CN102925692A - Method for treating waste hard alloy - Google Patents
Method for treating waste hard alloy Download PDFInfo
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- CN102925692A CN102925692A CN2012103751906A CN201210375190A CN102925692A CN 102925692 A CN102925692 A CN 102925692A CN 2012103751906 A CN2012103751906 A CN 2012103751906A CN 201210375190 A CN201210375190 A CN 201210375190A CN 102925692 A CN102925692 A CN 102925692A
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Abstract
The invention provides a method for treating waste hard alloy. The method comprises the following steps of: oxidizing the waste hard alloy to convert tungsten into tungsten oxide; and reacting the oxidized waste hard alloy with alkali to convert the tungsten oxide into tungstate. By the method, the waste hard alloy can be effectively treated.
Description
Technical field
The present invention relates to field of metallurgy.Particularly, the present invention relates to process the method for hard alloy scraps.
Background technology
Along with the fast development of world economy, the whole world is increasing to the needs of hart metal product, but tungsten is as a kind of limited resources, and reserves are also reducing day by day.Utilize the recovery tungsten resource of hard alloy scraps can not only improve the comprehensive utilization ratio of tungsten resource, and can reduce hard alloy scraps to the pollution of environment.
Yet, process at present the method for hard alloy scraps, still remain to be improved.
Summary of the invention
The present invention is based on contriver's following discovery and finishes:
The treatment process of hard alloy scraps mainly contains both at home and abroad at present: mechanical crushing method, the molten method of zinc and electrodissolution method.Mechanical crushing method is a kind of the simplest recovery method, and it does not change the chemical constitution of waste hand alloy material; Also need not separate with cobalt tungsten, after only need making surperficial clean to waste hand alloy material, carry out Mechanical Crushing and ball milling, can obtain with the chemical constitution of waste hand alloy material almost identical (except iron level increase to some extent reduce to some extent with carbon content) carbide alloy mixture.Although it is short that the method has flow process, the characteristics of less investment, crushing efficiency is low, and the impurity content of powder of producing is higher, and particle size uniformity is relatively poor, and the Wimet that sintering is again made has many disadvantageous effects.The molten method of zinc is processed Wimet, under 900 ℃～1000 ℃, cobalt in zinc and the Wimet cobaltiferous waste material forms the zinc cobalt-base alloy, zinc immerses the cobalt-based body and causes that this expands mutually, dezincify through vacuum distilling, Wimet then becomes loose porous body, then obtains the tungsten-cobalt carbide mixed powder through broken, grinding, produces hart metal product with this powder again.The method exists facility investment large, the shortcoming that production cost and energy consumption are high, and the molten powder of zinc has certain pollution to environment.The electrodissolution method, under electric field action, take hard alloy scraps as anode, use suitable ionogen, usually in acidic medium, by the control anode potential, cakingagent cobalt in the useless piece material of Wimet is optionally dissolved in the ionogen, process with the chemical metallurgy method, wherein wolfram varbide is with the form output of the anode sludge, to can obtain carbonization hard alloy scraps end after its deoxidation, and then produce hart metal product.But this method generally only is suitable for processing cobalt contents greater than 8% hard alloy scraps material, and technical process is longer, and a whole set of electrolyzer is complicated.
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent also or at least provides a kind of useful commerce to select.For this reason, one object of the present invention is to propose a kind of method that hard alloy scraps is recycled.
In one aspect of the invention, the present invention proposes a kind of method that hard alloy scraps is processed.According to embodiments of the invention, the method may further comprise the steps: hard alloy scraps is carried out oxide treatment, in order to the tungsten in the hard alloy scraps is converted into Tungsten oxide 99.999.Thus, hard alloy scraps can be emitted some heats in oxidising process, takes full advantage of this part heat and can reduce power consumption in the oxidising process, thereby reduced to a certain extent the cost that hard alloy scraps is processed.In addition, according to embodiments of the invention, will react through hard alloy scraps and the alkali of oxide treatment, in order to Tungsten oxide 99.999 is converted into tungstate.Thus, can effectively make useless tungsten resource be recycled utilization, and then enlarge the use value of hard alloy scraps.
In addition, according to the embodiment of the invention, this method that hard alloy scraps is processed can also have following additional technical characterictic:
According to one embodiment of present invention, this hard alloy scraps is to be selected from scrap hard alloy product, Wimet at least a of the powder scrap, Wimet desktop material and the Wimet ground fabric that get off of polishing.Thus, can effectively make useless tungsten resource be recycled utilization, and then enlarge the use value of hard alloy scraps.
In one embodiment of the invention, described hard alloy scraps being carried out oxide treatment, is in retort furnace, in the situation that there is oxygen, described hard alloy scraps heated finish.Thus, can improve the oxidation efficiency of processing hard alloy scraps, thereby further improve the efficient of hard alloy scraps recycling.
Wherein, according to one embodiment of present invention, in retort furnace, the boat charge of hard alloy scraps is 0.5 ~ 1.0kg/ boat, pushes away boat speed and be 2 boats/20 ~ 40 minute.
According to a concrete example of the present invention, adopt four pipe retort furnaces to carry out oxide treatment.
