloride solution, and filtering, most backward filtrate adds counts excess coefficient as 0.01~0.1 using calcium ion Ammonium bicarbonate soln, filtering, the chloride liquid after being purified；（4）The preparation of ammonium chloride：The pH value of chloride liquid is first adjusted to 4.5~7.5 with hydrochloric acid, then ions screen is added into solution Agent, most obtain arrival ammonium chloride product through being evaporated under reduced pressure, condensing, crystallizing afterwards；Wherein, ion sequestering agent is added by every cube of chloride liquid Enter 0.5~3 L；（5）The purification of zincate solution：By step（3）In caused purification slag add step（2）In in caused zincate solution, and dissolve Liquid containing zinc is obtained, then adjusts liquid containing zinc by the use of zinc powder as pH adjusting agent, the pH value of the liquid containing zinc is adjusted to 5.0~6.5, filtered, Obtain filter residue and containing zinc purification fluid, then ion sequestering agent is added into liquid containing zinc, most obtained afterwards through being evaporated under reduced pressure, condensing, crystallizing Sulfuric acid zinc product；Wherein, ion sequestering agent adds 0.5~4 L by every cube of chloride liquid.
- A kind of 2. technique for preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia according to claim 1, it is characterised in that： Step（4）With（5）Described in ion sequestering agent for ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, citric acid, citric acid Sodium, ammonium citrate, tren, maleopimaric acid, dimercaprol dimercaptopropanol, DMPS, Succimer, double hydrogen benzene One or more in glycine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710745323.7A CN107555469B (en) | 2017-08-26 | 2017-08-26 | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710745323.7A CN107555469B (en) | 2017-08-26 | 2017-08-26 | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107555469A true CN107555469A (en) | 2018-01-09 |
| CN107555469B CN107555469B (en) | 2019-03-19 |
Family
ID=60976828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710745323.7A Active CN107555469B (en) | 2017-08-26 | 2017-08-26 | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107555469B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040763A (en) * | 2019-05-10 | 2019-07-23 | 河北远大中正生物科技有限公司 | It is a kind of using high chlorine secondary zinc oxide as the technique of raw material coproduction low sulfuric chlorohydrin zinc and common salt |
| CN115353142A (en) * | 2022-08-23 | 2022-11-18 | 云南驰宏资源综合利用有限公司 | Method for producing zinc sulfate heptahydrate from high-chlorine zinc ash |
| CN115386734A (en) * | 2022-08-23 | 2022-11-25 | 云南驰宏资源综合利用有限公司 | Method for producing zinc ingot from high-chlorine zinc ash |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132698A (en) * | 2015-09-27 | 2015-12-09 | 常州市奥普泰科光电有限公司 | Technology for extracting aluminum and zinc from high-aluminum zinciferous aluminum-zinc residues |
| CN106115768A (en) * | 2015-10-05 | 2016-11-16 | 李果 | A kind of comprehensive cyclic utilization method of steel plant zinc smoke ash |
-
2017
- 2017-08-26 CN CN201710745323.7A patent/CN107555469B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132698A (en) * | 2015-09-27 | 2015-12-09 | 常州市奥普泰科光电有限公司 | Technology for extracting aluminum and zinc from high-aluminum zinciferous aluminum-zinc residues |
| CN106115768A (en) * | 2015-10-05 | 2016-11-16 | 李果 | A kind of comprehensive cyclic utilization method of steel plant zinc smoke ash |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110040763A (en) * | 2019-05-10 | 2019-07-23 | 河北远大中正生物科技有限公司 | It is a kind of using high chlorine secondary zinc oxide as the technique of raw material coproduction low sulfuric chlorohydrin zinc and common salt |
| CN115353142A (en) * | 2022-08-23 | 2022-11-18 | 云南驰宏资源综合利用有限公司 | Method for producing zinc sulfate heptahydrate from high-chlorine zinc ash |
| CN115386734A (en) * | 2022-08-23 | 2022-11-25 | 云南驰宏资源综合利用有限公司 | Method for producing zinc ingot from high-chlorine zinc ash |
| CN115386734B (en) * | 2022-08-23 | 2023-11-17 | 云南驰宏资源综合利用有限公司 | Method for producing zinc ingot by high-chlorine zinc ash |
| CN115353142B (en) * | 2022-08-23 | 2023-11-24 | 云南驰宏资源综合利用有限公司 | Method for producing zinc sulfate heptahydrate by high-chlorine zinc ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107555469B (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104017995B (en) | A kind of from containing the method reclaiming copper-indium-galliun-selenium copper-indium-galliun-selenium waste material | |
| CN1332046C (en) | Zinc recovery process | |
| CN106967884B (en) | A kind of method of silver separating residue of copper anode slime step by step arithmetic | |
| CN102409180B (en) | Metallurgical process for recovering metal copper, lead, zinc and tin from copper refining waste slag | |
| CN101451185B (en) | Comprehensive recovery method for ferro-sulphur ore containing copper, zinc and iron multi-metal | |
| CN107287432B (en) | A method of recycling zinc, copper, cadmium from the copper-cadmium slag of zinc hydrometallurgy | |
| CN106048217A (en) | Comprehensive recycling method for zinc oxide powder | |
| CN111575491B (en) | Resource comprehensive utilization method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt | |
| CN107555469B (en) | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia | |
| CN107557570A (en) | Method for comprehensively recovering valuable metals from cyanidation tailings | |
| CN104108740B (en) | A kind of novel method of selectivity production high-quality copper sulfate from copper-bearing waste material | |
| CN107673400A (en) | Method for producing zinc sulfate heptahydrate from copper-cadmium slag | |
| CN103374658A (en) | Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof | |
| CN104911366A (en) | Method for recovering valuable metals from silver-bismuth slag through using aqua regia | |
| CN106715729B (en) | A kind of processing method of the secondary material containing chlorine zinc oxide complex | |
| CN105907972B (en) | A kind of method of a variety of valuable metals of the synthetical recovery from electroplating sludge | |
| CN107190151B (en) | In a kind of zinc hydrometallurgy and the comprehensive recovering process of heavy scum | |
| CN103320624A (en) | Method for selectively extracting gold and silver from copper anode slime | |
| CN104386737A (en) | Method for preparing cadmium oxide by using cadmium-containing smoke dust generated by zinc smelting | |
| CN109055764B (en) | Comprehensive recovery method of high-chlorine low-zinc material | |
| CN104789784B (en) | A kind of pyrometallurgy of zinc fume recovery handling process | |
| CN104513899A (en) | Process for treating xanthate cobalt slag | |
| CN1686842A (en) | Technique for preparing sodium fluosilicate by using raffinate extracted from smelting columbite-tantalite ore | |
| CN112607782B (en) | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime | |
| CN109371245A (en) | Nickel refining system copper ashes recycling processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |