CN108913907A - A method of zinc being recycled from ferrous acid zinc resource using calcification baking-ammonia leaching process - Google Patents
A method of zinc being recycled from ferrous acid zinc resource using calcification baking-ammonia leaching process Download PDFInfo
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- CN108913907A CN108913907A CN201810878691.3A CN201810878691A CN108913907A CN 108913907 A CN108913907 A CN 108913907A CN 201810878691 A CN201810878691 A CN 201810878691A CN 108913907 A CN108913907 A CN 108913907A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a kind of methods for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, belong to technical field of mineral processing, include the following steps：(1) raw ore is subjected to break process, obtains the ferrous acid zinc resource of predetermined fineness；(2) calcification agent is added into ferrous acid zinc resource, pelletizes after mixing well, mixture is subjected to calcification baking under oxidizing atmosphere, so that zinc ferrite is carried out ore phase reconstruction, is converted into zinc oxide, obtains calcification baking product；(3) calcification baking product is subjected to break process, is handled by ammonia leaching, leached zinc oxide dissolution, after separation of solid and liquid, obtain zinc filtrate and leached mud.The present invention makes ferrous acid zinc resource carry out ore phase reconstruction by calcification baking, it is converted into zinc oxide, it is easy to subsequent ammonia extraction to take, leach it is at low cost, selectivity it is good, the calcification agent of use is cheap and easy to get, compared with pyrogenic process carbonizing reduction, addition coke or reduction coal are not required to as reducing agent, and reaction rate is fast, zinc leaching rate is up to 90% or more.
Description
Technical field
The invention belongs to technical field of mineral processing, and in particular to a kind of to be provided using calcification baking-ammonia leaching process from zinc ferrite
The method of zinc is recycled in source.
Background technique
Zinc is important strategic basic material, and application is very extensive, and consumption is only second to copper and aluminium in non-ferrous metal, with
The quickening of China's modernization construction, the demand of zinc product increasingly increase.The primary raw material of zinc abstraction is zinc sulfide ore at present,
Reserves are increasingly reduced, and limit the development of Zn Cr coating, recycle zinc oxide ore and secondary zinc resource is that there is lack of raw materials for solution zinc
Effective way, secondary zinc resource includes zinc leaching residue, Dust of Iron And Steel Works, lead and zinc smelting dreg etc..Iron and Steel Enterprises in China is annual
About 100,000,000 tons of the dust of generation, but utilization rate, less than 20%, these dust contain a large amount of zinc resource but can not effectively recycle benefit
With, cause the serious wasting of resources and environmental pollution, therefore, recycle the secondary zinc resource of steel plant's zinc-containing dust to solution
There is lack of raw materials and environmental protection is of great significance for China's Zn Cr coating.
It is mutually zinc ferrite that ferrous acid zinc resource, which mainly contains zinc object, and zinc ferrite structure is sufficiently stable, is difficult to be destroyed, at present steel
Factory's dust treating method includes wet-leaching, pyrometallurgical smelting and wet process-pyrogenic process process integration etc., is to recycle oxidation
It is bad to the zinc resource recovering effect in zinc ferrite object phase based on zinc resource in zinc.Wet-leaching mainly include the acid-hatching of young eggs and
Alkaline leaching, the acid-hatching of young eggs needs high temperature peracid condition that could obtain higher zinc leaching rate, but iron is largely leached simultaneously, after causing
Continuous heavy iron process is complicated, and the overall recovery of zinc is low.Method mainly includes NaOH highly basic lixiviation process and two kinds of ammonia lixiviation process when alkali soaks, with
The acid-hatching of young eggs is compared, and alkaline leaching has good selectivity leaching characteristic, especially ammonia leaching process, but is used for zinc when dregs containing zinc resource
Leaching rate is low.Fire reduction method needs to rely on reduction coal or Jiaozhuo is reducing agent and fuel, the side volatilized by high temperature reduction
Method recycles zinc.When handling ferrous acid zinc resource, reduction volatilization temperature is higher than the reduction temperature of conventional oxidation zinc resource, and reduction is difficult
Degree is bigger, energy consumption is higher, economic difference.Up to the present, clear suitable for the middle zinc of recycling ferrous acid zinc resource there are no developing
Clean Efficient utilization method.
Summary of the invention
The purpose of the present invention is to provide a kind of zinc recovery height, the utilization calcification baking-that production cost is low, environmentally protective
The method that ammonia leaching process recycles zinc from ferrous acid zinc resource.
The present invention provides a kind of method for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, including following
Step：
(1) raw ore is subjected to break process, obtains the ferrous acid zinc resource of predetermined fineness；
(2) calcification agent is added into ferrous acid zinc resource obtained by step (1), pelletizes after mixing well, mixture is being aoxidized
Calcification baking is carried out under atmosphere, zinc ferrite is made to carry out ore phase reconstruction, is converted into zinc oxide, is obtained calcification baking product after cooling；
(3) calcification baking product obtained by step (2) is subjected to break process, is handled by ammonia leaching, make zinc oxide dissolution leaching
Out, after separation of solid and liquid, zinc filtrate and leached mud are obtained.
Preferably, the calcification agent is one of calcium carbonate, calcium oxide or calcium hydroxide or a variety of.
Preferably, effective CaO content and the molar ratio of zinc ferrite are (2.4~3.0) in the calcification agent：1.
Preferably, the fineness extremely -1.0mm in the step (1), after controlling crushing raw ore.
Preferably, in the step (2), the partial size (D of mixture90) it is 3.0~20mm.
Preferably, the calcification baking carries out in rotary kiln, and maturing temperature is 1220~1280 DEG C, and calcining time is
120~180min.
Preferably, the calcification baking product uses natural cooling or water quenching cooling.
Preferably, in the step (3), the control broken fineness of zinc oxide ore to -3.0mm.
Preferably, in the step (3), using leaching mode, leaching device is closed.
Preferably, the ammonia degree of being soaked is：Leaching solid-to-liquid ratio is 30~150g/L, and extraction temperature is 40~60 DEG C, is leached
100~120min of time.
Preferably, the ammonia leaching processing uses NH4Cl-NH3·H2O solution is as leachate, NH4Cl and NH3·H2O's rubs
Your concentration ratio is 1：1, total ammonia density is 6~7mol/L in leachate.
Preferably, the raw ore is one of Dust of Iron And Steel Works, zinc leaching residue and lead and zinc smelting dreg or a variety of, master
Wanting object is mutually zinc ferrite.
The present invention extracts zinc using ferrous acid zinc resource as raw material, using calcification baking-ammonia leaching process, compared to zinc ferrite, oxidation
Zinc structure is simple, dissolves in alkaline solution, is based on this principle, the present invention is by the calcification agent of excessive addition under oxidizing atmosphere
It is roasted, by the zinc oxide of the zinc ferrite conversion simple structure of stable structure, ammonia leaching process is recycled to select calcification baking product
Selecting property dissolution, and then realize from dregs containing zinc resource high efficiente callback zinc resource, the invention mainly relates to chemical reaction it is as follows：
ZnFe2O4+2CaCO3=ZnO+Ca2Fe2O5+2CO2↑
ZnO+4NH3·H2O=[Zn (NH3)4](OH)2+3H2O
ZnO+2NH4Cl=Zn (NH3)2Cl2+H2O
Compared with prior art, advantageous effects of the invention：
(1) method of the present invention for being recycled zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, is roasted by calcification
Burning makes ferrous acid zinc resource carry out ore phase reconstruction, is converted into zinc oxide, is easy to subsequent ammonia extraction and takes, and leaching is at low cost, and selectivity is good,
The impurity such as calcium, silicon are not leached, and the calcification agent of use is cheap and easy to get, compared with pyrogenic process carbonizing reduction, are not required to addition coke or are gone back
Raw coal is as reducing agent, and reaction rate is fast, and zinc leaching rate is up to 90% or more.
(2) method of the present invention for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, leached mud are main
Ingredient is calcium ferrite (CaFe2O4), recoverable does iron-smelting raw material, reduces environmental pollution caused by steel plant's zinc-containing dust
Problem, leachate can heat resolve recycle, the present invention with acid system leach compared with, silica gel will not be generated, be easy to subsequent leaching
It is separated by filtration, process energy consumption is low, environmentally protective.
