CN103555950A - Recycling method of samarium cobalt magnetic waste material - Google Patents
Recycling method of samarium cobalt magnetic waste material Download PDFInfo
- Publication number
- CN103555950A CN103555950A CN201310475027.1A CN201310475027A CN103555950A CN 103555950 A CN103555950 A CN 103555950A CN 201310475027 A CN201310475027 A CN 201310475027A CN 103555950 A CN103555950 A CN 103555950A
- Authority
- CN
- China
- Prior art keywords
- waste material
- cobalt
- oxalic acid
- recoverying
- samarium
- 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.)
- Pending
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a recycling method of a samarium cobalt magnetic waste material. The method is characterized by comprising the steps of: a, leaching a samarium cobalt waste material with dilute hydrochloric acid, and after the complete reaction, filtering to remove substances insoluble in acid; b, regulating pH of a leaching solution, precipitating rare earth elements in the solution with oxalic acid to generate a grey and white oxalate precipitate, filtering, drying and calcining the precipitate to obtain solid samarium oxide; c, precipitating samarium, oxidizing Fe<2+> into Fe<3+> in a filtrate by an oxidant, regulating the pH value to precipitate iron in the solution before cobalt, and filtering; and d, removing iron, adjusting the pH value of filtrate, adding oxalic acid to obtain a cobalt oxalate precipitate, and conducting filtration, drying and calcination to obtain cobalt oxide. The method has the following advantages: hydrochloric acid optimal solution, oxalic acid precipitation, iron removal by oxidation and calcination method are employed according to the chemical properties of the elements contained in the waste material, so as to successfully extract valuable elements in the samarium cobalt in waste material; the recycling process is simple in process and low in production cost and the does not produce secondary pollution of the environment; and the prepared samarium oxide and cobalt oxide products have high extraction rate.
Description
Technical field
The present invention relates to a kind of recoverying and utilizing method of SmCo magnetic waste material, reclaim the valuable element in SmCo magnetic waste material, finally obtain Samarium trioxide and cobalt oxide product.Belong to hydrometallurgy field.
Background technology
Along with the continuous expansion of magneticsubstance range of application, people have developed the permanent magnet material of many excellent performances.Rare-earth cobalt alloy in RE permanent magnetic alloy, composition can be divided into 2 large classes, and a class forms and is about RECo
5, the another kind of RE that is about
2co
17.The raw material that the present invention adopts is samarium-cobalt permanent-magnetic material, conventionally uses RECo
5represent.The production process of samarium-cobalt permanent-magnetic material detects to last product from the pre-treatment of raw material, and each procedure all inevitably produces waste material or waste product, mainly contains: the loss of each the single raw material producing at the pretreatment stage of raw material; Waste product in operation process; Machine adds scrap stock and the skiving powder in process; Unacceptable product; The Fe alloy slag producing in alloy melting process etc.Waste material generation is about 30%, 2011 year of output and produces samarium-cobalt magnet 1100t, and the waste material of formation is about 330t, and wherein the content of samarium and cobalt is higher and have to extract and be worth.Therefore, from SmCo waste material, extract valuable element as cobalt and rare earth, can make resource recovery, and obtain corresponding economic benefit.
The method of current hydrometallurgic recovery SmCo magnetic waste material, as: Shen Xiaodong, Hou Yonggen, the utilization of magnetic waste material [J], chemical industry in Jiangsu Province, 2003,31 (3): 45-47, SmCo waste material 1:1 sulfuric acid dissolution is proposed, remove by filter acid non-soluble substance.Regulate pH to 2～3, add excessive saturated oxalic acid solution, solution rare earth elements generates canescence oxalate precipitation.Filter, after the deironing of gained filtrate, add excessive NaOH solution, filter to obtain Co (OH)
2precipitation, after dry, calcination CoO.This kind of Co (OH) that method obtains
2precipitation is difficult for filtering, and wherein carries a large amount of Na ions secretly, and on the other hand, sulfuric acid waste water acidity extremely low to the dissolution rate of SmCo waste material and that generate is high.And for example: Zhang Xiaodong, Xu Tao, the comprehensive utilization of resources of waste and old Co-base alloy material [J], rare earth, 2009,30 (2): 98-101, proposes to adopt sulfuric acid leaching, Sodium Persulfate oxidation, alkali neutralization, precipitate and separate rare earth and cobalt and iron, ferro-cobalt sedimentation acidified is controlled pH separation of cobalt and iron, finally realizes the recovery to rare earth and cobalt.In technological process, have equally the problem that sulfuric acid leaching rate is low, and add a large amount of oxygenant Sodium Persulfates, the oxide product purity obtaining is lower.
