CN108754164B - Method for recovering zinc from zinc ferrite resource by using ore phase reconstruction method - Google Patents
Method for recovering zinc from zinc ferrite resource by using ore phase reconstruction method Download PDFInfo
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- CN108754164B CN108754164B CN201810879356.5A CN201810879356A CN108754164B CN 108754164 B CN108754164 B CN 108754164B CN 201810879356 A CN201810879356 A CN 201810879356A CN 108754164 B CN108754164 B CN 108754164B
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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
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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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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Abstract
The invention discloses a method for recovering zinc from zinc ferrite resources by using an ore phase reconstruction method, which belongs to the technical field of mineral processing and comprises the following steps: (1) crushing raw ore to obtain zinc ferrite resource with preset fineness; (2) adding a calcification agent into a zinc ferrite resource, granulating after fully and uniformly mixing, and carrying out calcification roasting on the mixture in an oxidizing atmosphere to reconstruct an ore phase of the zinc ferrite, so as to convert the zinc ferrite into zinc oxide and dicalcium ferrite and obtain a calcification roasting product; (3) carrying out reduction roasting on the calcified roasted product to reduce and convert dicalcium ferrite in the calcified roasted product into magnetite to obtain a reduction roasted product; (4) and crushing the reduction roasting product, and performing magnetic separation to obtain zinc oxide ore and magnetite. According to the invention, the zinc ferrite resource is subjected to ore phase reconstruction through calcification roasting and converted into zinc oxide, so that the subsequent zinc-iron separation is easy, the adopted calcification agent is cheap and easy to obtain, the reaction rate is high, and the recovery rate of zinc after magnetic separation is high.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to a method for recovering zinc from a zinc ferrite resource by using a mineral phase reconstruction method.
Background
Zinc is an important strategic basic material, the application is very wide, the demand of zinc products is increasingly increased along with the acceleration of the modern construction of China, the main raw material of the zinc smelting at present is zinc sulfide ore, the storage capacity is increasingly reduced, and the development of the zinc industry is limited. The recycling of zinc oxide ore and secondary zinc resources is an effective way to solve the shortage of zinc raw materials, the secondary zinc resources mainly comprise iron and steel plant dust, zinc-containing leaching slag and lead-zinc smelting slag, and the zinc leaching slag generated in China is about 500 million tons each year, but the utilization rate is less than 5%. Iron and steel enterprises generate about 1 hundred million tons of dust every year, the utilization rate is less than 20%, the dust contains a large amount of zinc and iron resources but cannot be effectively recycled, and serious resource waste and environmental pollution are caused, so that recycling secondary zinc resources is of great significance for solving the shortage of zinc industrial raw materials and protecting the environment in China.
The zinc ferrite resource is an important secondary zinc resource, the yield is high, the zinc content is high, the main zinc-containing phase is the zinc ferrite, the zinc ferrite has a very stable structure and is difficult to damage, and the zinc ferrite cannot be effectively recycled at present. At present, dust treatment methods of steel plants comprise wet leaching, pyrometallurgical and wet-pyrometallurgical combined processes, and the like, which mainly recycle zinc resources in zinc oxide, and have poor recovery effect on zinc resources in a zinc ferrite phase. The wet leaching mainly comprises an acid leaching method and an alkali leaching method, wherein the acid leaching method needs high-temperature and high-acid conditions to obtain higher zinc leaching rate, and simultaneously leaches zinc and iron, so that the subsequent iron precipitation process is complicated, and the total recovery rate of zinc is low. The alkaline leaching method mainly comprises a NaOH strong alkali leaching method and an ammonia leaching method, and compared with the acid leaching method, the alkaline leaching method has good selective leaching characteristics, particularly the ammonia leaching method, but when the alkaline leaching method is used for zinc ferrite-containing resources, the zinc leaching rate is low. The pyrometallurgical reduction process requires recovery of zinc by high temperature reduction volatilization processes relying on reduced coal or coke as a reductant and fuel. When the zinc ferrite resource is treated, the reduction volatilization temperature is higher than that of the traditional zinc oxide resource, the reduction difficulty is higher, the energy consumption is higher, and the economy is poor. So far, no clean and efficient utilization method suitable for recycling zinc in zinc ferrite resources is developed.
