CN101781718A - Method for extracting metal cobalt and tungsten from scrap hard alloy and special calcining device - Google Patents
Method for extracting metal cobalt and tungsten from scrap hard alloy and special calcining device Download PDFInfo
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- CN101781718A CN101781718A CN201010107919A CN201010107919A CN101781718A CN 101781718 A CN101781718 A CN 101781718A CN 201010107919 A CN201010107919 A CN 201010107919A CN 201010107919 A CN201010107919 A CN 201010107919A CN 101781718 A CN101781718 A CN 101781718A
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Abstract
The invention discloses a method for extracting metal cobalt and tungsten from a scrap hard alloy and a special calcining device, belonging to the technical field of recovery of the scrap hard alloy. The method comprises the following steps of: placing the scrap hard alloy into a hydrogen environment inside a tubular calcining furnace, and calcining at the temperature of 1700-1750 DEG C; then separating powder through crashing and ball-milling; and then extracting the metal cobalt and the metal tungsten by using a chemical method. In an extraction process of the metal cobalt and the metal tungsten, the scrap hard alloy is firstly calcined so that it is extremely easy to obtain the powder through the ball-milling, and the efficiency of extracting the metal cobalt, the metal tungsten and other metal elements by utilizing the scrap hard alloy is greatly enhanced.
Description
Technical field
The invention belongs to the recycling technical field of scrap hard alloy, relate in particular to the method and the special calcining device that from scrap hard alloy, extract cobalt metal and tungsten.
Background technology
Along with rapid development of economy, industries such as machinofacture, geology and mine, building, electronics and chemical industry are increasing to the tungsten and the cobalt materials demand amount that constitute the Wimet principal element.And tungsten, cobalt is as rare elements, and its ore deposit storage capacity is seldom exploited also more and more difficult.Therefore, extracting again to the recovery of tungsten in the scrap hard alloy and cobalt element material, utilization also seems more and more important.
At present, from scrap hard alloy, extract the technology of cobalt metal and tungsten, comprise the powder that forms after the scrap hard alloy that will reclaim is by classification, fragmentation, ball milling, electrolysis, pass through the technology of chemical extraction again cobalt and tungsten are separated.As China Patent No. is the disclosed method of extracting rare metal from scrap hard alloy of patent of invention of 200510012779.X, comprise the scrap hard alloy fragmentation, clay into power, calcine, react with sodium hydroxide solution, utilize obtained sodium tungstate solution adding sulfuric acid and ammoniacal liquor to generate ammonium tungstate solution through extraction and back extraction, again through heating evaporation, crystallization, oven dry, once more calcining add hydrogen reducing become metal tungsten powder and utilize described solids through and sulfuric acid, ammonium oxalate extract cobalt powder and nickel powder and metal tantalum, metal niobium.This extracting method all is to obtain the last method of passing through chemical extraction again of cemented carbide powder by scrap hard alloy is directly broken, ball milling to extract cobalt metal and tungsten, but because scrap hard alloy extreme hardness, therefore directly obtain powder by broken and this method of ball milling, the hanging down of its efficient well imagines that a general production cycle is at least at 20 days.In addition can also be by directly utilizing electrolytic mode to extract cobalt metal and tungsten to scrap hard alloy, but scrap hard alloy is carried out electrolysis, and it is high and because electrolytic solution volatilization and get rid of the defective that electrolytic solution causes environmental pollution in electrolytic process then to exist power consumption; Also have the cobalt metal of 10-15% and tungsten to be dissolved in the electrolytic solution in addition and discharge, therefore also exist the problem low the rate of recovery of cobalt metal and tungsten as waste liquid.
In addition, above-mentioned from the waste and old technology of from scrap hard alloy, extracting rare metal, employed calcining furnace is because the calcining compartment that constitutes only is provided with a public discharge port and discharge port, therefore the calcining of Wimet can only be firing of stove one stove, the i.e. material body of the quantitative scrap hard alloy of disposable adding in stove, material is got in heat then calcining, cooling, in stove, add the pan feeding body again and calcine cooling again and get material, therefore use this body of heater that scrap hard alloy is calcined and exist that efficient is low, the problem of waste heat energy.
The content of invention
First purpose of the present invention just provides a kind of method of extracting cobalt metal and tungsten from scrap hard alloy low, that extracting cycle is short that consumes energy.
Realize that the technical scheme that above-mentioned purpose of the present invention adopted is:
From scrap hard alloy, extract the method for cobalt metal and tungsten, it is characterized in that comprising the following steps:
The first step, calcining
Scrap hard alloy is calcined under 1700-1750 ℃ temperature;
Second step, fragmentation
Wimet block after the calcining is inserted and carried out ball mill crushing in the ball mill;
The 3rd step, sieving separating
To carry out sieving separating through the Wimet behind the broken ball milling of ball mill, isolated bulk Wimet comes back to and carries out ball mill crushing in the ball mill;
The 4th step, the extraction of cobalt metal and tungsten
Cemented carbide powder and sodium hydroxide solution that ball mill crushing is obtained react, utilize obtained sodium tungstate solution adding sulfuric acid and ammoniacal liquor to generate ammonium tungstate solution through extraction and back extraction, again through heating evaporation, crystallization, oven dry, once more calcining add hydrogen reducing become metal tungsten powder and utilize described solids through and sulfuric acid, ammonium oxalate extract cobalt powder and nickel powder and metal tantalum, metal niobium.
Its additional technical feature comprises: described calcining is to fire in the environment of hydrogen 15-30 minute; Described broken process is the Wimet block after not having incinerating scrap hard alloy block and calcining to be inserted simultaneously carry out ball milling in the ball mill; The weight proportion of the Wimet block after not having incinerating scrap hard alloy block and calcining is 5-1: 1; The fineness of powder of isolated Wimet is 120 behind the described ball milling---180 orders.
Second purpose of the present invention just provides the above-mentioned employed special calcining device of method that extracts cobalt metal and tungsten from scrap hard alloy
Realize that the technical scheme that above-mentioned second purpose of the present invention is adopted is:
From scrap hard alloy, extract the special calcining device of cobalt metal and tungsten, comprise calcining compartment that is provided with opening for feed and discharge port and the heating arrangements made by graphite material, be provided with hydrogen in the discharge port end of described calcining compartment and blow into mouth.
In addition: described calcining compartment is a tubular structure, and this tubulose calcining compartment is divided into feed zone, calcining section and discharging section, and described heating arrangements is fixed in this calcining section place, and is provided with heat preservation mechanism; Remove at described heating arrangements and to be provided with cooling mechanism; In described calcining compartment, be provided with the crystal vessel that is used for splendid attire Wimet material; Opening for feed place at described calcining compartment is provided with thumb wheel mechanism.
After utilizing calcining isolated plant provided by the present invention with the Wimet calcining, form cemented carbide powder through broken ball milling again, the method of extraction cobalt metal and tungsten and other metals compared with prior art has the following advantages from resulting cemented carbide powder:
1, owing at first scrap hard alloy is calcined, make it form powder nest shape, and then broken ball milling, the efficient of from scrap hard alloy, extracting cobalt metal and tungsten and other metals therefore improved greatly;
2, because the calcining compartment of employed special-purpose calcining furnace is the tubular structure that two ends are set to opening for feed and discharge port, and be provided with supporting graphite boat, therefore the graphite boat that is loaded with scrap hard alloy can be advanced by opening for feed and from discharge port, releases, thereby realize the calcining serialization of scrap hard alloy, improved calcination efficiency greatly;
3, because the fineness that ball mill crushing is obtained is 120---180 purpose cemented carbide powders react by sodium hydroxide solution, utilize obtained sodium tungstate solution to add sulfuric acid and by extraction and back extraction evaporation, crystallization, dry, extract metal tungsten powder and cobalt powder, therefore have the high characteristics of extraction yield;
4, because the special-purpose calcining furnace that present patent application provided, because constituting the calcining compartment of this calcining furnace is tubular structure, and its two ends are set to opening for feed and discharge port respectively, therefore in use, in calcining compartment, advance required incinerating Wimet at opening for feed, can take out the good Wimet of calcining as required at discharge port, therefore utilize this calcining furnace can realize the serialization of scrap hard alloy is calcined, and need not fire extinguishing cooling, this shows that this special use calcining furnace has the high and energy-conservation characteristics of calcination efficiency.
Description of drawings
Fig. 1: for from scrap hard alloy, extracting the structural representation of cobalt metal and the special-purpose calcining furnace of tungsten;
Fig. 2: be the cross section structure synoptic diagram of above-mentioned special-purpose calcining furnace
Embodiment
Below in conjunction with the accompanying drawings special-purpose calcining furnace provided by the present invention and the technology of utilizing this calcining furnace to extract cobalt metal and tungsten from scrap hard alloy being described in further detail:
Be illustrated in figure 1 as the structural representation that from scrap hard alloy, extracts cobalt metal and the special-purpose calcining furnace of tungsten provided by the present invention.Promptly the structure of this calcining furnace comprises: the tubular structure calcining compartment of being made by graphite material 14 that is made of feed zone 1, calcining section 2 and discharging section 3, its two ends are opening for feed 4 and discharge port 5, around the outer setting that constitutes calcining compartment calcining section 2 electrically heated mechanism 6 and thermal insulation layer 7 are arranged, be provided with hydrogen at the discharging section that constitutes calcining compartment and blow into pipe 8.
In said structure, in order to prevent the electrode burn of high temperature, remove at heating arrangements and to be provided with the cooling mechanism that constitutes by the cycle down warm water tube 9 that coils around electrically heated mechanism electrode electrically heated mechanism; Be used for splendid attire Wimet material 11 for constituting graphite boat 10 as shown in Figure 2 by graphite material, with the graphite boat 10 that is loaded with Wimet 11 sending into continuously in the tubular structure calcining compartment one by one, can be so that the Wimet high-temperature calcination in the graphite boat; The fixing thumb wheel mechanism that is made of the driving lever 13 in rotating shaft 12 and setting and this rotating shaft at opening for feed 4 places of calcining compartment, this thumb wheel mechanism are used for hard alloy blocks or are loaded with the graphite boat propelling calcining compartment calcining of hard alloy blocks material and release calcining compartment.
From scrap hard alloy, extract the method for cobalt metal and tungsten, comprise the following steps:
The first step, calcining
At first, make the temperature of calcining compartment calcining section reach 1700-1750 ℃, start cooling mechanism simultaneously and make the heating electrode cooling, to prevent its electrode burn with the calcining furnace heating; Wimet is put into graphite boat, and with it sending into continuously in the tubular structure calcining compartment one by one, the time that makes each graphite boat enter the calcining section calcining was controlled at 15-30 minute by thumb wheel mechanism; Blow into simultaneously in the above-mentioned incinerating process and blow into hydrogen in the pipe 8 and blow out, make calcining in the environment of anaerobic, fire by opening for feed 4 at hydrogen.In order to accelerate incinerating speed, with the broken particle diameter of hard alloy blocks be not more than 3 centimetres the most suitable;
Second step, fragmentation
With the calcining after the Wimet block take out from discharge port, and with do not have incinerating scrap hard alloy piece in 1: 1---5 mixed is inserted and is carried out ball mill crushing in the ball mill; Above-mentioned the two the ratio of inserting in the ball mill of Wimet block after incinerating scrap hard alloy piece and the calcining that do not have is selected, and does not have the shared ratio of incinerating scrap hard alloy piece big more, and the speed of its broken ball milling is just fast more, and efficient can reduce simultaneously;
The 3rd step, sieving separating
To carry out sieving separating through the Wimet behind the broken ball milling of ball mill, isolated bulk Wimet comes back to and carries out ball mill crushing in the ball mill;
The 4th step, the extraction of cobalt metal and tungsten
Isolated fineness is 120 behind above-mentioned ball milling---extract cobalt metal and tungsten the 180 purpose powder.
Be about to cemented carbide powder and sodium hydroxide solution reaction that ball mill crushing is obtained, utilize obtained sodium tungstate solution adding sulfuric acid and ammoniacal liquor to generate ammonium tungstate solution through extraction and back extraction, again through heating evaporation, crystallization, oven dry, once more calcining add hydrogen reducing become metal tungsten powder and utilize described solids through and sulfuric acid, ammonium oxalate extract cobalt powder and nickel powder and metal tantalum, metal niobium.The extraction yield that utilizes this technology to extract cobalt metal and tungsten from scrap hard alloy can reach more than 98%.
In the above-mentioned method of from scrap hard alloy, extracting cobalt metal and tungsten, first, it is to calcine in 1700-1750 ℃ the high temperature that the Wimet material of bulk is directly inserted temperature, because the fusing point of cobalt metal is between 1460-1500 ℃, make the cobalt metal fusing in the Wimet that constitutes by cobalt metal coated metal tungsten separate out through calcining back, make hard hard alloy blocks form the numb nest shape piece just as the carbon slag, i.e. cobalt metal and tungsten that fusion is separated out present separate stage; Alloy block through the numb nest shape of calcining formation is easy to grind the needed powder of formation like this, promptly shortens the time of the broken ball milling of ball mill greatly; The second, when calcining, in calcining compartment, blow into hydrogen, can prevent effectively that the carbon formation carbonic acid gas in the alloy from running away, promptly reduce carbon and run off, thus the cobalt metal that assurance is extracted from the obtained powder of calcining ball milling and the quality of tungsten.
Claims (10)
1. from scrap hard alloy, extract the method for cobalt metal and tungsten, it is characterized in that comprising the following steps:
The first step, calcining
Scrap hard alloy is calcined under 1700-1750 ℃ temperature;
Second step, fragmentation
Wimet block after the calcining is inserted and carried out ball mill crushing in the ball mill;
The 3rd step, sieving separating
To carry out sieving separating through the Wimet behind the broken ball milling of ball mill, isolated bulk Wimet comes back to and carries out ball mill crushing in the ball mill;
The 4th step, the extraction of cobalt metal and tungsten
From the cemented carbide powder of above-mentioned ball milling gained, extract cobalt metal and tungsten.
2. the method for extracting cobalt metal and tungsten from scrap hard alloy as claimed in claim 1, it is characterized in that: described calcining is to fire in the environment of hydrogen 15-30 minute.
3. the method for extracting cobalt metal and tungsten from scrap hard alloy as claimed in claim 1 is characterized in that: described broken process is the Wimet block after not having incinerating scrap hard alloy block and calcining to be inserted simultaneously carry out ball milling in the ball mill.
4. the method for extracting cobalt metal and tungsten from scrap hard alloy as claimed in claim 3 is characterized in that: the weight proportion of the Wimet block after not having incinerating scrap hard alloy block and calcining is 5-1: 1.
5. the method for from scrap hard alloy, extracting cobalt metal and tungsten as claimed in claim 1, it is characterized in that: the fineness of powder of isolated Wimet is 120 behind the described ball milling---180 orders.
6. as the described special calcining device that from scrap hard alloy, extracts cobalt metal and tungsten of above-mentioned claim, it is characterized in that: comprise calcining compartment that is provided with opening for feed and discharge port and the heating arrangements made by graphite material, be provided with hydrogen in the discharge port end of described calcining compartment and blow into mouth.
7. the special calcining device that from scrap hard alloy, extracts cobalt metal and tungsten as claimed in claim 6, it is characterized in that: described calcining compartment is a tubular structure, this tubulose calcining compartment is divided into feed zone, calcining section and discharging section, described heating arrangements is fixed in this calcining section place, and is provided with heat preservation mechanism.
8. as claim 6 or the 7 described special calcining devices that from scrap hard alloy, extract cobalt metal and tungsten, it is characterized in that: remove at described heating arrangements and be provided with cooling mechanism.
9. as claim 6 or the 7 described special calcining devices that from scrap hard alloy, extract cobalt metal and tungsten, it is characterized in that: in described calcining compartment, be provided with the crystal vessel that is used for splendid attire Wimet material.
10. the special calcining device that extracts cobalt metal and tungsten from scrap hard alloy as claimed in claim 6, it is characterized in that: the opening for feed place at described calcining compartment is provided with thumb wheel mechanism.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010107919 CN101781718B (en) | 2010-02-02 | 2010-02-02 | Method for extracting metal cobalt and tungsten from scrap hard alloy and special calcining device |
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| CN 201010107919 CN101781718B (en) | 2010-02-02 | 2010-02-02 | Method for extracting metal cobalt and tungsten from scrap hard alloy and special calcining device |
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| CN101781718A true CN101781718A (en) | 2010-07-21 |
| CN101781718B CN101781718B (en) | 2012-12-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784918A (en) * | 2012-08-23 | 2012-11-21 | 蓬莱市超硬复合材料有限公司 | Method for producing roll collars by recycling tungsten carbide from waste hard alloy roll collars |
| CN106498172A (en) * | 2016-12-14 | 2017-03-15 | 荆门市格林美新材料有限公司 | Hard-alloy grinding material tungsten-cobalt disperses the recovery method of tungsten in separating |
| CN107032127A (en) * | 2016-11-11 | 2017-08-11 | 湖南顺泰钨业股份有限公司 | A kind of palletizing method of Preburning material cake for the tungsten compacting sintering that gives up |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2804757Y (en) * | 2005-07-28 | 2006-08-09 | 段立成 | Calcar for waste hard alloy |
| CN101525700A (en) * | 2009-04-28 | 2009-09-09 | 株洲硬质合金集团有限公司 | Recovery processing method of hard alloy scraps |
| CN201390707Y (en) * | 2009-02-26 | 2010-01-27 | 支亮 | Magnesium oxide preparation device |
-
2010
- 2010-02-02 CN CN 201010107919 patent/CN101781718B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2804757Y (en) * | 2005-07-28 | 2006-08-09 | 段立成 | Calcar for waste hard alloy |
| CN201390707Y (en) * | 2009-02-26 | 2010-01-27 | 支亮 | Magnesium oxide preparation device |
| CN101525700A (en) * | 2009-04-28 | 2009-09-09 | 株洲硬质合金集团有限公司 | Recovery processing method of hard alloy scraps |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784918A (en) * | 2012-08-23 | 2012-11-21 | 蓬莱市超硬复合材料有限公司 | Method for producing roll collars by recycling tungsten carbide from waste hard alloy roll collars |
| CN107032127A (en) * | 2016-11-11 | 2017-08-11 | 湖南顺泰钨业股份有限公司 | A kind of palletizing method of Preburning material cake for the tungsten compacting sintering that gives up |
| CN106498172A (en) * | 2016-12-14 | 2017-03-15 | 荆门市格林美新材料有限公司 | Hard-alloy grinding material tungsten-cobalt disperses the recovery method of tungsten in separating |
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| CN101781718B (en) | 2012-12-26 |
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Granted publication date: 20121226 Termination date: 20160202 |