CN102653404B - Method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste - Google Patents
Method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste Download PDFInfo
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- CN102653404B CN102653404B CN2011102714676A CN201110271467A CN102653404B CN 102653404 B CN102653404 B CN 102653404B CN 2011102714676 A CN2011102714676 A CN 2011102714676A CN 201110271467 A CN201110271467 A CN 201110271467A CN 102653404 B CN102653404 B CN 102653404B
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- tungsten carbide
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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
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- 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 relates to a method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste, and the method comprises the following steps of: (1) separating graphite particles, carbon black and silico-calcium impurity which are lighter in specific gravity from the tungsten-containing soft waste with heavier specific gravity through a concentrating table or a chute; (2) removing metal impurities: putting the tungsten-containing soft waste into 3-10% of diluted hydrochloric acid for leaching, and stirring in an agitation tank; (3) filtering, cleaning, and removing chloride residue in the material, thus obtaining tungsten carbide; (4) drying; (5) carrying out ball-milling and mixing; (6) carrying out high-temperature smelting, pouring and forming a cast tungsten carbide alloy bar; and (7) crushing and screening to obtain cast tungsten carbide powder of different specifications. According to the invention, a simpler process flow with lower production manufacture cost is selected according to the characteristics of the impurity components of the soft waste, and Fe, Si, Ca, the graphite particles, the carbon black, Al, Ni and other impurities which are higher in content in the soft waste can be removed, so that the quality of the obtained tungsten carbide powder reaches the raw material requirement in production of the cast tungsten carbide.
Description
Technical field
The present invention relates to the production method of cast tungsten carbide, particularly utilize tungstenic hard material soft waste material to produce the method for cast tungsten carbide.
Background technology
The recycling of tungstenic hard material soft waste material is subject to manufacturing always and payes attention to.Domestic existing tungstenic hard material comprises cast tungsten carbide, monocrystalline tungsten carbide, tungsten cobalt spray coating powder etc., be easy to produce some soft waste materials in the hard material production process, comprise the suction iron charge that produces in the process of producing cast tungsten carbide, macrocrystalline tungsten carbide, fabric, exhausting material, blower fan material, defective material etc., these soft waste material kinds are assorted, contain the impurity such as higher iron, silicon, calcium, be difficult for processing, can't directly return to produce and utilize.All generally it to be carried out low price as tungsten waste sell or directly as waste hand alloy material, process, as directly tungsten waste being obtained sodium wolframate → wolframic acid → tungstic oxide → tungsten powder (" metal cobalt reclaims tungsten and cobalt from useless top hammer " the 25 volume second phases of ground " Hunan institute journal " in April, 2004) through metal cobalt, the shortcoming of this way is to control that parameter is many, long flow path, waste time and energy; Perhaps directly use electric smelting method recovered WC, this method is at 900 ℃ of temperature, add zinc to make cobalt and zinc in discarded hard alloy form the zinc cobalt-base alloy, dezincify and process through vacuum distilling at a certain temperature, form spongy alloy block, then broken, batching grinds to form raw material powder, and technique is produced hart metal product routinely finally.The method shortcoming exists facility investment large, and productive expense and energy consumption are high, and is difficult to thoroughly remove dezincify, causes quality product, unstable properties,, because molten powder zinc has certain harm to environment, also has problem of environmental pollution in addition.
CN 101575675A patent discloses the method for utilizing the hard-alloy grinding material to produce cast tungsten carbide, the method is to belong to the electrodissolution method, cobalt in grinding material, ferrous metal are dissolved in leach liquor, obtain the regeneration tungsten-carbide powder dissolve the metals such as cobalt in grinding material, iron, nickel by electrochemical method after, still there are the metallic impurity such as cobalt, iron, nickel after washing drying, have a strong impact on quality and the application of wolfram varbide, and the electrolytic process activity duration is long, efficiency is low, also has certain problem of environmental pollution.
Summary of the invention
The present invention is directed to the deficiency that existing tungstenic hard material soft waste material recovery method exists, a kind of new recovery method has been proposed, not only technique is simple, running cost is low, and utilizes quality and the quality of the tungsten carbide powder after processing, and reaches the ingredient requirement of producing cast tungsten carbide.
In order to solve above technical problem, technical scheme of the present invention comprises the steps:
(1) except graphite granule, carbon black and silico-calcium impurity: through cleaning table or chute, the graphite granule that proportion is lighter, carbon black and silicon, calcium impurities separate from heavier tungsten-contained soft waste material with tungstenic hard material soft waste material;
(2) except metallic impurity: it is that 3%～10% dilute hydrochloric acid leaches in steel basin that the tungsten-contained soft waste material that step (1) is obtained is placed in mass percent concentration, churning time 2～6 hours, 50～80 ℃ of temperature, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:3～1:5; After the soaking and stirring of long period, sufficient chemical reaction occurs in soft waste material and dilute hydrochloric acid, obtains the solid phase wolfram varbide, and the metallic impurity such as the iron in soft waste material, nickel, aluminium and hydrochloric acid reaction generation iron protochloride, nickelous chloride, aluminum chloride, be removed;
(3) filter, clean: the liquid with in vacuum pump suction strainer material, clean material with deionized water, remove the muriate residue in material, obtain wolfram varbide;
(4) oven dry: the wolfram varbide that step (3) obtains is sent into baking oven, dried through 10～24 hours under 60～100 ℃ of conditions;
(5) ball milling mix: the tungsten carbide powder that step (4) obtains is analyzed, join carbon or join tungsten according to analytical results, and ball milling is mixed;
(6) high melt: the material that step (5) obtains is sent in high temperature melting furnace, carried out melting at the temperature of 2600～2900 ℃, and pour into the cast tungsten carbide alloy bar.
(7) crushing and screening: the cast tungsten carbide alloy bar that step (6) obtains is broken, as to be sieved into different size casting tungsten carbide powder.
Further improve and be, described step (2) deironing is agitation leach impurity in containing 5% hydrochloric acid soln, churning time 4 hours, and temperature 70 C, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:4.
Further improvement is, described step (4), and it is 90 ℃ that tungsten carbide powder cleans the post-drying temperature, drying time is 24 hours.
Further improving is that described smelting furnace temperature is at 2800 ℃.
Adopt the production method of above step, higher iron, silicon, calcium, graphite granule, carbon black, aluminium and the nickel etc. that contain in soft waste material can't directly return to the impurity of producing utilization and be removed one by one, the quality of the tungsten carbide powder that obtains and quality, reach the ingredient requirement of producing cast tungsten carbide.Above-mentioned production stage, more existing technical process is simple, production cost is low, also can be to environment.
Embodiment
, in order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
With 200kg tungstenic hard material soft waste material process cleaning table, after removing lighter graphite granule, carbon black and silico-calcium impurity, it is that 3% dilute hydrochloric acid leaches in steel basin that this soft waste material is inserted mass percent concentration, churning time 2 hours, temperature 60 C, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:3.Fall to soak afterwards the dilute hydrochloric acid liquid of material with the vacuum pump suction strainer, then with deionized water, clean material 5 times, remove the muriate residue in material.This powder was dried 24 hours at 80 ℃ of temperature, obtain powder 190kg, composition analysis is carried out in sampling,, according to analytical results, allocates carbon or tungsten powder into and mix in powder, makes the powder composition meet the proportioning process of routine casting wolfram varbide.Then powder is distributed in some boats melting in the high temperature melting furnace of sending into successively 2750 ℃, and pours into the cast tungsten carbide alloy bar.The cast tungsten carbide alloy bar passes through section inspection, fragmentation, is sieved into the casting tungsten carbide powder of 10-400 order different size, detect and analyze through instrument, total carbon content is 3.90%, and needle-like eutectic structure content is 81%, this quality product GB/T2967-2008 that is up to state standards.
The ground general plan that embodiment 2:(is identical with embodiment 1)
200kg tungstenic hard material soft waste material, through after mineral processing chute removes lighter impurity, is inserted 6% dilute hydrochloric acid and leached in steel basin, churning time 4 hours, temperature 50 C, solid-to-liquid ratio is 1:4., with this material process vacuum pump suction strainer, with deionized water, clean 6 times afterwards, remove the muriate residue in material.This powder was dried 16 hours at 90 ℃ of temperature; The powder 187kg that obtains,, according to the proportioning process of cast tungsten carbide, allocate carbon or tungsten powder into and mix, and minute some boats are sent into the interior melting of high temperature melting furnace of 2800 ℃, and pour into the cast tungsten carbide alloy bar.Through casting tungsten carbide powder broken, that be sieved into 10-400 order different size, detect and analyze through instrument, total carbon content is 3.91%, needle-like eutectic structure content is 83%, this quality product GB/T2967-2008 that is up to state standards.