In one embodiment of the invention, described oxygen is that the form with air provides, and described oxide treatment was finished 800 ~ 980 degrees centigrade of lower lasting oxidations in 6 ~ 12 hours.In one embodiment of the invention, with 10 ~ 40m
3The flow velocity of/h air supply in the described retort furnace.Thus, can improve the oxidation efficiency of processing hard alloy scraps, thereby further improve the efficient of hard alloy scraps recycling.
In one embodiment of the invention, described retort furnace has the first to the 5th band warm area, wherein, the first temperature with warm area is 800 ~ 900 ℃, the second temperature with warm area is 820 ~ 900 ℃, the 3rd temperature with warm area is 880 ~ 920 ℃, and the temperature of four-tape warm area is 900 ~ 950 ℃, and the 5th temperature with warm area is 920 ~ 980 ℃.According to the preferred processing condition of setting hard alloy scraps is carried out oxidation, can make hard alloy scraps obtain sufficient oxidation, further can improve utilization efficiency of heat energy, electric quantity consumption is reduced, and then can Effective Raise production efficiency, reduce production costs, thereby be applicable to large-scale batch production.In addition, the characteristic of heat release can reduce electric quantity consumption, thereby reduce production costs when taking full advantage of the tungsten oxidation in the hard alloy scraps.
In one embodiment of the invention, make react through the hard alloy scraps of oxide treatment and alkali before, to carry out successively ball-milling processing and screen filtration through the hard alloy scraps of oxide treatment in advance, then screen underflow and alkali are reacted, the aperture of wherein said screen cloth is 150 ~ 180 microns.According to a concrete example of the present invention, alloy ball and the hard alloy scraps that passes through oxide treatment were carried out ball-milling processing 45 ~ 60 minutes according to weight ratio 5 ~ 6:1.Thus, by ball-milling processing and screen filtration can be effectively with through in the hard alloy scraps of oxide treatment not the part of complete oxidation remove, and then can obtain efficiently to comprise the screen underflow of Tungsten oxide 99.999, tungstate and a small amount of oxide impurity, thereby can further improve efficient and the effect that hard alloy scraps is processed.
In one embodiment of the invention, hard alloy scraps and alkali through oxide treatment are reacted, be to mix with sodium hydroxide solution by the hard alloy scraps with described process oxide treatment, and under preset temperature and predetermined pressure, keep finishing in 1 ~ 3 hour.Thus, can make through the hard alloy scraps of oxide treatment and complete reaction after sodium hydroxide solution fully mixes, thereby can greatly improve the rate of recovery of hard alloy scraps.
In one embodiment of the invention, the concentration of described sodium hydroxide solution is 3 ~ 5mol/L, and described preset temperature is 140 ~ 160 degrees centigrade, and described predetermined pressure is 5 ~ 6 standard atmospheric pressures.Thus, can make through the hard alloy scraps of oxide treatment and complete reaction after sodium hydroxide solution fully mixes, further can improve and to be converted into the efficient of tungstate through the hard alloy scraps of oxide treatment by alkaline purification, thereby can improve processing efficiency and the effect of hard alloy scraps, in addition, can also progressively separate other contained in hard alloy scraps metallic elements, such as Fe, Co, Ni and Mn etc. by alkaline purification.
In one embodiment of the invention, the method that hard alloy scraps is processed of the present invention further comprises and utilizes tungstate to prepare ammonium paratungstate.For example, according to one embodiment of present invention, by the sodium wolframate that obtains is carried out ion-exchange and crystallization treatment, can prepare ammonium paratungstate.Thus, can obtain final tungsten and reclaim product from hard alloy scraps, impurity can be used as normal tungsten product raw material after qualified and uses after testing, thereby the recycling that can improve hard alloy scraps is worth.
The treatment process of hard alloy scraps can realize that following advantages is one of at least according to an embodiment of the invention:
1, the treatment process of hard alloy scraps according to an embodiment of the invention adopts four pipe retort furnaces for processing the major equipment of hard alloy scraps, can improve the oxidation efficiency of processing hard alloy scraps, improves day output, thereby is applicable to large-scale batch production;
2, the treatment process of hard alloy scraps is carried out oxide treatment to hard alloy scraps according to an embodiment of the invention, can take full advantage of the oxidation heat liberation characteristic of tungsten in the hard alloy scraps, and rationally adjusting process reduces energy consumption, thereby can reduce cost recovery; And, very easily broken through the hard alloy scraps of oxide treatment, thus, can improve organic efficiency and the rate of recovery.Particularly, the 80 order screen underflows of hard alloy scraps behind a ball mill crushing through oxide treatment can reach more than 99%;
3, the treatment process of hard alloy scraps according to an embodiment of the invention, when after the hard alloy scraps oxidation, using alkaline solution that it is carried out alkaline purification, by control alkali lye solubility, temperature and pressure the solubleness of Tungsten oxide 99.999 is reached more than 98%, thereby can significantly improve the reclaim of tungsten rate.In addition, tungsten is separated with other valuable metal element, can reclaim other metal simultaneously, thereby can improve using rate of metal, reduce the pollution to environment;
4, the treatment process of hard alloy scraps according to an embodiment of the invention, the powder of producing again that obtains after processing, no matter foreign matter content or particle size uniformity all can reach the powder standard that tungsten concentrate is made can satisfy subsequent product to the specification of quality of raw material.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the schematic flow sheet of the treatment process of hard alloy scraps according to an embodiment of the invention.
Embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
Need to prove, described hard alloy scraps in the present invention, its mainly comprise tungsten, cobalt, nickel, iron and manganese etc. metallic element, thus, utilize the treatment process that hard alloy scraps is carried out of the present invention, by described hard alloy scraps is carried out oxide treatment and alkaline purification successively, various metals of Separation and Recovery effectively just.Concrete grammar is as described below:
In one aspect of the invention, the present invention proposes a kind for the treatment of process that hard alloy scraps is carried out.According to embodiments of the invention, the method may further comprise the steps:
S100: hard alloy scraps is carried out oxide treatment, tungsten is oxidized to Tungsten oxide 99.999
In this step, hard alloy scraps is carried out oxide treatment, thus, following reaction can mainly occur with oxygen in hard alloy scraps:
WC+Co+O
2(g)(heating) → WO
3+ CoWO
4+ CO
2(g),
WC+Ni+O
2(g)(heating) → WO
3+ NiWO
4+ CO
2(g),
Thereby, by hard alloy scraps is carried out oxide treatment, the metals such as useless tungsten that comprise in the hard alloy scraps can be converted into the mixture that contains tungstic oxide.
Wherein, according to embodiments of the invention, the source of this hard alloy scraps is not particularly limited.According to concrete example of the present invention, hard alloy scraps can be for being selected from scrap hard alloy product, Wimet at least a of the powder scrap, Wimet desktop material and the Wimet ground fabric that get off of polishing.Thus, can effectively make useless tungsten resource be recycled utilization, and then enlarge the use value of hard alloy scraps.
According to embodiments of the invention, be not particularly limited for the means of hard alloy scraps being carried out oxide treatment, can utilize any any means known that hard alloy scraps is carried out oxide treatment.According to embodiments of the invention, hard alloy scraps is carried out oxide treatment, be in retort furnace, in the situation that there is oxygen, described hard alloy scraps heated finish.Thus, can improve the oxidation efficiency of processing hard alloy scraps, effectively obtain comprising the hard alloy scraps of process the oxide treatment of Tungsten oxide 99.999 and other impurity, thereby can further improve the efficient that hard alloy scraps recycles.
Wherein, according to embodiments of the invention, the model of retort furnace also is not particularly limited, and according to a particular embodiment of the invention, can adopt four pipe retort furnaces (the new large Wimet equipment company limited of Xiangtan, Hunan Province).According to one embodiment of present invention, the four pipe retort furnace gross weights that adopt are about 22 tons, body of heater physical dimension is 10024*2302*2452(mm), the boiler tube specification is 7500*300*70(mm) what adopt is chromium nickel high temperaturesteel, 1000 ℃ of maximum operating temperatures, stove uses five band heating, and total power is 180 ~ 190KW.Because this furnace construction is simple, four boiler tubes are the furnace chamber uniform temperature fields altogether, and thermo-efficiency is high, and power consumption is few, can improve the quality of products, and overcome furnace tube temperature uneven and cause and the shortcoming that former granularity is inhomogeneous can be suitable for large-scale production.
In addition, according to embodiments of the invention, when in retort furnace, carrying out oxide treatment, the boat charge of hard alloy scraps and push away boat speed and be not particularly limited.According to a concrete example of the present invention, in retort furnace, the boat charge of hard alloy scraps is 0.5 ~ 1.0kg/ boat, pushes away boat speed and be 2 boats/20 ~ 40 minute.
According to some embodiments of the present invention, when utilizing retort furnace that hard alloy scraps is carried out oxide treatment, the time of the form of described oxygen, the temperature of oxide treatment and oxide treatment all is not particularly limited.According to concrete examples more of the present invention, described oxygen is that the form with air provides.In one embodiment of the invention, with 10 ~ 40m
3The flow velocity of/h air supply in the described retort furnace.Thus, can provide sufficient oxygen for oxide treatment, thereby can improve oxidation efficiency, make the abundant oxidation of hard alloy scraps, and can take full advantage of the heat that the tungsten oxidation is sent in the hard alloy scraps, and then can significantly reduce current consumption, reduce processing cost.According to some embodiments of the present invention, described oxide treatment was finished 800 ~ 980 degrees centigrade of lower lasting oxidations in 6 ~ 12 hours.Thus, can improve the oxidation efficiency of processing hard alloy scraps, thereby further improve the efficient of hard alloy scraps recycling.According to concrete example of the present invention, the retort furnace that the present invention adopts has the first to the 5th band warm area.In an embodiment of the present invention, it is 800 ~ 980 degrees centigrade with the temperature of warm area that retort furnace first to the 5th is set, wherein the first temperature with warm area is 800 ~ 900 ℃, the second temperature with warm area is 820 ~ 900 ℃, the 3rd temperature with warm area is 880 ~ 920 ℃, the temperature of four-tape warm area is 900 ~ 950 ℃, and the 5th temperature with warm area is 920 ~ 980 ℃.Thus, the five temperature settings with warm area that retort furnace has raise gradually, first with warm area in the hard alloy scraps preferential oxidation at a lower temperature of easier oxidation, and dysoxidizable hard alloy scraps is oxidized at the temperate zones of rear one-level gradually.Can improve by retort furnace the first to the 5th temperature with warm area is set thus the oxidation rate of hard alloy scraps, further improve the processing efficiency of hard alloy scraps.According to embodiments of the invention, by arrange retort furnace five with the temperature of warm area by the first to the 5th processing method that raises gradually with warm area, can be so that furnace chamber temperature be even, thermo-efficiency is higher, power consumption is few, can when saving hard alloy scraps oxidation energy consumption, make hard alloy scraps obtain fully oxidation, overcome furnace tube temperature uneven and cause the shortcoming that former granularity is inhomogeneous.This five processing methodes that raise gradually with the warm area temperature can be suitable for large-scale production, finally improve the quality of products.Thereby further improved quality and the efficient of hard alloy scraps recycling, reduced cost recovery.In addition, utilize foregoing the first to the 5th band warm area, can discharge heat release in the time of can taking full advantage of the hard alloy scraps oxidation, can reduce electric quantity consumption, thereby reduce production costs.
