CN1023235C - Recovery and processing method of waste hand alloy material - Google Patents
Recovery and processing method of waste hand alloy material Download PDFInfo
- Publication number
- CN1023235C CN1023235C CN91107165A CN91107165A CN1023235C CN 1023235 C CN1023235 C CN 1023235C CN 91107165 A CN91107165 A CN 91107165A CN 91107165 A CN91107165 A CN 91107165A CN 1023235 C CN1023235 C CN 1023235C
- Authority
- CN
- China
- Prior art keywords
- tungsten
- cobalt
- powder
- carbide
- wimet
- 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.)
- Expired - Fee Related
Links
Images
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 present invention discloses a method for recovering and treating hard alloy waste materials. With the method, waste block materials, waste powder materials, waste metal tungsten blocks, tungsten filaments, tungsten powder and tungsten dioxide generated in the course of using and producing hard alloy are prepared into cobalt and carbon tungsten which are uniformly distributed by the working procedures of the breakage, the cleaning, the baking, the reduction, the carbonization, the adjustment and the preparation of the hard alloy. The crystal size of tungsten carbide is the crystal size of tungsten cobalt or tungsten cobalt titanium hard alloy of 0.6 to 1.0 mum or hard alloy spraying (weld) powder. The method has a stable process and no special requirements for equipment, and the method is the recovery and treatment method having the advantages of multiple species, high quality and simple process equipment.
Description
The present invention relates to a kind of recovery and treatment method of waste hand alloy material, use waste hand alloy material and produce useless powder or the useless piece material that produces in the Wimet process, and scrap metal tungsten piece, tungsten filament, tungsten powder and Tungsten oxide, make the tungsten carbide-cobalt composite powder end by operations such as roasting, reduction, carbonization and adjustment, produce the method for hart metal product then.
The method of recycling waste hand alloy material in the prior art is more, and selective electro-dissolving of wherein the most frequently used method and zinc melt method.The selectivity electro-dissolving is under electric field action, use suitable leaching agent that the binding agent cobalt in the useless piece material of Wimet is dissolved in the leaching liquid, be processed into cobalt oxide with the chemical metallurgy method again, the useless piece material that has dissolved away binding agent obtains tungsten-carbide powder after cleaning, crushing grinding, deoxidation, and then produces hart metal product.The weak point of this way is to be only limited to handle cobalt contents greater than the useless piece material of 8% W-Co kind Wimet, can not handle powder and cobalt contents less than the useless piece material of 8% Wimet, and technological process and a whole set of electrolyzer are comparatively complicated.The molten method of zinc is that cobalt and zinc that hard is closed in the waste material form the zinc cobalt-base alloy, dezincifies through vacuum distilling and handles, and crushing grinding obtains the tungsten-cobalt carbide mixed powder then, produces hart metal product with this powder again.Though this method can be handled the piece material of various cobalt contentss, but be not suitable for the processing powder scrap, exist in the CEMENTED CARBIDE PRODUCTION process simultaneously that zinc pollution, product properties are not high, productive expense and problems such as energy consumption height, high-temperature vacuum technology and equipment requirement complexity.
In sum, the molten method of selectivity electro-dissolving and zinc all can only be handled the useless piece material of Wimet, can not handle other secondary tungsten raw materials such as powder material and tungsten piece, tungsten filament, tungsten powder, and tungsten carbide crystal grain degree and size-grade distribution in the hart metal product that obtains are wayward, be subjected to having a strong impact on of tungsten carbide crystal grain degree in the processed waste hand alloy material and size-grade distribution, therefore the hart metal product quality that exists production is low, the problem of unstable properties, and these two kinds of methods of while are mainly used in the production, coarse-grain granularity hart metal product.
The recovery and treatment method that the purpose of this invention is to provide a kind of waste hand alloy material, use present method and can handle useless powder and the useless piece material that produces in the tungsten-cobalt hard alloy waste material of various cobalt contentss and the production process thereof, and, make one or more tungsten-cobalt composite powders, tungsten carbide-cobalt composite powder or Wimet spraying (weldering) powder product by operations such as roasting, reduction, carbonization and adjustment such as secondary tungsten raw materials such as scrap metal tungsten piece, tungsten filament, tungsten powder and Tungsten oxides.
Design of the present invention is achieved in that its technical process is: secondary tungsten raw material-fragmentation cleaning-roasting-ball milling-reduce-sieve-join carbon-to-carbonization-ball milling screening-adjustment-wet-milling-compacting-sintering-W-Co kind or W-Co-Ti kind Wimet; Or by adjustment-sintering-ball milling screening-Wimet spraying (weldering) powder.Utilize the useless piece material of Wimet through grinding, clean and remove foreign material such as copper, iron, in the process furnace of airiness into about 5-30mm, temperature is lower than under 1000 ℃, ball milling after roasting 4-16 hour, temperature is that logical hydrogen carries out reduction reaction under 760-960 ℃ the condition in stove then.Also in stove, send into warm air or oxygen-rich air during roasting, dehydrogenation makes also can use outside the reductive agent reducing gas such as carbon monoxide, reduction can be that the branch secondary reduction promptly is reduced into for the first time intermediate compound, for the second time restore into tungsten-Co composite powder, but preferably once directly be reduced into tungsten-Co composite powder.Under guaranteeing that abundant carbonization is with the prerequisite that forms wolfram varbide; in the composite powder that reduction obtains, allocate carbon black into; under hydrogen shield, carry out carburizing reagent completely not being higher than under 1200 ℃ the temperature behind the thorough mixing, also can adopt the mode of vacuum carburization to carry out carburizing reagent without hydrogen shield.Because the existence of cobalt, carbonization temperature is related to the hard degree of carbonized product, also is related to carbonation reaction, so carbonization temperature is crucial, should be controlled between 800-1200 ℃.Correct carbonization temperature and technological process can obtain loose frangible, uncombined carbon less than 0.1% tungsten carbide-cobalt composite powder end.According to the requirement of hart metal product, in the tungsten carbide-cobalt composite powder end, replenish or reduce the cobalt amount, or add other additive and adjust, thereby make one or more W-Co kinds, W-Co-Ti kind Wimet or tungsten-cobalt carbide Wimet spraying (weldering) powder.Adjust and both can before reduction, also can before carbonization, carry out.
The tungsten-cobalt hard alloy that effect of the present invention is to make various cobalt contentss use and production process in secondary tungsten raw material regeneration hard metal article and Wimet spraying (weldering) powder such as various useless piece material, useless powder, scrap metal tungsten piece, tungsten powder and Tungsten oxide of producing, and provide a kind of approach that inferior carefully tungsten carbide crystal grain degree Wimet and Wimet spray (weldering) powder of producing.Reclaim secondary tungsten raw material with roasting, reduction, carbonization and adjustment, thereby make W-Co kind or W-Co-Ti kind Wimet or tungsten-cobalt carbide Wimet spraying (weldering) powder, and the tungsten carbide crystal grain degree of the hart metal product of making and size-grade distribution are not subjected to the influence of secondary tungsten raw material, cobalt and wolfram varbide distribution simultaneously is very even, and the tungsten carbide crystal grain degree reaches 0.6-1.0 μ m.Listed the performance that recycles the Wimet that secondary tungsten raw material produces with the present invention in the following table.(seeing Table)
Can find out that by performance data in the table regeneration hart metal product performance is all above the standard of performance of like product.
Figure one is the SEI figure of tungsten-Co composite powder of producing with the present invention;
Figure two is the SEI figure at the tungsten carbide-cobalt composite powder end of producing with the present invention;
Figure three is to be 1 Wimet phasor with the group number that the present invention produces;
Figure four is to be 2 Wimet metallograph with the group number that the present invention produces.