Detailed description of the invention
Fig. 1 is the process flow for recycling zinc in the embodiment of the present invention 1 from ferrous acid zinc resource using calcification baking-ammonia leaching process
Figure.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Embodiment 1
Certain steel plant's zinc-containing dust (TZn 5.67%, ZnFe2O455.72%), by crushing raw ore to -1mm, carbonic acid is added
Calcium, controlling effective CaO content and the molar ratio of zinc ferrite in calcium carbonate is 2.4：1, the small of 3~20mm is granulation into after mixing well
Mixture is placed in rotary kiln and carries out calcification baking by ball, completes ore phase reconstruction, and maturing temperature is 1220 DEG C, and calcining time is
120min, natural cooling are crushed to -3mm, carry out ammonia leaching processing, and ammonia degree of being soaked is：Solid-to-liquid ratio is 100g/L, extraction temperature 40
DEG C, extraction time 120min, leachate uses NH4Cl-NH3·H2O solution (NH4Cl and NH3·H2The molar concentration rate of O is 1：
1), in leachate total ammonia density be 6mol/L, leachate after filtering, zinc leaching rate 93.65%.
Embodiment 2
Certain steel plant's zinc-containing dust (TZn 5.67%, ZnFe2O455.72%), by crushing raw ore to -1mm, carbonic acid is added
Calcium, controlling effective CaO content and the molar ratio of zinc ferrite in calcium carbonate is 2.4：1, the small of 3~20mm is granulation into after mixing well
Mixture is placed in rotary kiln and carries out calcification baking by ball, completes ore phase reconstruction, and maturing temperature is 1240 DEG C, and calcining time is
120min, natural cooling are crushed to -3mm, carry out ammonia leaching processing, and ammonia degree of being soaked is：Solid-to-liquid ratio is 120g/L, extraction temperature 40
DEG C, extraction time 100min, leachate uses NH4Cl-NH3·H2O solution (NH4Cl and NH3·H2The molar concentration rate of O is 1：
1), in leachate total ammonia density be 6mol/L, leachate after filtering, zinc leaching rate 93.31%.
Embodiment 3
Certain steel plant's zinc-containing dust (TZn 5.67%, ZnFe2O455.72%), by crushing raw ore to -1mm, oxidation is added
Calcium, the molar ratio for controlling effective CaO content and zinc ferrite is 2.5：1, it is granulation into the bead of 3~20mm after mixing well, will mix
It closing and expects to be placed in rotary kiln to carry out calcification baking, complete ore phase reconstruction, maturing temperature is 1220 DEG C, calcining time 120min,
Natural cooling is crushed to -3mm, carries out ammonia leaching processing, and ammonia degree of being soaked is：Solid-to-liquid ratio is 100g/L, 60 DEG C of extraction temperature, is leached
Time 110min, leachate use NH4Cl-NH3·H2O solution (NH4Cl and NH3·H2The molar concentration rate of O is 1：1) it, leaches
In liquid total ammonia density be 6mol/L, leachate after filtering, zinc leaching rate 94.71%.
Comparative example 1
Certain steel plant's zinc-containing dust (TZn 5.67%, ZnFe2O455.72%), by crushing raw ore to -1mm, 3 are granulation into
The bead of~20mm, is roasted in rotary kiln, and maturing temperature is 1220 DEG C, calcining time 120min, and natural cooling is broken
It is broken to -3mm, carries out ammonia leaching processing, solid-to-liquid ratio 100g/L, 60 DEG C of extraction temperature, extraction time 110min, leachate is
NH4Cl-NH3·H2O solution, NH4Cl and NH3·H2The molar concentration rate of O is 1：1, total ammonia density is 6mol/L, leaching in leachate
Out liquid after filtering, zinc leaching rate 42.07%.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, which is characterized in that including following step
Suddenly：
(1) raw ore is subjected to break process, obtains the ferrous acid zinc resource of predetermined fineness；
(2) calcification agent is added into ferrous acid zinc resource obtained by step (1), pelletizes after mixing well, by mixture in oxidizing atmosphere
Lower carry out calcification baking makes zinc ferrite carry out ore phase reconstruction, is converted into zinc oxide, obtains calcification baking product after cooling；
(3) calcification baking product obtained by step (2) is subjected to break process, is handled by ammonia leaching, leach zinc oxide dissolution, Gu
After liquid separation, zinc filtrate and leached mud are obtained.
2. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, the calcification agent is one of calcium carbonate, calcium oxide or calcium hydroxide or a variety of.
3. the method according to claim 1 or 2 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process,
It is characterized in that, effective CaO content and the molar ratio of zinc ferrite are (2.4~3.0) in the calcification agent：1.
4. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, the fineness extremely -1.0mm in the step (1), after controlling crushing raw ore.
5. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, in the step (2), the partial size (D of mixture90) it is 3.0~20mm.
6. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, the calcification baking carries out in rotary kiln, and maturing temperature is 1220~1280 DEG C, and calcining time is 120~180min.
7. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, in the step (3), the control broken fineness of zinc oxide ore to -3.0mm.
8. the method according to claim 1 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, the ammonia degree of being soaked is：Leaching solid-to-liquid ratio is 30~150g/L, and extraction temperature is 40~60 DEG C, extraction time 100~
120min。
9. the method according to claim 8 for recycling zinc from ferrous acid zinc resource using calcification baking-ammonia leaching process, feature
It is, the ammonia leaching processing uses NH4Cl-NH3·H2O solution is as leachate, NH4Cl and NH3·H2The molar concentration rate of O is
1：1, total ammonia density is 6~7mol/L in leachate.
10. according to claim 1, being returned from ferrous acid zinc resource described in any one of 2,4~9 using calcification baking-ammonia leaching process
The method for receiving zinc, which is characterized in that the raw ore is one of Dust of Iron And Steel Works, zinc leaching residue and lead and zinc smelting dreg or more
Kind, main object is mutually zinc ferrite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810878691.3A CN108913907A (en) | 2018-08-03 | 2018-08-03 | A method of zinc being recycled from ferrous acid zinc resource using calcification baking-ammonia leaching process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810878691.3A CN108913907A (en) | 2018-08-03 | 2018-08-03 | A method of zinc being recycled from ferrous acid zinc resource using calcification baking-ammonia leaching process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110863219A (en) * | 2019-12-04 | 2020-03-06 | 北京环丁环保大数据研究院 | Method for resource utilization of zinc-containing converter dust and sludge |
| CN113373318A (en) * | 2021-05-31 | 2021-09-10 | 张家港江苏科技大学产业技术研究院 | High-alkalinity furnace charge for strengthening zinc recovery from zinc-containing electric furnace dust and method for recovering zinc by using high-alkalinity furnace charge |
| CN113637840A (en) * | 2021-07-29 | 2021-11-12 | 上海第二工业大学 | Method for recovering zinc from zinc ferrite resource by using calcification ball-milling roasting-alkaline leaching method |
| CN113652539A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for comprehensively recycling neodymium iron boron waste by calcification roasting |
| CN115232983A (en) * | 2022-07-25 | 2022-10-25 | 西安建筑科技大学 | Method for recovering zinc resources in dust removed by electric arc furnace |
| CN115627360A (en) * | 2022-10-31 | 2023-01-20 | 西安建筑科技大学 | Method for preparing high-purity nano zinc powder from arc furnace dust |
-
2018
- 2018-08-03 CN CN201810878691.3A patent/CN108913907A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| ZEQIANG XIE 等: "The Extraction of Zinc from Zinc Ferrite by Calcified-Roasting and Ammonia-Leaching Process", 《8TH INTERNATIONAL SYMPOSIUM ON HIGH-TEMPERATURE METALLURGICAL PROCESSING，THE MINERALS，METALS & MATERIALS SERIES》 * |
| 华一新: "《有色冶金概论第3版》", 31 May 2014, 冶金工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110863219A (en) * | 2019-12-04 | 2020-03-06 | 北京环丁环保大数据研究院 | Method for resource utilization of zinc-containing converter dust and sludge |
| CN110863219B (en) * | 2019-12-04 | 2021-04-16 | 北京环丁环保大数据研究院 | Method for resource utilization of zinc-containing converter dust and sludge |
| CN113373318A (en) * | 2021-05-31 | 2021-09-10 | 张家港江苏科技大学产业技术研究院 | High-alkalinity furnace charge for strengthening zinc recovery from zinc-containing electric furnace dust and method for recovering zinc by using high-alkalinity furnace charge |
| CN113652539A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for comprehensively recycling neodymium iron boron waste by calcification roasting |
| CN113637840A (en) * | 2021-07-29 | 2021-11-12 | 上海第二工业大学 | Method for recovering zinc from zinc ferrite resource by using calcification ball-milling roasting-alkaline leaching method |
| CN115232983A (en) * | 2022-07-25 | 2022-10-25 | 西安建筑科技大学 | Method for recovering zinc resources in dust removed by electric arc furnace |
| CN115232983B (en) * | 2022-07-25 | 2024-05-14 | 西安建筑科技大学 | Method for recycling dust and zinc resources of electric arc furnace |
| CN115627360A (en) * | 2022-10-31 | 2023-01-20 | 西安建筑科技大学 | Method for preparing high-purity nano zinc powder from arc furnace dust |
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Application publication date: 20181130 |