S200: Tungsten oxide 99.999 is converted into tungstate by alkaline purification
In one embodiment of the invention, make react through the hard alloy scraps of oxide treatment and alkali before, can in advance the hard alloy scraps through oxide treatment be carried out ball-milling processing and screen filtration successively, then screen underflow and alkali are reacted.Thus, by ball-milling processing and screen filtration can be effectively with through in the hard alloy scraps of oxide treatment not the part of complete oxidation remove, effectively obtain to comprise the screen underflow of Tungsten oxide 99.999, ammonium tungstate and a small amount of oxide impurity, and then screen underflow carried out alkaline purification, can be effectively with tungsten and other metal separation, re-start oxide treatment and the screen overflow of complete oxidation not can be returned, thereby can fully effectively reclaim tungsten resource, avoid waste final efficient and the effect that hard alloy scraps is processed that improve.
According to embodiments of the invention, the actual conditions that carries out ball-milling processing is not particularly limited.According to a concrete example of the present invention, the hard alloy scraps of alloy ball and process oxide treatment can be carried out ball-milling processing 45 ~ 60 minutes according to weight ratio 5 ~ 6:1.Thus, the hard alloy scraps through oxide treatment fully can be ground, reduce its granular size, be conducive to that it is carried out follow-up screen filtration and process.In addition, according to embodiments of the invention, the model of the screen cloth that can adopt also is not particularly limited, and can select screen cloth according to the subsequent technique characteristics, and according to a concrete example of the present invention, the mesh size size is 150 ~ 180 microns.Thus, utilize the screen cloth in this pore diameter range that the hard alloy scraps through peroxidation and ball-milling processing is carried out the screen filtration processing, can shorten process cycle and not waste under the prerequisite of a large amount of manpowers, effectively remove the already oxidised or unoxidized hard alloy scraps of bulk, thereby be conducive to carry out subsequent disposal.
Place alkaline solution to carry out alkaline purification resulting hard alloy scraps through oxide treatment among the step S100, as previously mentioned, contain Tungsten oxide 99.999 through in the hard alloy scraps of oxide treatment, following reaction can occur in Tungsten oxide 99.999 in alkaline solution:
WO
3+2OH
-=WO
4 2-+H
2O，
Thus, can will be converted into tungstate through contained Tungsten oxide 99.999 in the hard alloy scraps of oxide treatment.
According to embodiments of the invention, broad understanding should be done in employed term " alkali " in this article, can be highly basic, weak base, organic bases, mineral alkali, strong base-weak acid salt, also can be can provide OH when water-soluble
-Metal oxide, these materials can provide OH under solution state usually
-According to embodiments of the invention, preferably adopt sodium hydroxide, thus, can by so that the hard alloy scraps of process oxide treatment and sodium hydroxide react, Tungsten oxide 99.999 can be converted into sodium wolframate.
According to embodiments of the invention, hard alloy scraps and alkali through oxide treatment are reacted, be to mix with sodium hydroxide solution by the hard alloy scraps with described process oxide treatment, and under preset temperature and predetermined pressure, keep finishing in 1 ~ 3 hour.According to embodiments of the invention, utilize alkaline solution that the processing parameter that the hard alloy scraps through oxide treatment carries out alkaline purification also is not particularly limited.Those skilled in the art can as required, perhaps determine by in advance experiment.But, need to prove, suitable naoh concentration can make hard alloy scraps fully be alkalized and not waste too much sodium hydroxide.Arrange suitable preset temperature and pressure and can further improve and to be converted into the efficient of tungstate through the hard alloy scraps of oxide treatment by alkaline purification, thereby can further improve processing efficiency and the effect of hard alloy scraps.According to one embodiment of present invention, the processing parameter of alkaline purification is: the concentration of sodium hydroxide solution is 3 ~ 5mol/L, and preset temperature is 140 ~ 160 degrees centigrade, and predetermined pressure is 5 ~ 6 standard atmospheric pressures, and the treatment time is 1 ~ 3 hour.Thus, can make through the hard alloy scraps of oxide treatment and fully reaction after sodium hydroxide solution mixes.The contriver is surprised to find, by above-mentioned alkaline purification condition, can in the alkaline purification process, progressively be separated in other contained in hard alloy scraps metallic elements, metallic elements such as the Fe that exists with ionic species, Cu and Mn can be separated respectively step by step with the form of precipitation, thereby improved on the one hand the purity of resulting tungstate, the metallic elements such as Fe, Cu and Mn can also be reclaimed on the other hand, and separating of Fe, Cu and the metallic elements such as Mn can be realized.After carrying out alkaline purification, by being filtered, solution can obtain tungstate solution, also can reclaim throw out.Thus, in the process that Tungsten oxide 99.999 alkalizes, obtained simultaneously the addition products such as other precipitated metal things, for example, hydroxide two iron, manganous hydroxide etc., and these precipitated metal things are separated gradually and are obtained.