Embodiments of the invention are as follows:
Embodiment one:
Cleaned waste hand alloy material loosely is laid in the boat, in the stove that the warm air that opens wide fire door flows, temperature under 750-950 ℃ condition roasting 4-16 hour.Press ball with sintered carbide ball: the ratio of material=3: 1, ground 1-5 hour at Wimet ball grinding cylinder endosphere, separate ball and material and also remove insufficiently burnt block of material, the WO that obtains
3-CoWo
4Composite powder once is reduced into tungsten-cobalt composite powder by bed thickness 5-30mm dress boat at 760-960 ℃ of temperature subinverse hydrogen, crosses 60 mesh sieves, allocates carbon black into and mixes by generating the required carbon amount of Wc again, in the boat of packing into.Temperature is that 800-1200 ℃ of charing generates the compound material of Wc-Co under hydrogen shield, presses ball with the Wimet ball mill device: expected=3: 1 ball milling 1-5 hour, and crossed 80 mesh sieves and promptly obtain the Wc-Co composite powder; Another kind of useless tungsten piece or the tungsten powder used produced the Wc-Co composite powder that contains cobalt 0-3% by said process.Adjust cobalt contentss with these two kinds of composite powders and be 6% and add an amount of Tac, add behind the ethanol wet-milling 48-72 hour, drying and screening, compacting and at 1420-1430 ℃ of sintering temperature obtain tungsten-cobalt hard alloy, (figure three).
Embodiment two:
Wo with two kinds of cobalt contentss
3-CoWo
4It is 6.7% that composite powder is adjusted cobalt contents, make the Wc-Co composite powder by embodiment one, in the Wimet ball mill device, suppress after the wet-milling 24-48 hour drying and screening after adding ethanol, and under 1410-1430 ℃ of temperature, carry out normal sintering and obtain tungsten-cobalt hard alloy, (figure four).
Embodiment three:
Adjusting cobalt contents with the W-Co composite powder of two kinds of cobalt contentss is 13.17%, makes W by embodiment one
c-C
oComposite powder adds W
c-Tic composite carbide makes titanium content reach 11.3%, adds ethanol and in the Wimet ball grinding cylinder wet-milling 56-72 hour, and compacting and carry out normal sintering under 1510-1530 ℃ of temperature after the drying and screening makes W-Co-Ti carbide alloy, (group number 3 in the table).
Embodiment four
The W that makes by embodiment one
c-C
oComposite powder, adjusting cobalt contents is 17%, mixes the back granulation and crosses 60 mesh sieves, uses the hydrogen shield sintering under 1000-1300 ℃ of temperature, suitably sieves after the fragmentation, obtains Wimet spraying (weldering) powder.
Remarks: all by taylor criteria, relative content is calculated by weight sieve in this specification sheets " order ".
Group number title Co% Ti% bending strength hardness magnetic force Wc crystal grain Co crystal grain
N/mm
2HRA KA/m size Um size Um
1 tungsten cobalt hard 6 1,846 92.1 21.4 0.6＜1
The matter alloy
2 tungsten cobalts hard 8 2,093 92.4 21.3 0.8＜1
The matter alloy
3 tungsten cobalt titaniums 8 11.3 1,790 92.0 15.8 0.8＜1
Wimet
Claims (6)
1; a kind of recovery and treatment method of waste hand alloy material; it is characterized in that by secondary tungsten raw material through grinding into about 5～30mm; copper is removed in cleaning; iron; in the process furnace of airiness; temperature is lower than under 1000 ℃; after the roasting 4～16 hours; carry out ball milling; temperature in stove then; be under 760～960 ℃ the condition, feed hydrogen and carry out reduction reaction, form tungsten-Co composite powder; allocate carbon black into; under the hydrogen shield condition, temperature is controlled at carries out carburizing reagent between 800～1200 ℃, forms the tungsten carbide-cobalt composite powder end of uncombined carbon less than 0.1% (weight); adjust cobalt contents then and/or add other additives, make one or more W-Co kinds; W-Co-Ti kind Wimet or tungsten-cobalt carbide Wimet spraying (weldering) powder.
2, method according to claim 1, it is characterized in that can be to WO before and after reduction
3-COWo
4, the cobalt amount is adjusted in tungsten-cobalt composite powder, or after carbonization to W
c-C
oCobalt amount in the composite powder is adjusted.
3, method according to claim 1 is characterized in that making W
cGrain fineness number be the W-Co kind of 0.61.0 μ m or W-Co-Ti kind Wimet and tungsten-cobalt carbide Wimet spraying (weldering) powder product.