Summary of the invention
The object of the invention is for above problem, provide that a kind of technique is simple, production cost is low, samarium, the cobalt rate of recovery are high, and the oxide product purity obtaining is high, and recycling process does not produce the recoverying and utilizing method of the SmCo magnetic waste material of secondary environmental pollution.
The SmCo magnetic waste material middle-weight rare earths that experiment is used is mainly samarium, also has copper, iron etc. and replace part cobalt in alloy.For realizing the recovery of samarium and cobalt, first each element in magnetic waste material is carried out to rough segmentation, then valuable element is purified one by one, and remove wherein impurity, enable to reach corresponding product standard.The present invention is achieved by the following scheme:
A. SmCo waste material leaches with dilute hydrochloric acid, after reacting completely, filters to remove acid non-soluble substance;
B. leach liquor regulates pH=2 ~ 4, with the rare earth element in oxalic acid precipitation solution, generates canescence oxalate precipitation, filtration drying, after calcination, obtains solid oxidation samarium;
C. precipitate filtrate after samarium with oxygenant by Fe
2+be oxidized to Fe
3+, regulate pH=2 ~ 4, make the ferro element in solution generate precipitation prior to cobalt element, filter, reach the object of removing iron from solution;
D. the filtrate after deironing, regulates pH=2 ~ 4, adds oxalic acid to obtain cobalt oxalate precipitation, filters, obtains cobalt oxide after dry, calcination.
Described SmCo waste material, through crushing grinding, is crossed 20 ~ 40 mesh sieves.
The acidity of described dilute hydrochloric acid is 2 ~ 4M.
During dissolving with hydrochloric acid SmCo magnetic waste material, solid-to-liquid ratio is 1:8 ~ 1:10.
Described adjusting pH is all used ammoniacal liquor to regulate.
Described oxalic acid is oxalic acid solid or saturated oxalic acid solution.
Described with the rare earth element in oxalic acid precipitation solution, the mol ratio of oxalic acid and rare earth is 3:2; Described with the cobalt element in oxalic acid precipitation solution, the mol ratio of oxalic acid and cobalt is 1:1, consumption of oxalic acid excessive 10% ~ 30%.
Described oxygenant is hydrogen peroxide, and the add-on of hydrogen peroxide and the mol ratio of iron level are 1:2, and excessive.
In removal process, dilute hydrochloric acid Leaching reaction temperature is between 60 ~ 80 ℃.
Samaric oxalate and cobalt oxalate that precipitation obtains, obtain oxide compound in 700 ~ 850 ℃ of calcinations after 2 ~ 4 hours.
Advantage of the present invention is: technique is simple, production cost is low.Recycling process does not produce secondary environmental pollution, is applicable to industrialization and produces continuously; Prepared Samarium trioxide, cobalt oxide product extracted amount are high, and quality index all meets industry standard or Customer Standard.
four, embodiment
Embodiment mono-
Get 20g SmCo waste material and dissolve with 200ml 2.5M dilute hydrochloric acid, 80 ℃ remove by filter acid non-soluble substance after reacting completely.Leach liquor regulates after pH=2, the saturated solution that slowly adds 11g oxalic acid to be made into, and 60 ℃ are filtered after reacting completely and obtain rare earth oxalate precipitation.