According to embodiments of the invention, will through hard alloy scraps and the sodium hydroxide generation quaternization of oxide treatment, the Tungsten oxide 99.999 in the hard alloy scraps be converted into sodium wolframate.Owing to can be subject to the impact of impurity in the hard alloy scraps after the oxidation in the alkalization process, can increase the difficulty that sodium hydroxide solution alkalizes to Tungsten oxide 99.999.Strengthen the alkalization degree if solely increase the concentration of sodium hydroxide, excessively strong basic solution may corrosion reaction equipment, even damage equipment, reduces duration of service.By increasing temperature of reaction or pressure quaternization is easily carried out, but excessive the carrying out that is unfavorable on the contrary quaternization of excess Temperature or pressure can increase extra energy consumption simultaneously, the hard alloy scraps cost recovery is increased.For this reason, in an embodiment of the present invention, the contriver is optimized naoh concentration, temperature of reaction and reaction pressure.According to examples more of the present invention, in the alkalization process, pass through comprehensive selection, adopting concentration is that the sodium hydroxide solution of 3 ~ 5mol/L, 140 ~ 160 degrees centigrade temperature of reaction and the reaction pressure of 5 ~ 6 standard atmospheric pressures are controlled the W-response condition, in with the alkalization process required energy consumption reduce to minimum in so that the Tungsten oxide 99.999 in the hard alloy scraps is fully alkalized.Thus, can effectively make useless tungsten resource be recycled utilization, the processing efficiency that improves hard alloy scraps reduces production costs simultaneously, and then enlarges the use value of hard alloy scraps.
After according to the method for the embodiment of the invention hard alloy scraps being processed, can effectively the tungsten that comprises in the hard alloy scraps be converted into tungstate, for example sodium wolframate.In addition, the contriver finds that the resulting sodium wolframate of the method according to this invention can be effectively for the preparation of para-tungstate, for example ammonium paratungstate.Because the purity of the resulting sodium wolframate of the method according to this invention is higher, thereby those skilled in the art can adopt any known method, and resulting sodium wolframate is converted into for example ammonium paratungstate of para-tungstate.According to one embodiment of present invention, can further carry out ion-exchange and crystallization treatment to sodium wolframate, thereby reach the purpose of utilizing sodium wolframate to prepare ammonium paratungstate.Thus, can further utilize tungstate to prepare ammonium paratungstate.About the actual conditions of these aftertreatments, those skilled in the art can adopt any currently known methods and equipment, do not repeat them here.After obtaining ammonium paratungstate, can utilize it to prepare various tungsten products, make the hard alloy scraps resource obtain the high efficiente callback utilization.And in the prior art, hard alloy scraps then is mainly used in the making of the instruments such as oil drilling, coal probing, shovel snowflake, safety stud, perhaps can mix with tungsten as casting hard alloy scraps raw material, the spray material that is used for various break-out materials, range of application is little, can only be used for producing low and middle-grade Wimet again.The method that hard alloy scraps is processed provided by the invention can obtain highly purified tungstate, and then can access highly purified ammonium para-tungstate crystal, it can be used as normal tungsten product raw material and uses, thereby the recycling that can effectively improve hard alloy scraps is worth.
In addition, after according to the method for the embodiment of the invention hard alloy scraps being processed, can utilize the reaction waste residue of hydrochloric acid soln after obtaining tungstate and prepare cobalt chloride, and then change the cobalt chloride that obtains over to cobalt and reclaim in the technical process, can effectively reclaim cobalt, thereby the recycling that can further improve hard alloy scraps is worth.
This that hard alloy scraps is recycled the tungsten product raw materials cost that makes is low, remedies tungsten resource shortage, expensive defective on the market.Tungsten ore is Nonrenewable resources, and the open pit mining of tungsten has not only been avoided the wasting of resources, has avoided simultaneously a large amount of hard alloy scraps contaminate environment, destruction eubiosiss.Processed the method for hard alloy scraps, efficient is low, energy consumption is high, equipment is complicated or the regeneration Wimet is unstable in the past.Hard alloy scraps treatment process provided by the invention, equipment, processing method are simple, only need to can finish under the control suitable process conditions, and hard alloy scraps recycling efficient are high, and the tungsten quality of recovery is good.
Below by specific embodiment, the present invention will be described, need to prove that these embodiment only are for illustration purpose, and can not be construed to by any way limitation of the present invention.In addition, if not otherwise specified, the equipment that then adopts and material are commercially available in the following example.
General method:
Raw material: the concentration of hard alloy scraps (ultimate analysis of hard alloy scraps sees the following form 1), sodium hydroxide solution is 3 ~ 5mol/L and pressurized air.
Equipment: four pipe retort furnaces, chromium nickel stainless steel boat, ball mill, sintered carbide ball, screen(ing) machine, decomposer.
Table 1. hard alloy scraps principal element is analyzed (%)
| Co | Fe | Mn | Si | Ca | Ni | Cr | Al | C |
| 7.5 | 0.0100 | 0.0034 | 0.0020 | 0.0020 | 0.0050 | 0.0030 | 0.0010 | 6.05 |
Wherein, four pipe retort furnace gross weights are about 22 tons, and body of heater physical dimension is 10024*2302*2452(mm), the boiler tube specification is 7500*300*70(mm) what adopt is chromium nickel high temperaturesteel, 1000 ℃ of maximum operating temperatures, stove are used five band heating, and total power is 180 ~ 190KW.This furnace construction is simple, and four boiler tubes are the furnace chamber uniform temperature fields altogether, and the high power consumption of thermo-efficiency is few, improves the quality of products, and has overcome furnace tube temperature uneven and cause and the shortcoming that former granularity is inhomogeneous can be suitable for large-scale production.
In the following example, useless useless hard closed the key step of processing be:
1) adjust processing parameter: five band warm areas are set between 800 ~ 980 ℃, push away boat speed and be 2 boats/20 ~ 40 minute, according to 10 ~ 40m
3The speed of/h is introduced pressurized air.
2) with the hard alloy scraps paperback in the chromium nickel stainless steel boat, push the material boat by processing requirement.Carry out oxide treatment after 6 ~ 12 hours, hard alloy scraps will be oxidized to yellow Tungsten oxide 99.999.
3) hard alloy scraps with alloy ball and process oxide treatment carried out ball-milling processing 45 ~ 60 minutes according to weight ratio 5 ~ 6:1, and cross 80 ~ 100 eye mesh screens so that obtain to comprise Tungsten oxide 99.999 and cobaltous tungstate etc. the screen underflow (return re-start oxide treatment with screen overflow) of oxide impurity.
4) under 5 ~ 6 normal atmosphere, the NaOH solution of screen underflow and 3 ~ 5mol/L concentration is heated to 140 ~ 160 degrees centigrade of fully dissolvings, separablely go out Na
2WO
4Solution and partial impurities throw out such as Fe (OH)
2, Mn (OH)
2Deng.
5) various contamination precipitation things can be recycled, then, according to traditional means, with Na
2WO
4Solution passes through the further removal of impurities of ion-exchange evaporative crystallization again, produces ammonium para-tungstate crystal, can do normal tungsten product raw material after checked for impurities is qualified and use.
Embodiment 1
According to the program described in the general method hard alloy scraps is processed.Wherein, push away boat speed and be 2 boats/25 minute, technological temperature is: the first band warm area is 800 ℃, and the second band warm area is 820 ℃, and the 3rd band warm area is 880 ℃, and four-tape warm area is 900 ℃, and the 5th band warm area is 920 ℃, according to 25m
3The flow velocity of/h passes into pressurized air from the stove tail.
Get 30kg hard alloy scraps ball and lie in the boat by every boat 0.7kg, open front fire door and push the material boat by processing requirement, front fire door stays open state, is convenient to discharge the gas of reaction generation and excessive air.The continuous boat pushing operation, after processing in more than 6 hours, the waste alloy ball of oxidation is split inwards by table, and flaking is arranged.With alloy ball with through the hard alloy scraps of oxide treatment according to the weight ratio 6:1 grinding of ball grinder 45min that packs into, then cross 80 eye mesh screens (aperture is 180 microns), in order to obtain screen overflow and screen underflow.Wherein, screen overflow accounts for 20%, mainly is the not saturating tiny lump that forms of oxidation of alloy ball, it can be carried out again oxidation, fragmentation; Screen underflow accounts for 80%, is mainly the mixed powder of Tungsten oxide 99.999 and cobaltous tungstate and a small amount of oxide impurity, and sampling analysis C content is 1.4%.According to this explained hereafter, can process 322kg every day, and current consumption is about 2500 ~ 3000 degree/ton by calculating.
Embodiment 2
According to the program described in the general method hard alloy scraps is processed.Wherein, push away boat speed and be 2 boats/35 minute, technological temperature is: the first band warm area is 840 ℃, and the second band warm area is 860 ℃, and the 3rd band warm area is 880 ℃, and the four or five band warm area is 920 ℃, according to 25m
3The flow velocity of/h passes into pressurized air from the stove tail.
Get 30kg hard alloy scraps ball and lie in the boat by every boat 0.7kg, open front fire door and push the material boat by processing requirement, front fire door stays open state, is convenient to discharge the gas of reaction generation and excessive air.The continuous boat pushing operation, after more than 8 hours processing, the waste alloy ball of oxidation is split inwards by table, and flaking is arranged.With alloy ball with through the hard alloy scraps of oxide treatment according to the weight ratio 6:1 grinding of ball grinder 60min that packs into, then cross 80 eye mesh screens (aperture is 180 microns), in order to obtain screen overflow and screen underflow.Wherein, screen overflow accounts for 7%, it can be carried out again oxidation broken; Screen underflow accounts for 93%, and sampling analysis C content is 0.4%.According to this explained hereafter, can process 230kg every day, and current consumption is about 1800 ~ 2200 degree/ton by calculating.