4, according to claim 1 or 3 described methods, it is characterized in that roasting temperature at 750～950 ℃, press ball with sintered carbide ball: the ratio ball milling of material=3: 1 1～5 hour, separate ball and material and remove insufficiently burnt block of material,, cross 60 mesh sieves then by the reduction of bed thickness 5～30mm dress boat, allocate carbon black into and mix in the boat of packing into, carry out carbonization, press ball again: material=3: 1 ball milling 1～5 hour, cross 80 mesh sieves and form W
c-C
oComposite powder is adjusted cobalt contents＜8%(weight then), and/or add an amount of T
aC, and added the ethanol wet-milling 48～72 hours, drying is sieved, compacting, sintering, makes tungsten-cobalt hard alloy.
5, according to claim 1 or 3 described methods, it is characterized in that W
o-Ti
cComposite carbide adds in the tungsten carbide-cobalt composite powder end, and adds the ethanol wet-milling, drying, sieves, suppresses, and sintering makes W-Co-Ti carbide alloy.
6, according to claim 1 or 3 described methods, it is characterized in that W
c-C
oComposite powder under 1000～1300 ℃ of temperature, is used the hydrogen shield sintering after adjusting cobalt contents, and ball milling sieves, and makes Wimet spraying (weldering) powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91107165A CN1023235C (en) | 1991-03-19 | 1991-03-19 | Recovery and processing method of waste hand alloy material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91107165A CN1023235C (en) | 1991-03-19 | 1991-03-19 | Recovery and processing method of waste hand alloy material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054270A CN1054270A (en) | 1991-09-04 |
| CN1023235C true CN1023235C (en) | 1993-12-22 |
Family
ID=4908523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91107165A Expired - Fee Related CN1023235C (en) | 1991-03-19 | 1991-03-19 | Recovery and processing method of waste hand alloy material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1023235C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575675B (en) * | 2009-05-25 | 2011-08-10 | 刘嵘 | Method for producing cast tungsten carbide by using hard-alloy grinding waste material |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064716C (en) * | 1998-05-19 | 2001-04-18 | 自贡硬质合金厂 | Recovering and regenerating treating process for waste hard alloy |
| CN1314818C (en) * | 2005-08-31 | 2007-05-09 | 段立成 | Method for extracting rare metal from waste and old carbide alloy |
| CN100404175C (en) * | 2006-05-30 | 2008-07-23 | 成都科力铁硬质合金有限公司 | Hard alloy recovery method |
| CN100451145C (en) * | 2007-05-21 | 2009-01-14 | 陈兆盈 | Vacuum high temperature treatment method for reducing oxygen content of electric dissolving regeneration WC |
| CN101658940B (en) * | 2009-09-25 | 2011-11-16 | 北京工业大学 | Method for recycling and regenerating hard alloy |
| EP2427286A4 (en) * | 2009-10-26 | 2012-06-27 | Minpro Aktiebolag | Recycling of tungsten carbides |
| CN102758089B (en) * | 2011-04-25 | 2013-11-27 | 自贡科瑞德新材料有限责任公司 | Recovering and regenerating method of cemented carbide scrap material |
| CN102294488A (en) * | 2011-08-23 | 2011-12-28 | 浙江锐利硬质合金有限公司 | Tungsten cobalt hard alloy recycling process |
| CN102974831B (en) * | 2011-09-05 | 2015-12-02 | 龙岩市华锐硬质合金工具有限公司 | The recovery and reusing and recycling method of waste and old tungsten carbide tipped tool |
| CN102699337B (en) * | 2012-05-14 | 2014-03-26 | 北京工业大学 | Method for synthesizing and preparing hard alloy powder by mixing original powder and regenerated powder |
| CN103911514B (en) * | 2013-01-06 | 2016-03-02 | 中石化上海工程有限公司 | The recovery and treatment method of scrap hard alloy grinding material |
| CN104294049B (en) * | 2014-09-23 | 2016-05-11 | 福建德隆硬质合金有限公司 | A kind of recycling technique of hard alloy scraps |
| CN104439239B (en) * | 2014-11-06 | 2017-05-03 | 金堆城钼业股份有限公司 | Method for repeatedly using medium-frequency inducing sintering furnace tungsten molybdenum waste heating body |
