CN102554260B - Application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder - Google Patents
Application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder Download PDFInfo
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Abstract
The invention discloses application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder, which comprises the steps of fully reacting metatungstic acid solution with certain concentration with cobalt carbonate to obtain first W-Co composite solution with uniform components; mixing EDTA powder and cobalt carbonate powder uniformly, and adding the mixed powder to the first W-Co composite solution for reaction to obtain second W-Co composite solution conforming the W-Co proportioning requirements of the process; and drying and pelletizing the second W-Co composite solution, spray drying, and removing water so as to obtain the W-Co composite oxide powder which has uniform components, contains Co content being more than 7 percent, can randomly adjust the Co content and is accurate in control, so that the process is simplified, the production efficiency is improved and the production consumption is reduced.
Description
Technical field
The invention belongs to metal material field, belong to cemented carbide powder and prepare category, be specially adapted to the preparation of tungsten-cobalt composite oxide powder of high cobalt content and the preparation of follow-up WC-Co composite powder.
Background technology
Carbide alloy is primary raw material with rare metals such as tungsten, cobalt, titaniums, wherein accounts for the principal status of public economy with tungsten carbide-cobalt hard alloy again.Carbide alloy has high rigidity, high density, property such as wear-resisting, is widely used in a plurality of fields such as machine-building, oil exploitation, military project, Aero-Space, is the novel force structure material with high-tech content, has very big market potential.The preparation method of tradition carbide alloy adopts methods such as fixed bed, rotary furnace, hydrogen plasma to make tungsten oxide be become tungsten powder by hydrogen reducing, tungsten (W) powder is mixed with carbon (C) sphere of powder mill, change into tungsten carbide (WC) through pyrocarbon, carrying out ball milling with prefabricated cobalt powder again mixes, obtain WC-Co (WC-Co) carbide alloy mixed-powder, and then prepare carbide alloy by compacting sintering.The method preparation technology's long flow path, efficient are low, tungsten carbide (WC) is difficult to even distribution at cobalt (Co) in mutually in the mixed-powder, influences follow-up carbide alloy performance.In cemented carbide industry to production high-performance, today of nanoscale hard alloy development cheaply, conventional method is difficult to effectively prepare the nanoscale hard alloy powder that is fit to production, and the production of carbide alloy is now developing to the direction that adopts WC-Co composite powder to prepare carbide alloy gradually.And as the important source material of producing the Nanometre grade tungsten carbide Co composite powder, it is even how to prepare composition, and the cobalt content adjustable range is big, control accurate tungsten-cobalt composite oxide powder, becomes the key of preparation high-performance nano level WC-Co composite powder.
The method that the preparation of tungsten-cobalt composite oxide powder is usually adopted is as described in the patent " production technology of nanoscale tungsten cobalt mixed-powder " (number of patent application 03150684.4): prepare certain density ammonium metatungstate solution, add a certain amount of cobaltous carbonate powder, heating, stirring, fully reaction is with the cooling of gained complex salt solution, filtration; The dry composite salting liquid obtains the complex salt powder, and heating tungsten cobalt complex salt powder obtains tungsten-cobalt composite oxide powder in fluid bed.Adopt these class methods to prepare tungsten-cobalt composite oxide powder, the sluggish of ammonium metatungstate and cobalt carbonate, production efficiency is low; Reaction is difficult to fully carry out, and the reaction residue of generation not only must increase the solution filtration step to be handled, and is difficult to the cobalt content in the composite solution is accurately controlled; The most important, these class methods are limited by the intrinsic tungsten cobalt ratio of chemical reaction, even reaction cmpletely, the mol ratio of W and Co also can only reach 4:1 in the tungsten-cobalt composite oxide, causes these composite oxides can't be applied in preparation and contains the cobalt amount above on 7% the WC-Co composite powder.In this case, expect that containing the cobalt amount is higher than 7% WC-Co composite powder two kinds of methods are generally arranged: a kind of is to prepare the WC-Co composite powder that contains cobalt amount 7% earlier, adds cobalt powder to improve cobalt content in the later stage then.This method causes powder property to descend because the cobalt powder of follow-up adding can't evenly disperse in original WC-Co composite powder, has also just lost the advantage of composite powder.Another kind method is to add solubility cobalt salt solutions such as cobalt nitrate, cobalt chloride in the preparation tungsten cobalt composite solution stage to promote cobalt content.Because the proportion of solubility cobalt salt solution is all lower, can bring a large amount of moisture into, cause the concentration of tungsten cobalt composite solution to descend, not only increased the processing time that concentrates, increased energy consumption cost.And in the subsequent drying process, the acid group impurity that cobalt salt solution is brought into must thoroughly be removed.This process both can cause a large amount of pernicious gases to influence equipment and personnel's safety, can produce harmful effect to intensity and the pattern of powder particle again, directly had influence on the production of follow-up WC-Co composite powder.