Disclosure of Invention
The invention aims to provide a method for recovering zinc from zinc ferrite resources by using an ore phase reconstruction method, which has the advantages of high zinc recovery rate, low production cost and environmental protection.
The invention provides a method for recovering zinc from a zinc ferrite resource by using an ore phase reconstruction method, which comprises the following steps:
(1) crushing raw ore to obtain zinc ferrite resource with preset fineness;
(2) adding a calcification agent into the zinc ferrite resource obtained in the step (1), granulating after fully and uniformly mixing, carrying out calcification roasting on the mixture in an oxidizing atmosphere to reconstruct the mineral phase of the zinc ferrite, converting the zinc ferrite into zinc oxide and dicalcium ferrite, and cooling to obtain a calcification roasting product;
(3) carrying out reduction roasting on the calcified roasted product obtained in the step (2) to reduce and convert dicalcium ferrite in the calcified roasted product into magnetite to obtain a reduced and roasted product;
(4) and (4) crushing the reduction roasting product obtained in the step (3), and performing magnetic separation to obtain zinc oxide ore and magnetite.
Preferably, the calcification agent is one or more of calcium carbonate, calcium oxide or calcium hydroxide.
Preferably, the molar ratio of the effective CaO content in the calcification agent to the zinc ferrite is (2.0-2.4): 1.
preferably, in the step (1), the raw ore is crushed to a fineness of-1.0 mm.
Preferably, in the step (2), the particle size (D) of the mixture90) Is 3.0 to 20 mm.
Preferably, the calcification roasting is carried out in a rotary kiln or a sintering machine, the roasting temperature is 1230-1280 ℃, and the roasting time is 5-15 min.
Preferably, the calcified roasting product is cooled by natural cooling or water quenching.
Preferably, in the step (3), the reducing gas in the reducing roasting is CO, P (CO)/P (CO + N)2)＝40～50％。
Preferably, in the step (3), the reduction roasting temperature is 800-900 ℃, and the roasting time is 90-120 min.
Preferably, in the step (4), the fineness of the reduction roasting product after crushing is controlled to-1.0 mm.
Preferably, in the step (4), the magnetic field intensity in the magnetic separation is 0.1-0.4T.
Preferably, the raw ore is one or more of dust of a steel plant, zinc-containing leaching slag and lead-zinc smelting slag, and the main phase of the raw ore is zinc ferrite.
The invention takes zinc ferrite resources as raw materials, adopts calcification roasting-reduction roasting-magnetic separation method to extract zinc, compared with zinc ferrite, zinc oxide has simple structure and easy treatment, the invention converts zinc ferrite with stable structure into zinc oxide and dicalcium ferrite by adding excessive calcification agent to roast under oxidizing atmosphere, then reduces dicalcium ferrite into magnetite by adopting reduction roasting process, and finally separates and recovers zinc oxide by adopting magnetic separation method, thereby realizing high-efficiency recovery of zinc resources from zinc ferrite resources, the invention mainly relates to the following chemical reactions:
ZnFe2O4+2CaCO3＝ZnO+Ca2Fe2O5+2CO2↑
3Ca2Fe2O5+CO＝6CaO+2Fe3O4+CO2↑
compared with the prior art, the invention has the beneficial technical effects that:
(1) the method for recovering zinc from the zinc ferrite resource by using the ore phase reconstruction method disclosed by the invention has the advantages that the ore phase reconstruction of the zinc ferrite resource is carried out by calcified roasting, the zinc ferrite resource is converted into zinc oxide, the grain size is larger, the subsequent zinc and iron separation is easy, the adopted calcification agent is cheap and easy to obtain, compared with the pyrogenic process carbonization reduction, coke or reducing coal is not required to be added as a reducing agent, the reaction rate is high, and the recovery rate of zinc after magnetic separation reaches more than 90%.
(2) According to the method for recovering zinc from the zinc ferrite resource by using the ore phase reconstruction method, dicalcium ferrite can be reduced and converted into magnetite through reduction roasting, the conversion effect is good, the crystal grain growth is further promoted, the magnetic product obtained through magnetic separation is iron concentrate serving as an iron-making raw material, the nonmagnetic product is zinc oxide serving as a zinc-smelting raw material, and therefore the clean and efficient utilization of zinc-containing dust in steel plants is realized, the process energy consumption is low, and the method is green and environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the present invention for recovering zinc from zinc ferrite resources by using a phase reconstruction method.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
Zinc-containing dust (TZn 5.67%, ZnFe) of certain iron and steel works2O455.72 percent), crushing the raw ore to-1 mm, adding calcium carbonate, and controlling the molar ratio of the effective CaO content in the calcium carbonate to the zinc ferrite to be 2.4: 1, fully mixing the materials, granulating the mixture into pellets of 3-20 mm, placing the mixture in a rotary kiln for calcification roasting at 1230 ℃, wherein the roasting time is 15min, and placing the calcification roasted product in P (CO)/P (CO + N)2) Reducing roasting in 40% reducing atmosphere at 800 deg.c for 90min, cooling the product, crushing to-1 mm, magnetically separating zinc and iron at magnetic field strength of 0.2T and recovering zinc in tailings of magnetic separation of 95.31%.
Example 2
Zinc-containing dust (TZn 5.67%, ZnFe) of certain iron and steel works2O455.72 percent), crushing the raw ore to-1 mm, adding calcium oxide, and controlling the molar ratio of the effective CaO content to the zinc ferrite to be 2.2: 1, fully mixing the materials, granulating the mixture into pellets of 3-20 mm, placing the mixture in a rotary kiln for calcification roasting at 1250 ℃ for 10min, and placing the calcification roasted product in P (CO)/P (CO + N)2) Reduction atmosphere of 40%The original roasting is carried out, the roasting temperature is 850 ℃, the roasting time is 90min, the reduction roasting product is cooled and crushed to-1 mm, the zinc and iron are separated by a magnetic separation method, the magnetic field intensity is 0.2T, and the recovery rate of zinc in the magnetic separation tailings is 96.87%.
Example 3
Zinc-containing dust (TZn 5.67%, ZnFe) of certain iron and steel works2O455.72 percent), crushing the raw ore to-1 mm, adding calcium hydroxide, and controlling the molar ratio of the effective CaO content in the calcium hydroxide to the zinc ferrite to be 2.0: 1, fully mixing the materials, granulating the mixture into pellets of 3-20 mm, placing the mixture in a rotary kiln for calcification roasting at 1280 ℃ for 5min, and placing the calcification roasted product in P (CO)/P (CO + N)2) Carrying out reduction roasting in 45% reduction atmosphere at 850 ℃ for 90min, cooling the reduction roasting product, crushing to-1 mm, carrying out zinc-iron separation by adopting a magnetic separation method, wherein the magnetic field intensity is 0.2T, and the recovery rate of zinc in the magnetic separation tailings is 96.06%.
