CN104291379A - Method for preparing uniformly chromium-doped APT (ammonium paratungstate) - Google Patents

Method for preparing uniformly chromium-doped APT (ammonium paratungstate) Download PDF

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Publication number
CN104291379A
CN104291379A CN201410512136.0A CN201410512136A CN104291379A CN 104291379 A CN104291379 A CN 104291379A CN 201410512136 A CN201410512136 A CN 201410512136A CN 104291379 A CN104291379 A CN 104291379A
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Prior art keywords
chromium
apt
ammonium paratungstate
uniformly
solution
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CN201410512136.0A
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CN104291379B (en
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赵立夫
黄海
万林生
潘明然
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Jiangxi University of Science and Technology
Chongyi Zhangyuan Tungsten Co Ltd
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Jiangxi University of Science and Technology
Chongyi Zhangyuan Tungsten Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten

Abstract

The invention belongs to the technical field of tungsten smelting and production and in particular relates to a method for preparing uniformly chromium-doped APT (ammonium paratungstate). The method for preparing the uniformly chromium doped APT comprises the following steps: (1) dissolving WO3 with ammonia; (2) adding soluble chromic salt, heating, and carrying out evaporation crystallization; (3) after liquid in a crystallizing pan is completely boiled, stopping steam introduction while stirring continuously; (4) when crystal nucleuses appear in the crystallizing pan, regulating a rotating speed, and maintaining a steam pressure; (5) when density of a solution reaches 1.1g/cm<3>, controlling a stirring speed, and maintaining the steam pressure; and (6) when the pH of the solution is 6.7-7.0, stopping heating, cooling and emptying. The method for preparing the uniformly chromium doped APT has the beneficial effects that APT powder with chromium uniformly distributed can be prepared, chromium is uniformly distributed at each APT crystal boundary, and molecular scale mixing is realized; and the prepared chromium doped APT can be used for effectively inhibiting abnormal growth of WC crystal grains in a liquid phase sintering process, so that properties of a hard alloy are greatly improved.