Embodiment 3
According to the program described in the general method hard alloy scraps is processed.Wherein, push away boat speed 2 boats/40 minutes, technological temperature is: the first band warm area is 860 ℃, and the second band warm area is 880 ℃, and the 3rd band warm area is 900 ℃, and four-tape warm area is 940 ℃, and the 5th band warm area is 950 ℃, according to 25m
3The speed of/h passes into pressurized air from the stove tail.
Get 30kg hard alloy scraps ball and lie in the boat by every boat 0.7kg, open front fire door and push the material boat by processing requirement, front fire door stays open state, is convenient to discharge the gas of reaction generation and excessive air.The continuous boat pushing operation, after more than 10 hours processing, the waste alloy ball of oxidation is split inwards by table, and flaking is arranged.With alloy ball with through the hard alloy scraps of oxide treatment according to the weight ratio 6:1 grinding of ball grinder 60min that packs into, then cross 80 eye mesh screens (aperture is 180 microns), in order to obtain screen overflow and screen underflow.Wherein, screen overflow accounts for 1%, it can be carried out again oxidation broken; Screen underflow accounts for 99%, and sampling analysis C content is 0.0140%.According to this explained hereafter, can process 201kg every day, and current consumption is about 1500 ~ 2000 degree/ton by calculating.
Embodiment 4
According to the program described in the general method hard alloy scraps is processed.Wherein, push away boat speed and be 2 boats/45 minute, technological temperature is: the first band warm area is 900 ℃, and the second band warm area is 900 ℃, and the 3rd band warm area is 920 ℃, and the four or five band warm area is 950 ℃, according to 25m
3The flow velocity of w/h passes into pressurized air from the stove tail.
Get 30kg hard alloy scraps ball and lie in the boat by every boat 0.7kg, open front fire door and push the material boat by processing requirement, front fire door stays open state, is convenient to discharge the gas of reaction generation and excessive air.After more than 11 hours processing, the waste alloy ball of oxidation is split inwards by table, and flaking is arranged.With alloy ball with through the hard alloy scraps of oxide treatment according to the weight ratio 6:1 grinding of ball grinder 60min that packs into, then cross 80 eye mesh screens (aperture is 180 microns), in order to obtain screen overflow and screen underflow.Wherein, screen overflow accounts for 0.9%, it can be carried out again oxidation broken; Screen underflow accounts for 99.1%, and sampling analysis C content is 0.015%.According to this explained hereafter, can process 179kg every day, and current consumption is about 2000 ~ 2500 degree/ton by calculating.
Comprehensively repeatedly instance analysis contrasts under each processing condition the impact on each side such as hard alloy scraps degree of oxidation, treatment capacity and energy consumptions, and the contriver finds, it is low that the hard alloy scraps degree of oxidation is high among the embodiment 3, treatment capacity reaches greatly energy consumption.Thus, the present invention determines that the processing condition described in the embodiment 3 are optimum process condition.
Embodiment 5
Get the screen underflow that obtains in the example 3, utilize the equipment such as Raman spectrometer, x-ray diffractometer, X-gamma spectrometer, X-Ray fluorescence spectrophotometer, infrared carbon sulfur analyzer that it is carried out impurity analysis, the results are shown in following table 2.
Waste alloy ball major impurity constituent content (%) after table 2. oxidation
| Co | Fe | Mn | Si | Ca | Ni | Cr | Al | C |
| 7.3 | 0.0360 | 0.0034 | 0.0020 | 0.0020 | 0.0500 | 0.0100 | 0.0010 | 0.0130 |
Then, with obtain in the example 3 screen underflow carry out alkaline purification, concrete steps are as follows:
Be that the NaOH solution of 3 ~ 5mlo/L places in the decomposer with screen underflow and concentration, be forced into 5 ~ 6 normal atmosphere and be heated to 140 ~ 160 ℃ of abundant stirring and dissolving, boil the Co in the powder after more than 2 hour
2+, Fe
3+, Ni
2+, Mn
2+Deng foreign ion precipitate and separate progressively, then solution is filtered, in order to obtain coarse sodium tungstate and throw out.Respectively coarse sodium tungstate and throw out are carried out sampling analysis, and throw out is reclaimed, in order to strictly control tungsten slag content in the throw out.Wherein, the sampling analysis result is: the throw out tungstenic is 0.9%, and then the hard alloy scraps after the oxidation can reach more than 99% in the dissolving of alkali lye; The impurity content analytical results of coarse sodium tungstate (being the filtrate behind the disgorging) sees the following form 3.
The major impurity constituent content (%) of table 3. coarse sodium tungstate (solution after filtering)
| Co | Fe | Mn | Si | Ca | Ni | Cr | Al | C |
| 0.0090 | 0.0050 | ＜0.0005 | 0.0008 | ＜0.0005 | 0.0005 | 0.0100 | 0.0010 | 0.0120 |
Embodiment 6
With resulting coarse sodium tungstate among the embodiment 5, pass through traditionally ion-exchange, the further removal of impurities of evaporative crystallization, in order to obtain order of ammoniumparatungstate crystal APT.Concrete steps are as follows:
1) utilizes pump that the coarse sodium tungstate that obtains among the embodiment 5 is beaten to pressure filter, reject filter residue, in order to this coarse sodium tungstate is diluted to 15 ~ 30g/L;
2) utilize strong anion-exchange resin, will carry out through the coarse sodium tungstate of dilution the ionic adsorption exchange, particularly: utilize absorbent pump to be evacuated to ion exchange column through the coarse sodium tungstate of dilution, with 2 ~ 3m
3The flow velocity of/hr the exchange column of flowing through makes the WO in the solution
4 2-By resin absorption, do not play ion AsO for example a little less than exchange interaction or the exchange capacity for those
4 3-, MoO
4 2-, PO
4 3-, SiO
3 2-, SnO
3 2-Deng then flowing out with solution.Upon adsorption saturated after,, clean with deionized water again the resin washes clean with clear water, then utilize ammonium chloride and solution of ammonium hydroxide to carry out resin desorption, in order to obtain to resolve product;
3) with parsing product evaporative crystallization in stirring tank of above-mentioned acquisition, in order to obtain the order of ammoniumparatungstate crystal (APT) of white.
Then, utilize the equipment such as X-Ray fluorescence spectrophotometer, infrared carbon sulfur analyzer that the order of ammoniumparatungstate crystal (APT) that obtains is detected.After testing as can be known, the APT quality for preparing meets APT GB/T 10116-20070 level product standard, quite in addition to be better than tungsten concentrate APT(result processed as shown in table 4 below), this product can be done normal tungsten product raw material use.
The major impurity constituent content (%) of table 4.APT
| Co | Fe | Mn | Si | Ca | Ni | Cr | Al | C |
| 0.0020 | ＜0.0005 | ＜0.0005 | 0.0005 | ＜0.0005 | ＜0.0003 | ＜0.0005 | ＜0.0005 | 0.0020 |
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or the example in conjunction with specific features, structure, material or the characteristics of this embodiment or example description.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that do not break away from principle of the present invention and aim can be carried out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. the method that hard alloy scraps is processed is characterized in that, comprising:
Described hard alloy scraps is carried out oxide treatment, in order to tungsten is converted into Tungsten oxide 99.999; And
Hard alloy scraps and alkali through oxide treatment are reacted, in order to described Tungsten oxide 99.999 is converted into tungstate,
Randomly, described hard alloy scraps is to be selected from scrap hard alloy product, Wimet at least a of the powder scrap, Wimet desktop material and the Wimet ground fabric that get off of polishing.
2. method according to claim 1 is characterized in that, described hard alloy scraps is carried out oxide treatment, is in retort furnace, in the situation that there is oxygen, described hard alloy scraps heated finish.
3. method according to claim 2 is characterized in that, the boat charge of described hard alloy scraps is 0.5 ~ 1.0kg/ boat, pushes away boat speed and be 2 boats/20 ~ 40 minute.
4. according to claim 2 or 3 described methods, it is characterized in that, described oxygen is that the form with air provides, and described oxide treatment was finished 800 ~ 980 degrees centigrade of lower lasting oxidations in 6 ~ 12 hours,
Randomly, with 10 ~ 40m
3The flow velocity of/h air supply in the described retort furnace.
5. method according to claim 4, it is characterized in that, described retort furnace has the first to the 5th band warm area, wherein, the first temperature with warm area is 800 ~ 900 ℃, and the second temperature with warm area is 820 ~ 900 ℃, and the 3rd temperature with warm area is 880 ~ 920 ℃, the temperature of four-tape warm area is 900 ~ 950 ℃, and the 5th temperature with warm area is 920 ~ 980 ℃.
6. method according to claim 1, it is characterized in that, make react through the hard alloy scraps of oxide treatment and alkali before, to carry out successively ball-milling processing and screen filtration through the hard alloy scraps of oxide treatment in advance, then screen underflow and alkali are reacted, the aperture of wherein said screen cloth is 150 ~ 180 microns.
7. method according to claim 6 is characterized in that, alloy ball and the described hard alloy scraps that passes through oxide treatment were carried out described ball-milling processing 45 ~ 60 minutes according to weight ratio 5 ~ 6:1.
8. method according to claim 1, it is characterized in that, hard alloy scraps and alkali through oxide treatment are reacted, be to mix with sodium hydroxide solution by the hard alloy scraps with described process oxide treatment, and under preset temperature and predetermined pressure, keep finishing in 1 ~ 3 hour.
9. method according to claim 8 is characterized in that, the concentration of described sodium hydroxide solution is 3 ~ 5mol/L, and described preset temperature is 140 ~ 160 degrees centigrade, and described predetermined pressure is 5 ~ 6 standard atmospheric pressures.
10. method according to claim 1 is characterized in that, further comprises utilizing described tungstate to prepare ammonium paratungstate.
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| CN104046782A (en) * | 2014-07-02 | 2014-09-17 | 李海波 | Method for recycling industrial waste material containing tungsten and iron and low-grade refractory ferberite |
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