The ground general plan that embodiment 3:(is identical with embodiment 1)
200kg tungstenic hard material soft waste material through cleaning table, after removing lighter impurity, is inserted this soft waste material in 10% dilute hydrochloric acid and leached in steel basin, churning time 1 hour, temperature 70 C, solid-to-liquid ratio is 1:5., with this material process vacuum pump suction strainer, with deionized water, clean 7 times afterwards, remove the muriate residue in material.This powder was dried 10 hours at 90 ℃ of temperature; The powder 185kg that obtains,, according to the proportioning process of cast tungsten carbide, allocate carbon or tungsten powder into and mix, and minute some boats are sent into the interior melting of high temperature melting furnace of 2900 ℃, and pour into the cast tungsten carbide alloy bar.Through casting tungsten carbide powder broken, that be sieved into 10-400 order different size, detect and analyze through instrument, total carbon content is 3.92%, needle-like eutectic structure content is 80%, this quality product GB/T2967-2008 that is up to state standards.
The foregoing is only preferred embodiment of the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a method of utilizing tungstenic hard material soft waste material to produce cast tungsten carbide, is characterized in that, comprises the following steps:
(1) except graphite granule, carbon black and silico-calcium impurity: through cleaning table or chute, the graphite granule that proportion is lighter, carbon black and silico-calcium impurity separate from heavier tungsten-contained soft waste material with tungstenic hard material soft waste material;
(2) except metallic impurity: it is that 3%～10% dilute hydrochloric acid leaches in steel basin that the tungsten-contained soft waste material that step (1) is obtained is placed in mass percent concentration, churning time 2～6 hours, 50～80 ℃ of temperature, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:3～1:5;
(3) filter, clean: the liquid with in vacuum pump suction strainer material, clean material with deionized water, remove the muriate residue in material, obtain wolfram varbide;
(4) oven dry: the wolfram varbide that step (3) obtains is sent into baking oven, dried through 10～24 hours under 60～100 ℃ of conditions;
(5) ball milling mix: the tungsten carbide powder that step (4) obtains is analyzed, join carbon or join tungsten according to analytical results, and ball milling is mixed;
(6) high melt: the material that step (5) obtains is sent in high temperature melting furnace, carried out melting at the temperature of 2600～2900 ℃, and pour into the cast tungsten carbide alloy bar;
(7) crushing and screening: the cast tungsten carbide alloy bar that step (6) obtains is broken, as to be sieved into different size casting tungsten carbide powder.
2. the method for utilizing tungstenic hard material soft waste material to produce cast tungsten carbide according to claim 1, it is characterized in that described step (2) is is agitation leach impurity in 6% hydrochloric acid soln at mass percent concentration, churning time 4 hours, temperature 50 C, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:4.
3. the method for utilizing tungstenic hard material soft waste material to produce cast tungsten carbide according to claim 1, it is characterized in that described step (2) is is agitation leach impurity in 3% hydrochloric acid soln at mass percent concentration, churning time 2 hours, temperature 60 C, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:3.
4. the method for utilizing tungstenic hard material soft waste material to produce cast tungsten carbide according to claim 1, it is characterized in that described step (2) is is agitation leach impurity in 10% hydrochloric acid soln at mass percent concentration, churning time 1 hour, temperature 70 C, the solid-liquid mass ratio of tungsten-contained soft waste material and hydrochloric acid is 1:5.
5. the method for utilizing tungstenic hard material soft waste material to produce cast tungsten carbide according to claim 1, is characterized in that described step (4), and it is 90 ℃ that tungsten carbide powder cleans the post-drying temperature, and drying time is 16 hours.
6. the method for utilizing tungstenic hard material soft waste material to produce cast tungsten carbide according to claim 1, is characterized in that described step (6) smelting furnace temperature is at 2800 ℃.
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| US6524366B1 (en) * | 2000-09-22 | 2003-02-25 | N.V. Union Miniere S.A. | Method of forming nanograin tungsten carbide and recycling tungsten carbide |
| CN1485450A (en) * | 2003-04-11 | 2004-03-31 | 自贡硬质合金有限责任公司 | Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap |
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| JP2000072430A (en) * | 1998-08-28 | 2000-03-07 | Wada Kogyo Kk | Repowdering technique for spent sintered hard alloy part by tin impregnation method |
| CN101239720A (en) * | 2008-03-17 | 2008-08-13 | 株洲京株硬质合金新材料有限公司 | Method for fast crushing separating extracting tungsten carbide and cobalt carbonate by using waste ultra-fine hard alloy body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6524366B1 (en) * | 2000-09-22 | 2003-02-25 | N.V. Union Miniere S.A. | Method of forming nanograin tungsten carbide and recycling tungsten carbide |
| CN1485450A (en) * | 2003-04-11 | 2004-03-31 | 自贡硬质合金有限责任公司 | Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap |
Non-Patent Citations (2)
| Title |
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| 《化学化工大辞典》编委会，化学工业出版社辞书编辑部.碳化钨.《化学化工大辞典》.2003,第2236页. * |
| JP特开2000-72430A 2000.03.07 |
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