Description

A kind ofly prepare the method for evenly mixing chromium ammonium paratungstate
Technical field
The invention belongs to Tungsten smelting production technical field, be specifically related to one prepare evenly mix chromium APT(ammonium paratungstate) method.
Background technology
Wimet, because having a series of premium propertiess such as high-melting-point, high rigidity and high strength, is widely used in modern tool material, high-abrasive material, high temperature resistant and corrosion resistant material.Wherein superfine crystal particle wimet because of have high rigidity, high strength " two high " performance and become the developing direction of Wimet.Liquid phase sintering WC crystal grain fast growth is a large bottleneck of restriction ultra-fine cemented carbide development.Research shows, transition metal carbides (Cr 3c 2) effectively can suppress liquid sintering process WC grain growth.Therefore, below current preparation submicron wimet, usually adopts and adds grain growth inhibitor suppression WC grain growth.And the inhibition of inhibitor and the distribution of inhibitor are closely related.
Below current preparation submicron wimet, mainly adopts mechanical mixing, and the method mainly adds chromium powder or chromium carbide by demand in ultrafine tungsten powder, carbonization after mechanically mixing, compacting sintering preparation wimet.Because of the grain growth inhibitor skewness added, can cause that " WC crystal grain " is improper grows up, have a strong impact on " two high " performance of Wimet, constrains ultra-fine greatly the development of Wimet.
Summary of the invention
(1) technical problem that will solve
The present invention is in order to overcome inhibitor skewness, cause " WC crystal grain " improper shortcoming of growing up, the technical problem to be solved in the present invention is to provide a kind ofly prepares the method for evenly mixing chromium ammonium paratungstate, grain growth inhibitor is impelled to distribute more even, reach molecular level mixing, effective suppression liquid sintering process WC grain is improper grows up, and is conducive to improving the performance of ultra-fine cemented carbide.
(2) technical scheme
In order to solve the problems of the technologies described above, the invention provides and a kind ofly like this prepare the method for evenly mixing chromium ammonium paratungstate.
The present invention utilizes co-precipitation principle, adds solubility chromic salt in alkaline ammonium tungstate solution, and the uniform ammonium paratungstate of chromium is mixed in evaporative crystallization preparation, and chromium is present in ammonium paratungstate powder with chromium hydroxide form.
The present invention adopts following technical scheme:
Prepare a method of evenly mixing chromium ammonium paratungstate, its step is as follows:
(1) the molten WO of ammonia 3: add corresponding WO respectively 3with ammoniacal liquor in reactor, 100 DEG C of reaction 1 h, prepare ammonium tungstate solution, wherein WO 3concentration 150-350 g/L, NH 4oH concentration 1.8-5.0 mol/L;
(2) added by ammonium tungstate solution in titanium lined material crystallizing pan, stirring velocity is 70r/min, stirs and slowly adds solubility chromic salt chromium acetate, opens steam valve steam regulation to 0.10-0.30MPa; Temperature controls as 90-100 DEG C, heating evaporation crystallization.Controlling the mass ratio of chromium in ammonium paratungstate powder is 0.22 ~ 0.60%;
(3), after liquid level seethes with excitement completely in crystallizing pan, keep stirring constant, steam off;
(4) occur nucleus in pot to be crystallized, stirring velocity is adjusted to 30 r/min, opens steam valve and keeps vapor pressure to be 0.05-0.10MPa;
(5) when solution density is to 1.1 g/cm 3, control stirring velocity to 70 r/min, open steam valve and keep vapor pressure to be 0.20-0.30 MPa;
(6) when pH value of solution=6.7-7.0 stops heating, cooling, blowing.
(3) beneficial effect
The invention has the beneficial effects as follows: 1. the present invention can prepare chromium and to be evenly distributed ammonium paratungstate powder, and chromium is uniformly distributed in each ammonium paratungstate grain boundaries, achieves molecular level mixing. mix chromium and more do not mix ammonium paratungstate prepared by technique, Fuss granularity is less, size-grade distribution evenly. the mixing chromium ammonium paratungstate and effectively can suppress that liquid sintering process WC grain is improper grows up, larger raising of preparation cemented Carbide Properties. method of the present invention, can utilize the existing equipment of enterprise, does not need additionally to increase equipment, effectively can reduce the input of equipment, thus reduce costs.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Fig. 2 is that chromium APT electromicroscopic photograph (1100 times) is mixed in the preparation of example 1 processing condition.
Fig. 3 is that chromium APT electromicroscopic photograph (300 times) is mixed in the preparation of example 1 processing condition.
Fig. 4 is that chromium APT Electronic Speculum and energy spectrogram are mixed in the preparation of example 1 processing condition.
Fig. 5 is that chromium APT XRD result is mixed in the preparation of example 1 processing condition.
Fig. 6 is that example 1 processing condition are prepared by mixing chromium APT wimet metallograph.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
embodiment 1
Prepare a method of evenly mixing chromium ammonium paratungstate, its step is as follows:
(1) ammonia solvent WO in advance 3prepare ammonium tungstate solution wherein WO 3=276 g/L, NH 4oH=4.3 mol/L, adds corresponding WO respectively 3with ammoniacal liquor in reactor, 100 DEG C of reaction 1 h;
(2) by 2 m 3ammonium tungstate solution adds in titanium lined material crystallizing pan, and stirring velocity is 70 r/min, stirs and slowly adds chromium acetate 15.4 Kg, opens steam valve steam regulation to 0.10-0.30MPa; Temperature controls as 90-100 DEG C, heating evaporation crystallization;
(3), after liquid level seethes with excitement completely in crystallizing pan, keep stirring constant, steam off;
(4) occur nucleus in pot to be crystallized, turning speed is 30 r/min, keeps vapor pressure to be 0.05-0.10 MPa;
(5) when solution density is to 1.1 g/cm 3, control stirring 70 r/min, keep vapor pressure to be 0.20-0.30 MPa;
(6) when pH value of solution=7.0 stop heating, cooling, blowing.
Example 1 mixes the physicals of chromium APT powder in table 1.
This example SEM and EDS the results are shown in Figure 2, Fig. 3, Fig. 4, and XRD the results are shown in Figure 5.
Mix chromium APT powder and obtain WC-Co Wimet through processes such as calcining, hydrogen reduction, carbonization, shaping, liquid phase sinterings, metallographic the results are shown in Figure 6.
Embodiment 2
Prepare a method of evenly mixing chromium ammonium paratungstate, its step is as follows:
(1) ammonia solvent WO in advance 3prepare ammonium tungstate solution wherein WO 3=150 g/L, NH 4oH=1.8 mol/L, adds corresponding WO respectively 3with ammoniacal liquor in reactor, 100 DEG C of reaction 1 h;
(2) by 3 m 3ammonium tungstate solution adds in titanium lined material crystallizing pan, and stirring velocity is 70 r/min, stirs and slowly adds chromium acetate 18.3 Kg, opens steam valve steam regulation to 0.10-0.30MPa; Temperature controls as 90-100 DEG C, heating evaporation crystallization;
(3), after liquid level seethes with excitement completely in crystallizing pan, keep stirring constant, steam off;
(4) occur nucleus in pot to be crystallized, turning speed is 30 r/min, keeps vapor pressure to be 0.05-0.10 MPa;
(5) when solution density is to 1.1 g/cm 3, control stirring 70 r/min, keep vapor pressure to be 0.20-0.30 MPa;
(6) when pH value of solution=6.7 stop heating, cooling, blowing.
Example mixes the physicals of chromium APT powder in table 2.
Other results that example 2 mixes chromium APT powder are similar to example 1, therefore will not provide.
Embodiment 3
Prepare a method of evenly mixing chromium ammonium paratungstate, its step is as follows:
(1) ammonia solvent WO in advance 3prepare ammonium tungstate solution wherein WO 3=350 g/L, NH 4oH=5.0 mol/L, adds corresponding WO respectively 3with ammoniacal liquor in reactor, 100 DEG C of reaction 1 h;
(2) by 3 m 3ammonium tungstate solution adds in titanium lined material crystallizing pan, and stirring velocity is 70 r/min, stirs and slowly adds chromium acetate 17.8 Kg, opens steam valve steam regulation to 0.10-0.30 MPa; Temperature controls as 90-100 DEG C, heating evaporation crystallization;
(3), after liquid level seethes with excitement completely in crystallizing pan, keep stirring constant, steam off;
(4) occur nucleus in pot to be crystallized, turning speed is 30 r/min, keeps vapor pressure to be 0.05-0.10 MPa;
(5) when solution density is to 1.1 g/cm 3, control stirring 70 r/min, keep vapor pressure to be 0.20-0.30 MPa;
(6) when pH value of solution=6.8 stop heating, cooling, blowing.
Example 3 mixes the physicals of chromium APT powder in table 3.
Other results that example 3 mixes chromium APT powder are similar to example 1, therefore will not provide.
The above embodiment only have expressed the preferred embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion, improvement and substitute, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (3)

1. prepare a method of evenly mixing chromium ammonium paratungstate, it is characterized in that, its step is as follows:
(1) the molten WO of ammonia 3: add corresponding WO respectively 3with ammoniacal liquor in reactor, 100 DEG C of reaction 1 h, prepare ammonium tungstate solution, wherein WO 3concentration 150-350 g/L, NH 4oH concentration 1.8-5.0 mol/L;
(2) added by ammonium tungstate solution in titanium lined material crystallizing pan, stirring velocity is 70r/min, stirs and slowly adds solubility chromic salt, opens steam valve steam regulation to 0.10-0.30MPa; Temperature controls as 90-100 DEG C, heating evaporation crystallization;
(3), after liquid level seethes with excitement completely in crystallizing pan, keep stirring constant, steam off;
(4) occur nucleus in pot to be crystallized, stirring velocity is adjusted to 30 r/min, opens steam valve and keeps vapor pressure to be 0.05-0.10MPa;
(5) when solution density is to 1.1 g/cm 3, control stirring velocity to 70 r/min, keep vapor pressure to be 0.20-0.30 MPa;
(6) when pH value of solution=6.7-7.0 stops heating, cooling, blowing.
2. according to claim 1ly a kind ofly prepare the method for evenly mixing chromium ammonium paratungstate, it is characterized in that: in step (2), solubility chromic salt is chromium acetate.
3. according to claim 1ly a kind ofly prepare the method for evenly mixing chromium ammonium paratungstate, it is characterized in that: in step (2), controlling the mass ratio of chromium in ammonium paratungstate powder is 0.22 ~ 0.60%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109019690A (en) * 2018-09-13 2018-12-18 江西省科学院应用物理研究所 A kind of short flow process of rare-earth-doped modification ammonium paratungstate powder
CN109368701A (en) * 2018-11-29 2019-02-22 江西省科学院应用物理研究所 A kind of ammonium paratungstate composite granule preparation method containing rare earth
CN112209446A (en) * 2020-09-04 2021-01-12 崇义章源钨业股份有限公司 Method for recycling Cr-containing tungsten carbide waste and application thereof
CN112408485A (en) * 2020-11-26 2021-02-26 江西理工大学 Method for preparing tungsten oxide with array micro/nano structure

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CN102061524A (en) * 2010-11-08 2011-05-18 崇义章源钨业股份有限公司 Monocrystal ammonium paratungstate and preparation method thereof
CN102649586A (en) * 2012-05-24 2012-08-29 崇义章源钨业股份有限公司 Method for dissolving ammonium paratungstate and/or tungsten oxide
CN102912136A (en) * 2012-09-29 2013-02-06 崇义章源钨业股份有限公司 Method for processing tungsten powder wastes

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JPS5325290A (en) * 1976-08-20 1978-03-08 Mitsubishi Heavy Ind Ltd Production of denitration catalyst
CN102061524A (en) * 2010-11-08 2011-05-18 崇义章源钨业股份有限公司 Monocrystal ammonium paratungstate and preparation method thereof
CN102649586A (en) * 2012-05-24 2012-08-29 崇义章源钨业股份有限公司 Method for dissolving ammonium paratungstate and/or tungsten oxide
CN102912136A (en) * 2012-09-29 2013-02-06 崇义章源钨业股份有限公司 Method for processing tungsten powder wastes

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109019690A (en) * 2018-09-13 2018-12-18 江西省科学院应用物理研究所 A kind of short flow process of rare-earth-doped modification ammonium paratungstate powder
CN109019690B (en) * 2018-09-13 2020-07-03 江西省科学院应用物理研究所 Short-process preparation method of rare earth doped modified ammonium paratungstate powder
CN109368701A (en) * 2018-11-29 2019-02-22 江西省科学院应用物理研究所 A kind of ammonium paratungstate composite granule preparation method containing rare earth
CN112209446A (en) * 2020-09-04 2021-01-12 崇义章源钨业股份有限公司 Method for recycling Cr-containing tungsten carbide waste and application thereof
CN112408485A (en) * 2020-11-26 2021-02-26 江西理工大学 Method for preparing tungsten oxide with array micro/nano structure
CN112408485B (en) * 2020-11-26 2023-02-03 江西理工大学 Method for preparing tungsten oxide with array micro/nano structure

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