Filtrate adds 9.4ml hydrogen peroxide after regulating pH, keeps pH=4 to make the ferro element in solution generate precipitation prior to cobalt element, and the iron level in solution is reduced to below 0.10g/l, and the sedimentation and filtration of ironic hydroxide is removed.Cobalt filtrate after deironing, regulates pH=4, adds 60 ℃ of reaction oxalic cobalt precipitations of 18.8g solid oxalic acid.
After rare earth oxalate and cobalt oxalate precipitation is dry, in 850 ℃ of calcinations, after 2 hours, obtain rare earth oxide (Samarium trioxide), cobalt oxide.
Embodiment bis-
Getting 10g SmCo waste material dissolves with 80 ℃, 100ml 3.0M dilute hydrochloric acid.After leach liquor filters, regulate pH=2, slowly add 5.5g solid oxalic acid, 60 ℃ are filtered after reacting completely and obtain rare earth oxalate precipitation.
Filtrate adds 4.7ml hydrogen peroxide after regulating pH, keeps pH=4 to make the ferro element in solution generate precipitation, filters and removes.Cobalt filtrate after deironing, regulates pH=4, adds 60 ℃ of reaction oxalic cobalt precipitations of 9.4g solid oxalic acid.
After rare earth oxalate and cobalt oxalate precipitation is dry, in 800 ℃ of calcinations, after 2 hours, obtain rare earth oxide (Samarium trioxide), cobalt oxide.
Embodiment tri-
Getting 37g SmCo waste material dissolves with 80 ℃, 370ml 2.5M dilute hydrochloric acid.After filtering, leach liquor regulates pH=2, the saturated solution that slowly adds 22g oxalic acid to be made into, and 60 ℃ are filtered after reacting completely and obtain rare earth oxalate precipitation.
Filtrate adds excessive hydrogen peroxide after regulating pH, keeps pH=4 to make the ferro element in solution generate precipitation, filters and removes.Cobalt filtrate after deironing, regulates pH=4, adds 23g solid oxalic acid, 60 ℃ of reaction oxalic cobalt precipitations.
After rare earth oxalate and cobalt oxalate precipitation is dry, in 850 ℃ of calcinations, after 2 hours, obtain rare earth oxide (Samarium trioxide), cobalt oxide.
Embodiment tetra-
Get 100g SmCo waste material and add tune in 600ml water to incite somebody to action, slowly add after 210ml hydrochloric acid, 80 ℃ are reacted 1 hour.After filtering, leach liquor regulates pH=2, the saturated solution that slowly adds 65.7g oxalic acid to be made into, and 60 ℃ are filtered after reacting completely and obtain rare earth oxalate precipitation.
Filtrate adds 50ml hydrogen peroxide after regulating pH, keeps pH=4 to make the ferro element in solution generate precipitation, filters and removes.Cobalt filtrate after deironing, regulates pH=4, adds 96g solid oxalic acid, 60 ℃ of reaction oxalic cobalt precipitations.
After rare earth oxalate and cobalt oxalate precipitation is dry, in 700 ℃ of calcinations, after 3.5 hours, obtain rare earth oxide (Samarium trioxide), cobalt oxide.
Claims (10)
1. a recoverying and utilizing method for SmCo magnetic waste material, is characterized in that: a. SmCo waste material leaches with dilute hydrochloric acid, after reacting completely, filters to remove acid non-soluble substance; B. leach liquor regulates pH=2 ~ 4, with the rare earth element in oxalic acid precipitation solution, generates canescence oxalate precipitation, filtration drying, after calcination, obtains solid oxidation samarium; C. precipitate filtrate after samarium with oxygenant by Fe
2+be oxidized to Fe
3+, regulate pH=2 ~ 4, make the ferro element in solution generate precipitation prior to cobalt element, filter; D. the filtrate after deironing, regulates pH=2 ~ 4, adds oxalic acid to obtain cobalt oxalate precipitation, filters, obtains cobalt oxide after dry, calcination.
2. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: described SmCo waste material, through crushing grinding, is crossed 20 ~ 40 mesh sieves.
3. the recoverying and utilizing method of SmCo magnetic waste material according to claim 2, is characterized in that: the acidity of described dilute hydrochloric acid is 2 ~ 4M.
4. the recoverying and utilizing method of SmCo magnetic waste material according to claim 3, is characterized in that: during dissolving with hydrochloric acid SmCo magnetic waste material, solid-to-liquid ratio is 1:8 ~ 1:10.
5. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: described adjusting pH is all used ammoniacal liquor to regulate.
6. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: described oxalic acid is oxalic acid solid or saturated oxalic acid solution.
7. the recoverying and utilizing method of SmCo magnetic waste material according to claim 6, is characterized in that: described with the rare earth element in oxalic acid precipitation solution, the mol ratio of oxalic acid and rare earth is 3:2; Described with the cobalt element in oxalic acid precipitation solution, the mol ratio of oxalic acid and cobalt is 1:1, consumption of oxalic acid excessive 10% ~ 30%.
8. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: described oxygenant is hydrogen peroxide, and the add-on of hydrogen peroxide and the mol ratio of iron level are 1:2, and excessive.
9. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: in removal process, dilute hydrochloric acid Leaching reaction temperature is between 60 ~ 80 ℃.
10. the recoverying and utilizing method of SmCo magnetic waste material according to claim 1, is characterized in that: samaric oxalate and cobalt oxalate that precipitation obtains, obtain oxide compound in 700 ~ 850 ℃ of calcinations after 2 ~ 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310475027.1A CN103555950A (en) | 2013-10-12 | 2013-10-12 | Recycling method of samarium cobalt magnetic waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310475027.1A CN103555950A (en) | 2013-10-12 | 2013-10-12 | Recycling method of samarium cobalt magnetic waste material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103555950A true CN103555950A (en) | 2014-02-05 |
Family
ID=50010293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310475027.1A Pending CN103555950A (en) | 2013-10-12 | 2013-10-12 | Recycling method of samarium cobalt magnetic waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103555950A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388711A (en) * | 2014-12-11 | 2015-03-04 | 内蒙古科技大学 | Method for recovering rare earth by leaching rare earth oxide molten slag |
| CN104480316A (en) * | 2014-12-24 | 2015-04-01 | 连云港市兆昱新材料实业有限公司 | Simple and convenientindustrial method for recovering Co element from NdFeBmagnetwaste materials |
| CN104928479A (en) * | 2015-07-07 | 2015-09-23 | 中南大学 | Method for treating sm-co alloy |
| CN108251649A (en) * | 2018-01-23 | 2018-07-06 | 浙江新时代中能循环科技有限公司 | A kind of hydrometallurgical process technique of samarium-cobalt alloy resource recycling |
| CN110661052A (en) * | 2018-07-01 | 2020-01-07 | 临沂春光磁业有限公司 | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder |
| CN112591783A (en) * | 2020-12-24 | 2021-04-02 | 益阳鸿源稀土有限责任公司 | Preparation method for removing iron in high-purity cerium carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305694A (en) * | 2012-03-16 | 2013-09-18 | 青岛科技大学 | Method for recovering tungsten carbide and metal cobalt from waste hard alloy |
-
2013
- 2013-10-12 CN CN201310475027.1A patent/CN103555950A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305694A (en) * | 2012-03-16 | 2013-09-18 | 青岛科技大学 | Method for recovering tungsten carbide and metal cobalt from waste hard alloy |
Non-Patent Citations (4)
| Title |
|---|
| 周邦娜等: ""从氯化钴溶液中沉淀回收草酸钴"", 《上海金属（有色分册）》, vol. 11, no. 3, 30 June 1990 (1990-06-30), pages 7 - 10 * |
| 沈晓东等: ""磁性废料的利用"", 《江苏化工》, vol. 31, no. 3, 30 June 2003 (2003-06-30), pages 45 - 47 * |
| 越村英雄等: ""从钐-钴合金废料中回收衫"", 《湿法冶金》, 1 October 1990 (1990-10-01), pages 59 - 67 * |
| 黄明雯等: ""液相沉淀法制备草酸钴粉体的研究"", 《无机盐工业》, vol. 40, no. 4, 30 April 2008 (2008-04-30), pages 31 - 34 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388711A (en) * | 2014-12-11 | 2015-03-04 | 内蒙古科技大学 | Method for recovering rare earth by leaching rare earth oxide molten slag |
| CN104480316A (en) * | 2014-12-24 | 2015-04-01 | 连云港市兆昱新材料实业有限公司 | Simple and convenientindustrial method for recovering Co element from NdFeBmagnetwaste materials |
| CN104480316B (en) * | 2014-12-24 | 2016-12-07 | 连云港市兆昱新材料实业有限公司 | A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material |
| CN104928479A (en) * | 2015-07-07 | 2015-09-23 | 中南大学 | Method for treating sm-co alloy |
| CN104928479B (en) * | 2015-07-07 | 2017-03-01 | 中南大学 | A kind of method processing samarium-cobalt alloy |
| CN108251649A (en) * | 2018-01-23 | 2018-07-06 | 浙江新时代中能循环科技有限公司 | A kind of hydrometallurgical process technique of samarium-cobalt alloy resource recycling |
| CN108251649B (en) * | 2018-01-23 | 2019-06-18 | 浙江新时代中能循环科技有限公司 | A kind of hydrometallurgical process technique of samarium-cobalt alloy resource recycling |
| CN110661052A (en) * | 2018-07-01 | 2020-01-07 | 临沂春光磁业有限公司 | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder |
| CN112591783A (en) * | 2020-12-24 | 2021-04-02 | 益阳鸿源稀土有限责任公司 | Preparation method for removing iron in high-purity cerium carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103555950A (en) | Recycling method of samarium cobalt magnetic waste material | |
| CN103468979B (en) | The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag | |
| EP3034636B1 (en) | Method for processing laterite-nickel ore and method for recycling scandium | |
| KR101392307B1 (en) | Recovery method of rare earth elements from waste permanent magnet | |
| CN103468978B (en) | A kind of method carrying scandium from laterite nickel ore by sulfuric acid leaching liquid | |
| AU2013238535B2 (en) | Method for producing high-purity nickel sulfate | |
| CN103160689B (en) | Method of iron extraction and removal with solvent extraction agent | |
| CN102094119A (en) | Method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching | |
| CN103468972B (en) | The treatment process of red soil nickel ore synthetical recovery scandium and nickel cobalt | |
| CN103484695B (en) | Treatment method for comprehensively recovering valuable elements from laterite-nickel ore | |
| CN103966446A (en) | Method for separating and recovering copper, nickel and iron from electroplating sludge | |
| CN102121068A (en) | Method for preparing vanadium pentoxide | |
| CN103643044A (en) | Technology for directly extracting copper and zinc by using copper dust wet method | |
| CN112375910A (en) | Recovery processing method of waste power battery powder | |
| CN110607537A (en) | Method for synchronously and efficiently extracting rare earth and iron from high-value recycled neodymium iron boron waste | |
| CN104611565A (en) | A method of selectively recovering cobalt and copper from a cobalt-copper-zinc-manganese production waste solution | |
| CN105274352B (en) | A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate | |
| JP5631948B2 (en) | Nickel sludge treatment method | |
| CN104726724A (en) | Method for extracting scandium from nickel laterite ores | |
| CN105648234A (en) | Separating method for zinc and cobalt in materials containing zinc and cobalt | |
| CN109133178B (en) | Production process of manganese sulfate | |
| CN112941321B (en) | Method for strengthening leaching reaction of neodymium iron boron magnet by combining electrochemical anodic oxidation with ionic flocculant | |
| CN101693554A (en) | Method for extracting vanadium pentoxide from stone coal ores | |
| CN103074491A (en) | Method for extracting and separating copper, chromium and nickel in acid leaching solution | |
| CN104060093B (en) | A kind for the treatment of process of waste water neutralize gypsum tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140205 |