Comparative example 1
Zinc-containing dust (TZn 5.67%, ZnFe) of certain iron and steel works2O455.72 percent of raw ore is crushed to-1 mm and put in P (CO)/P (CO + N)2) Reducing roasting in 40% reducing atmosphere at 800 deg.c for 90min, cooling the product, crushing to-1 mm, magnetically separating zinc and iron at magnetic field strength of 0.2T and zinc recovering rate of 14.82%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (9)
1. A method for recovering zinc from a zinc ferrite resource by using an ore phase reconstruction method is characterized by comprising the following steps:
(1) crushing raw ore to obtain zinc ferrite resource with preset fineness;
(2) adding a calcification agent into the zinc ferrite resource obtained in the step (1), granulating after fully and uniformly mixing, carrying out calcification roasting on the mixture in an oxidizing atmosphere to reconstruct the mineral phase of the zinc ferrite, converting the zinc ferrite into zinc oxide and dicalcium ferrite, and cooling to obtain a calcification roasting product;
(3) carrying out reduction roasting on the calcified roasted product obtained in the step (2) to reduce and convert dicalcium ferrite in the calcified roasted product into magnetite to obtain a reduced and roasted product;
(4) crushing the reduction roasting product obtained in the step (3), and performing magnetic separation to obtain zinc oxide ore and magnetite ore;
the calcification roasting temperature is 1230-1280 ℃, and the roasting time is 5-15 min;
the reduction roasting temperature is 800 ~ 900 ℃, and the roasting time is 90-120 min.
2. The method for recovering zinc from a zinc ferrite resource by using the mineral phase reconstruction method according to claim 1, wherein the calcification agent is one or more of calcium carbonate, calcium oxide or calcium hydroxide.
3. The method for recovering zinc from a zinc ferrite resource by using the ore phase reconstruction method according to claim 1 or 2, wherein the molar ratio of the effective CaO content in the calcification agent to the zinc ferrite is (2.0-2.4): 1.
4. the method for recovering zinc from a zinc ferrite resource by using the mineral phase reconstruction method according to claim 1, wherein in the step (1), the raw ore is crushed to a fineness of-1.0 mm.
5. The method for recovering zinc from zinc ferrite resources by using the mineral phase reconstruction method according to claim 1, wherein in the step (2), the particle size D of the mixture is90Is 3.0 to 20 mm.
6. The method for recovering zinc from a zinc ferrite resource by using the mineral phase reconstruction method according to claim 1, wherein the calcification roasting is performed in a rotary kiln or a sintering machine.
7. The method for recovering zinc from a zinc ferrite resource by using the mineral phase reconstruction method according to claim 1, wherein in the step (3), the reducing gas in the reducing roasting is CO, P (CO)/P (CO + N)2)=40～50%。
8. The method for recovering zinc from a zinc ferrite resource by using the mineral phase reconstruction method according to claim 1, wherein in the step (4), the magnetic field intensity in the magnetic separation is 0.1-0.4T.
9. The method for recovering zinc from zinc ferrite resources by using the ore phase reconstruction method according to any one of claims 1, 2 and 4 to 8, wherein the raw ore is one or more of steel plant dust, zinc-containing leaching slag and lead-zinc smelting slag, and the main phase of the raw ore is zinc ferrite.
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| 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 |
| CN113912131B (en) * | 2021-10-11 | 2022-07-12 | 中南大学 | Zinc ferrite treatment method |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0474526A (en) * | 1990-07-13 | 1992-03-09 | Youyuu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai | Desulfurizing agent for high temperature reductive gas and preparation thereof |
| KR19980033470A (en) * | 1998-04-16 | 1998-07-25 | 구용회 | Selective Separation of Fe Component from Heavy Metal Mixed Solution Using Coal Fly Ash |
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| CN103540765B (en) * | 2013-10-12 | 2014-12-24 | 中南大学 | Zinc smelting technology |
| CN104451126B (en) * | 2014-12-05 | 2016-08-17 | 中南大学 | A kind of method strengthening the decomposition of zinc ferrite selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0474526A (en) * | 1990-07-13 | 1992-03-09 | Youyuu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai | Desulfurizing agent for high temperature reductive gas and preparation thereof |
| KR19980033470A (en) * | 1998-04-16 | 1998-07-25 | 구용회 | Selective Separation of Fe Component from Heavy Metal Mixed Solution Using Coal Fly Ash |
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