Chinese patent " the EDTA complexometry prepares the method for pre-alloyed powder for nanometer-level dispersion-strengthened metal " (Zl200810225897.2) provides a kind of method for preparing pre-alloyed powder for nanometer-level dispersion-strengthened metal.But it belongs to the category of liquid phase mixed metal oxide powders processed, and what EDTA played therein is to make parent metal and disperse phase oxide disperse effect uniformly, but also needs to add nitrate and ammoniacal liquor, is not suitable for using in CEMENTED CARBIDE PRODUCTION.
Summary of the invention
The object of the invention mainly be produce composition evenly, cobalt content is higher than 7% and can regulate cobalt content arbitrarily, control accurate tungsten-cobalt composite oxide powder, simplifies technology, enhances productivity, reduces to produce consuming.
The present invention solves the problems of the technologies described above the technical scheme that adopts to be: fully react by certain density meta-tungsten acid solution and cobalt carbonate, obtain the uniform first tungsten cobalt composite solution of composition; EDTA powder and cobaltous carbonate powder are evenly mixed, and mixed-powder added in the above-mentioned first tungsten cobalt composite solution react, obtain meeting the second tungsten cobalt composite solution of the required tungsten cobalt of technology proportioning; The described second tungsten cobalt composite solution is carried out drying and granulating, by spray-drying, remove moisture again, and then the acquisition composition is even, the cobalt content adjustable range is big, control accurate tungsten-cobalt composite oxide powder; Concrete processing step is:
A, with [H
+] ion concentration is 0.2～0.5mol/L, [NH
4 +] ion concentration is that the meta-tungsten acid solution of 0～0.01mol/L is heated to 50～80 ℃ and a certain amount of cobaltous carbonate powder and fully reacts, obtain in the first tungsten cobalt composite solution; The molar ratio range of W and Co is 4:1～4.2:1 in the described first tungsten cobalt composite solution; Solution pH value scope 2～3;
B, calculate the consumption of required cobaltous carbonate powder and EDTA powder according to processing compound, and it is mixed, drop in the first tungsten cobalt composite solution, under 80～100 ℃ condition, fully react, obtain meeting the second tungsten cobalt composite solution of the required tungsten cobalt of technology proportioning; The molar ratio range of W and Co is 2:1～4:1 in the described second tungsten cobalt composite solution; Solution pH value scope 3～5;
C, the second tungsten cobalt composite solution is concentrated, under 120～160 ℃ outlet temperature, carry out spray-drying, and the spraying powder that will obtain calcines at 300～600 ℃ rotary furnace, finally obtain composition evenly, the cobalt content adjustable range is big, control accurate tungsten-cobalt composite oxide powder.
In the described tungsten-cobalt composite oxide powder, cobalt quality percentage composition is 10.5% following arbitrary value, be applicable to the preparation contain the cobalt amount the WC-Co composite powder below 12%.
Principle of the present invention is: the preparation of tungsten-cobalt composite oxide powder adopts ammonium metatungstate or metatungstic acid adding cobalt salt to react usually, obtain containing the composite solution of metatungstic acid cobalt, other is compound to realize tungsten cobalt molecular level, and the method by drying and granulating obtains tungsten-cobalt composite oxide powder more afterwards.Reacting with metatungstic acid and cobalt carbonate is example, and the basic chemical equation of these class methods is as follows:
H
6H
2W
12O
40 ＋ 3CoCO
3 = Co
3 H
2W
12O
40 + 3CO
2 ↑ + 3H
2O
As can be seen, no matter adopt which kind of cobalt salt to react, final reacting product all is metatungstic acid cobalt (Co
3H
2W
12O
40), the mol ratio of W and Co is 4:1, and conversion is in WC-Co composite powder, and cobalt content is 7%.Want to obtain the more tungsten-cobalt composite oxide of high cobalt content, new acid group and cobalt must be arranged in conjunction with generating the solubility cobalt salt and the metatungstic acid cobalt liquor is compound or add cobalt powder in the later stage tungsten-cobalt composite oxide powder.The mode of adding cobalt powder can't reach molecular level, and other is compound, and uniformity influences powder property not as solution combined.So we need adopt the solubility cobalt salt, and the acid group of solubility cobalt salt must be removed in the middle of dry run, to avoid influencing product quality.Tradition solubility cobalt salt such as cobalt nitrate (Co (NO
3)
2) and cobalt chloride (CoCl
2), inorganic acid radical all is difficult to remove, and brings impurity into, also can destroy the powder particle pattern, and product quality is impacted; In acid group removal process, produce a large amount of pernicious gases simultaneously, influence equipment and personnel's personal safety.And cobalt acetate (CoC
4H
6O
44H
2O) though be organic acid, easily remove, can not bring impurity into, itself just contains the crystallization water, brings a large amount of moisture into, causes the concentration of tungsten cobalt composite solution to descend, and increases time and the cost of subsequent treatment.
EDTA (ethylenediamine tetra-acetic acid) is a kind of strong complexing agent, the carbide alloy field only as the analyzing and testing metallic element in indicator use.It can with periodic table in most of elements form the big complexing of stability constants, the formation of complex compound can significantly reduce the concentration of free metal ion in the solution, guarantee that metal ion evenly distributes in solution, prevent from concentration process, may occurring precipitation, influence uniformity.EDTA also is a kind of organic acid simultaneously, is white odorless, tasteless, colourless crystallization powder under the normal temperature.Be insoluble to cold water, be slightly soluble in hot water, its alkali metal salt can be water-soluble.EDTA powder energy and cobalt salt powder under the condition of control temperature and pH value, are reacted in the composite solution that contains the metatungstic acid cobalt, neither bring large quantity of moisture into, and organic acid is easy to volatilization again and removes.
Advantage of the present invention is that meta-tungsten acid solution and cobalt carbonate are swift in response, and is with short production cycle, the efficient height; EDTA exists with the powdered form form, and it is convenient to add, and control precisely; Need not obtain solution, production process simply and is not brought large quantity of moisture into, has reduced the time of concentrated solution, has not only saved to produce to consume, and has shortened the production cycle; As organic acid, volatile in spray-drying process, the easy removal of EDTA, do not bring the impurity element that influences product quality and little to the pattern influence of powder particle into, ensured the steady quality of product to the full extent; Because EDTA and cobalt salt are to react in solution, the tungsten cobalt element reaches molecular level, and other is compound, the powder composition evenly and cobalt content break through former chemical equation restriction, adjust in can be on a large scale, the cobalt content scope contains the main trade mark of existing CEMENTED CARBIDE PRODUCTION substantially, can be widely used in the production of all kinds carbide alloy.Therefore, the present invention possess skills the advanced person, technology is simple, flow process is short, control is accurate, consume little, characteristics such as production efficiency is high, wide accommodation, is fit to very much industrial production extensive, multiple product lines.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
The specific embodiment
Embodiment 1:
(1) gets meta-tungsten acid solution 750L, its [H
+]=0.281mol/L, [NH
4 +]=0mol/L;
(2) take by weighing cobaltous carbonate powder 15.366kg, 2.409kg is standby for the EDTA powder;
(3) meta-tungsten acid solution is heated to 80 ℃, adds the cobalt carbonate of 13.381kg, it is fully reacted, obtain the first tungsten cobalt composite solution;
(4) continue to be warmed up to 100 ℃, remaining cobaltous carbonate powder and EDTA powder are added in the above-mentioned first tungsten cobalt composite solution after evenly gradually, make its complete reaction, obtain the second tungsten cobalt composite solution;
(5) the gained second tungsten cobalt composite solution is concentrated, spray-drying, oven dry calcining obtains tungsten-cobalt composite oxide powder, cobalt quality percentage composition 6.72%;
(6) above-mentioned tungsten-cobalt composite oxide is carried out the WC-Co composite powder that reduction and carbonization obtains 8% cobalt content.
Embodiment 2:
(1) (utilizes the ammonium metatungstate clearing house to get) and get metatungstic acid 500L, its [H
+]=0.420mol/L, [NH
4 +]=0.005mol/L;
(2) take by weighing cobaltous carbonate powder 19.637kg, 7.592kg is standby for the EDTA powder;
(3) meta-tungsten acid solution is heated to 70 ℃, adds the cobalt carbonate of 13.478kg, it is fully reacted, obtain the first tungsten cobalt composite solution;
(4) continue to be warmed up to 90 ℃, remaining cobaltous carbonate powder and EDTA powder are added in the above-mentioned first tungsten cobalt composite solution after evenly gradually, make its complete reaction, obtain the second tungsten cobalt composite solution;
(5) the gained second tungsten cobalt composite solution is concentrated, spray-drying, oven dry calcining obtains tungsten-cobalt composite oxide powder, cobalt quality percentage composition 8.39%;
(6) above-mentioned tungsten-cobalt composite oxide is carried out the WC-Co composite powder that reduction and carbonization obtains 10% cobalt content.
Embodiment 3:
(1) (utilizes the ammonium metatungstate clearing house to get) and get meta-tungsten acid solution 750L, its [H
+]=0.461mol/L, [NH
4 +]=0.01mol/L;
(2) take by weighing cobaltous carbonate powder 48.206kg, 26.024kg is standby for the EDTA powder;
(3) meta-tungsten acid solution is heated to 60 ℃, adds the cobalt carbonate of 26.892kg, it is fully reacted, obtain the first tungsten cobalt composite solution;
(4) continue to be warmed up to 80 ℃, remaining cobaltous carbonate powder and EDTA powder are added in the above-mentioned first tungsten cobalt composite solution after evenly gradually, make its complete reaction, obtain the first tungsten cobalt composite solution;
(5) the gained second tungsten cobalt composite solution is concentrated, spray-drying, oven dry calcining obtains tungsten-cobalt composite oxide powder, cobalt quality percentage composition 10.05%;
(6) above-mentioned tungsten-cobalt composite oxide is carried out the WC-Co composite powder that reduction and carbonization obtains 12% cobalt content.
The application of EDTA in the preparation tungsten-cobalt composite oxide powder, make that the tungsten-cobalt composite oxide powder composition is even, the cobalt content adjustable range is big, substantially the main trade mark of containing existing CEMENTED CARBIDE PRODUCTION, control simultaneously accurately can be widely used in the production of all kinds carbide alloy.And produce and consume minimizing, production efficiency raising, be fit to very much industrial production extensive, multiple product lines.
Claims (2)
1.EDTA the application in the preparation tungsten-cobalt composite oxide powder is characterized in that: fully react by certain density meta-tungsten acid solution and cobalt carbonate, obtain the uniform first tungsten cobalt composite solution of composition; EDTA powder and cobaltous carbonate powder are evenly mixed, and mixed-powder added in the above-mentioned first tungsten cobalt composite solution react, obtain meeting the second tungsten cobalt composite solution of the required tungsten cobalt of technology proportioning; The described second tungsten cobalt composite solution is carried out drying and granulating, by spray-drying, remove moisture again, and then the acquisition composition is even, the cobalt content adjustable range is big, control accurate tungsten-cobalt composite oxide powder; Concrete processing step is:
A, with [H
+] ion concentration is 0.2～0.5mol/L, [NH
4 +] ion concentration is that the meta-tungsten acid solution of 0～0.01mol/L is heated to 50～80 ℃ and a certain amount of cobaltous carbonate powder and fully reacts, and obtains the first tungsten cobalt composite solution; The molar ratio range of W and Co is 4:1～4.2:1 in the described first tungsten cobalt composite solution; Solution pH value scope 2～3;
B, calculate the consumption of required cobaltous carbonate powder and EDTA powder according to processing compound, and it is mixed, drop in the first tungsten cobalt composite solution, under 80～100 ℃ condition, fully react, obtain meeting the second tungsten cobalt composite solution of the required tungsten cobalt of technology proportioning; The molar ratio range of W and Co is 2:1～4:1 in the described second tungsten cobalt composite solution; Solution pH value scope 3～5;
C, the second tungsten cobalt composite solution is concentrated, under 120～160 ℃ outlet temperature, carry out spray-drying, and the spraying powder that will obtain calcines at 300～600 ℃ rotary furnace, finally obtain composition evenly, the cobalt content adjustable range is big, control accurate tungsten-cobalt composite oxide powder.
2. the application of EDTA according to claim 1 in the preparation tungsten-cobalt composite oxide powder, it is characterized in that: in the tungsten-cobalt composite oxide powder, cobalt quality percentage composition is 10.5% following arbitrary value, is applicable to that preparation contains the cobalt amount at the WC-Co composite powder below 12%.
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Citations (4)
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|---|---|---|---|---|
| CN1565782A (en) * | 2003-06-12 | 2005-01-19 | 中南大学 | Method for preparing nano-grade tungsten-based composite powder by sol-spray drying-thermal reduction |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
| CN101559494A (en) * | 2009-06-02 | 2009-10-21 | 四川大学 | Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof |
| KR20100091533A (en) * | 2009-02-10 | 2010-08-19 | 서강대학교산학협력단 | Preparing method of cobalt powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565782A (en) * | 2003-06-12 | 2005-01-19 | 中南大学 | Method for preparing nano-grade tungsten-based composite powder by sol-spray drying-thermal reduction |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
| KR20100091533A (en) * | 2009-02-10 | 2010-08-19 | 서강대학교산학협력단 | Preparing method of cobalt powder |
| CN101559494A (en) * | 2009-06-02 | 2009-10-21 | 四川大学 | Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof |
Non-Patent Citations (2)
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| 超细碳化钨及其复合粉末的制备;徐志花,马淳安,甘永平;《化学通报》;20030831(第8期);第544页-第548页 * |
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Inventor after: Gong Nanyan Inventor after: Wen Jie Inventor after: Zhang Lu Inventor before: Gong Nanyan Inventor before: Wen Jie Inventor before: Zhang Lu |