| US10161017B2 (en) * | 2015-06-08 | 2018-12-25 | Korea Institute Of Geoscience And Mineral Resources | Method for crushing hard tungsten carbide scraps |
| CN106947865B (en) * | 2016-05-25 | 2018-08-24 | 江西理工大学 | A kind of energy-efficient method for oxidation of scrap hard alloy |
| CN108977664B (en) * | 2018-07-24 | 2019-10-29 | 中南大学 | The method for recycling tungsten carbide and cobalt in scrap hard alloy |
| CN109487075B (en) * | 2018-12-18 | 2020-07-07 | 清华大学 | Method for comprehensively recovering valuable elements in aluminum-based petroleum refining catalyst by utilizing reducing gas |
| CN109593965B (en) * | 2018-12-18 | 2020-07-07 | 清华大学 | Method for recovering valuable elements from aluminum-based petroleum refining waste catalyst |
| CN109652652B (en) * | 2018-12-18 | 2020-07-07 | 清华大学 | Method for recycling valuable elements from aluminum-based petroleum refining waste catalyst in clean and environment-friendly manner |
| CN111168073A (en) * | 2019-12-31 | 2020-05-19 | 武汉新锐合金工具有限公司 | Recycling process of hard alloy falling material and wire cleaning material |
| CN112209446B (en) * | 2020-09-04 | 2023-05-23 | 崇义章源钨业股份有限公司 | Method for recycling Cr-containing tungsten carbide waste and application thereof |
| CN113322378A (en) * | 2021-06-04 | 2021-08-31 | 广东正信硬质材料技术研发有限公司 | Recycling method of waste hard alloy |
| CN114317976B (en) * | 2021-12-24 | 2024-04-19 | 南昌硬质合金有限责任公司 | Short-process recycling method of hard alloy mixture |
| CN115896520A (en) * | 2022-12-29 | 2023-04-04 | 株洲长江硬质合金工具有限公司 | Method for preparing hard alloy round bar by using hard alloy waste |
-
1991
- 1991-03-19 CN CN91107165A patent/CN1023235C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575675B (en) * | 2009-05-25 | 2011-08-10 | 刘嵘 | Method for producing cast tungsten carbide by using hard-alloy grinding waste material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054270A (en) | 1991-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1023235C (en) | Recovery and processing method of waste hand alloy material | |
| DE3239718C2 (en) | ||
| US3779714A (en) | Dispersion strengthening of metals by internal oxidation | |
| EP1079950B1 (en) | Sinter-active metal and alloy powders for powder metallurgy applications and methods for their production and their use | |
| DE60201922T2 (en) | Spray powder and process for its preparation | |
| DE60016634T2 (en) | PREPARATION FOR FE-CR-AL ALLOYING AND SUCH ALLOYING | |
| CN102905822A (en) | Titanium alloy compound powder combined with copper powder, chrome powder or iron powder, titanium alloy material using said powder as raw material and production method thereof | |
| DE19945318A1 (en) | Process for the production of spheroidized hard material powder | |
| DE3806602C2 (en) | ||
| WO2007121931A2 (en) | Hard metal body formed from a mixture containing a tungsten-cobalt-carbon | |
| DE3010506A1 (en) | METAL GLASS POWDER AND METHOD FOR THE PRODUCTION THEREOF | |
| AT394188B (en) | METHOD FOR THE PRODUCTION OF FINE-GRINED, SINTER-ACTIVE NITRIDE AND CARBONITRIDE POWDERS OF TITANIUM | |
| CN102534277A (en) | New preparation method for coarse particles and super coarse particle hard alloy | |
| DE2750606C2 (en) | ||
| DE102018116728A1 (en) | SINTER POWDER AND SINTER CARBIDE COMPOSITIONS | |
| EP3041631B1 (en) | Chromium metal powder | |
| EP1285096A1 (en) | Method and device for producing pig iron or liquid steel pre-products from charge materials containing iron ore | |
| CN108504889A (en) | CrFeAlMgSi alloy composite materials and laser sintered synthetic method | |
| GB2150157A (en) | Wrought powder metallurgy processing | |
| DE3100926A1 (en) | "Sintered-metal hard alloys and method for preparing them" | |
| CH657152A5 (en) | METHOD FOR PRODUCING ALUMINUM-SILICON ALLOYS. | |
| DE3830111C2 (en) | ||
| CA1233678A (en) | Wrought p/m processing for master alloy powder | |
| DE1814557A1 (en) | Method and device for carrying out chemical reactions | |
| EP0839920B1 (en) | Process for preparing a starting powder material for fine grained hard metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |