CN107626930A - The method that nano-tungsten powder is prepared using ammonium tungstate - Google Patents
The method that nano-tungsten powder is prepared using ammonium tungstate Download PDFInfo
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Abstract
The invention discloses the method that nano-tungsten powder is prepared using ammonium tungstate, including：Production tungstic acid powder is taken to be dissolved into weak aqua ammonia, to obtain ammonium tungstate solution；The ammonium tungstate solution in autoclave is contacted and reacted with zinc salt, to obtain Zinc Tungstate precipitation；And the Zinc Tungstate is precipitated and carries out reduction treatment, to obtain the nano-tungsten powder.The present invention prepares tungsten powder using ammonium tungstate, and nano-tungsten powder not only can effectively be prepared, and the discharge capacity of waste water and the consumption of hydrochloric acid can also be greatly decreased, and effectively avoids pollution of the ammonia to environment.
Description
Technical field
The invention belongs to metal smelt field, in particular to the method that nano-tungsten powder is prepared using ammonium tungstate.
Background technology
Nano-tungsten powder is the primary raw material of a variety of critical function materials and structural material, during the production and sales of tungsten,
Main solid intermediate product is ammonium paratungstate (APT) and ammonium metatungstate (AMT).At present, researcher to how to obtain this two
Plant solid product and how subsequently using both materials comprehensively study extensively.However, from ammonium tungstate solution
To the process of APT solids, the actually volatilization of ammonia water and steam, the process needs the substantial amounts of energy, and the ammonia to volatilize is also
Environmental pollution can be caused, recovery ammonia tail gas is also required to substantial amounts of fund.In correlative technology field, have using high frequency argon gas, ammonia
The method for preparing spherical nano tungsten powder with gaseous mixture plasma direct-reduction ammonium paratungstate (APT) step of hydrogen, but should
What method needed has high reaction activity Ar+NH3+H2Gaseous mixture has certain danger, and needs to use high-frequency plasma to fill
Put, production cost is higher, and production efficiency is also up for improving；Received in addition, also having and being prepared using ammonium metatungstate (AMT) and citric acid
Rice tungsten powder body, this method need to use citric acid to carry out complex reaction, while also need to ammonia nitridation, and to tungsten nitride powder
It is heat-treated, technological process length, it is difficult to realize industrialization.
Therefore, ammonia how is avoided the occurrence of in the production process of tungsten and obtains the nano-tungsten powder of high-purity and is need into one
Step research.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is to propose the method for preparing nano-tungsten powder using ammonium tungstate.The present invention prepares tungsten powder by using ammonium tungstate, side
Method is simple and cost is low, and nano-tungsten powder not only can effectively be prepared, and the discharge capacity and salt of waste water can also be greatly decreased
The consumption of acid, and effectively avoid pollution of the ammonia to environment.
According to an aspect of the present invention, the present invention proposes a kind of method that nano-tungsten powder is prepared using ammonium tungstate, wraps
Include：
Production tungstic acid powder is taken, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；
The ammonium tungstate solution in autoclave is contacted and reacted with zinc salt, to obtain Zinc Tungstate precipitation；With
And
The Zinc Tungstate is precipitated and carries out reduction treatment, to obtain the nano-tungsten powder.
The above embodiment of the present invention prepares the method for nano-tungsten powder by the way that tungsten is entered into ammonium tungstate body using ammonium tungstate
In system, by zinc salts precipitate method, ammonium tungstate system is changed into Zinc Tungstate system, obtains pure Zinc Tungstate precipitation, Ran Houli
Zinc Tungstate is reduced with hydrogen, obtains required nano-tungsten powder.Thus, the present invention prepares nano-tungsten powder using ammonium tungstate
Method it is possible to prevente effectively from prepare Zinc Tungstate precipitation when introduce alkali metal impurity, obtain pure Zinc Tungstate, and then can keep away
Exempt to cause the phenomenon of tungsten powder coarse grains due to introducing impurity in Zinc Tungstate when sequential reduction processing prepares nano-tungsten powder, and
To required nano-tungsten powder, meanwhile, zinc simple substance can also be collected by suitable equipment.In addition, pass through directly profit in the present invention
Reacted, the step of eliminating acid adjustment when tungsten powder is prepared in correlative technology field, be greatly decreased with ammonium tungstate solution and zinc salt
The discharge capacity of waste water and the consumption of hydrochloric acid, both reduce labour cost, solve pollution problem of the ammonia to environment again.
In addition, it is according to the above embodiment of the present invention using ammonium tungstate prepare nano-tungsten powder method can also have it is as follows
Additional technical characteristic：
In some embodiments of the invention, the concentration of tungstic acid is 50-500g/L in the ammonium tungstate solution.By
This, can further improve the efficiency for preparing Zinc Tungstate precipitation.
In some embodiments of the invention, the zinc salt is in zinc chloride, zinc sulfate, zinc acetate and zinc nitrate
It is at least one.Thus, it is possible to further improve the efficiency for preparing Zinc Tungstate precipitation.
In some embodiments of the invention, mole of the zinc in the zinc salt and tungstic acid in the ammonium tungstate solution
Than for (1-1.5)：1.Thus, it is possible to ammonium tungstate is set fully to be reacted with zinc salt.
In some embodiments of the invention, by ammonium tungstate solution and zinc salt in autoclave, in 25-200 DEG C
1-9 hours are reacted under conditions of temperature and 100-500r/min mixing speeds, to obtain Zinc Tungstate precipitation.Thus, it is possible to make
Ammonium tungstate fully reacts with zinc salt and Zinc Tungstate precipitation is effectively prepared.
In some embodiments of the invention, the pressure in the autoclave is 0.1-1.5Mpa.Thus, it is possible to have
Effect promotes Zinc Tungstate to precipitate the transformation from amorphous state to crystalline state.
In some embodiments of the invention, the reduction treatment is by the way that Zinc Tungstate precipitation is supplied to tube furnace
In, and hydrogen progress is passed through into the tube furnace, the flow velocity of the hydrogen is 40L/h.Thus, it is possible to further improve also
The efficiency of original place reason.
In some embodiments of the invention, the temperature of the reduction treatment is 700-1000 degrees Celsius, and the time is that 1-6 is small
When.Thus, it is possible to Zinc Tungstate precipitation is set to be reduced sufficiently and obtain nano-tungsten powder.
In some embodiments of the invention, the nano-tungsten powder average grain diameter is 20-200nm.
Brief description of the drawings
Fig. 1 is the method flow diagram according to an embodiment of the invention that nano-tungsten powder is prepared using ammonium tungstate.
Fig. 2 is the XRD according to an embodiment of the invention that the Zinc Tungstate prepared is reacted using ammonium tungstate and zinc salt and is precipitated
Figure.
Fig. 3 is the SEM according to an embodiment of the invention that the Zinc Tungstate prepared is reacted using ammonium tungstate and zinc salt and is precipitated
Figure.
Fig. 4 is the another of the Zinc Tungstate precipitation according to an embodiment of the invention reacted and prepared using ammonium tungstate and zinc salt
Individual SEM figures.
Fig. 5 is the EDS according to an embodiment of the invention that the Zinc Tungstate prepared is reacted using ammonium tungstate and zinc salt and is precipitated
Figure.
Fig. 6 is the nano-tungsten powder of the method preparation according to an embodiment of the invention that nano-tungsten powder is prepared using ammonium tungstate
SEM figure.
Fig. 7 is the nano-tungsten powder of the method preparation according to an embodiment of the invention that nano-tungsten powder is prepared using ammonium tungstate
TEM figure.
Fig. 8 is the XRD according to the Zinc Tungstate of a comparative example of the invention.
Fig. 9 is the XRD according to the tungsten powder of a comparative example of the invention.
Figure 10 is the XRD according to the Zinc Tungstate of another comparative example of the invention.
Figure 11 is the XRD according to the tungsten powder of another comparative example of the invention.
Figure 12 is schemed according to the tungsten powder SEM of one comparative example of the present invention.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of method that nano-tungsten powder is prepared using ammonium tungstate, wraps
Include：Production tungstic acid powder is taken, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；By ammonium tungstate solution and zinc salt in height
Contact and react in pressure reactor, to obtain Zinc Tungstate precipitation；And Zinc Tungstate is precipitated and carries out reduction treatment, to obtain
Nano-tungsten powder.
The above embodiment of the present invention prepares the method for nano-tungsten powder by the way that tungsten is entered into ammonium tungstate body using ammonium tungstate
In system, by zinc salts precipitate method, ammonium tungstate system is changed into Zinc Tungstate system, obtains pure Zinc Tungstate precipitation, Ran Houli
Zinc Tungstate is reduced with hydrogen, obtains required nano-tungsten powder.Thus, the present invention prepares nano-tungsten powder using ammonium tungstate
Method it is possible to prevente effectively from prepare Zinc Tungstate precipitation when introduce alkali metal impurity, obtain pure Zinc Tungstate, and then can keep away
Exempt to cause the phenomenon of tungsten powder coarse grains due to introducing impurity in Zinc Tungstate when sequential reduction processing prepares nano-tungsten powder, and
To required nano-tungsten powder, meanwhile, zinc simple substance can also be collected by suitable equipment.In addition, pass through directly profit in the present invention
Reacted, the step of eliminating acid adjustment when tungsten powder is prepared in correlative technology field, be greatly decreased with ammonium tungstate solution and zinc salt
The discharge capacity of waste water and the consumption of hydrochloric acid, both reduce labour cost, solve pollution problem of the ammonia to environment again.
In prior art, multi-purpose sodium tungstate solution and zinc salt reaction precipitates to prepare Zinc Tungstate.However, invention human hair
Existing, when preparing Zinc Tungstate precipitation using sodium tungstate and zinc salt reaction, the alkali metal sodium in Zinc Tungstate precipitation is difficult completely clear
Wash clean, it is difficult to obtain pure Zinc Tungstate solid.And when carrying out reduction to Zinc Tungstate solid and preparing tungsten powder, taken in Zinc Tungstate
The alkali metal of band can cause tungsten powder coarse grains, it is difficult to obtain the less nano-tungsten powder of particle diameter.Inventor has found, by straight
Connect and prepare Zinc Tungstate using the ammonium tungstate solution in production and zinc salt reaction, it is possible to prevente effectively from introducing alkali metal impurity sodium, obtain
To pure Zinc Tungstate, and then can ensure to obtain the particle diameter of nano-tungsten powder when carrying out reduction treatment to Zinc Tungstate.In addition, and tungsten
Sour sodium reacts preparation Zinc Tungstate with zinc salt and compared, and is directly reacted using ammonium tungstate solution and zinc salt, may be omitted with neutralizing
The step of alkali during sodium tungstate is molten, the discharge capacity of waste water and the consumption of hydrochloric acid is greatly decreased, both reduces labour cost, solve again
Determine pollution problem of the ammonia to environment.
The method that nano-tungsten powder is prepared using ammonium tungstate of the above embodiment of the present invention is retouched in detail below with reference to Fig. 1
State.
According to an embodiment of the invention, ammonium tungstate solution in autoclave is contacted and reacted with zinc salt, so as to
Precipitated to Zinc Tungstate.Wherein, the leading ion that ammonium tungstate solution occurs with zinc salt, which reacts, is：
Zn2++WO4 2-=ZnWO4↓。
Reacted in the present invention using ammonium tungstate solution and zinc salt, tungsten can be directly extracted from ammonium tungstate solution, make tungsten with
The form of Zinc Tungstate precipitation is present, and can also avoid introducing impurity during extraction Zinc Tungstate precipitation, and then prevents at sequential reduction
There is the problem of tungsten powder coarse grains in reason when preparing nano-tungsten powder.May be used also in addition, directly being reacted using ammonium tungstate solution and zinc salt
The step of to save acid adjustment in correlative technology field, and then the discharge capacity of waste water and the consumption of hydrochloric acid is greatly decreased.
According to a particular embodiment of the invention, production tungstic acid powder is taken, is dissolved into weak aqua ammonia, it is molten to obtain ammonium tungstate
Liquid.The concentration of tungstic acid can be 50-500g/L in the ammonium tungstate solution.By using with above-mentioned three oxidations in the present invention
The ammonium tungstate solution of tungsten concentration, it can further promote Zn2++WO4 2-=ZnWO4↓ reaction is smoothed out, and raising prepares wolframic acid
The efficiency of zinc precipitation.
According to a particular embodiment of the invention, zinc salt can be selected from zinc chloride, zinc sulfate, zinc acetate and zinc nitrate extremely
Few one kind.Thus, it is possible to further improve the efficiency for preparing Zinc Tungstate precipitation.
According to a particular embodiment of the invention, the mol ratio of tungstic acid can be in the zinc and ammonium tungstate solution in zinc salt
(1-1.5)：1.Zn2+With WO4 2-Reaction as it was previously stated, from there through 1-1.5 times of zinc is added, that is, add relative to WO4 2-Cross
The zinc of amount, WO can be made4 2-Fully precipitation, and then improve the recovery of tungsten and the yield of tungsten powder.According to the specific implementation of the present invention
Example, if the mol ratio of zinc is less than 1 in tungstic acid and zinc salt in ammonium tungstate solution:1, then tungstate radicle can not precipitate completely, lead
Tungstate radicle is caused to waste；If the mol ratio of zinc is more than 1.5 in the tungstic acid and zinc salt in ammonium tungstate solution:1, due to tungstate radicle
Fully reacted with zinc salt, Zn can not be promoted2++WO4 2-=ZnWO4↓ reaction is carried out to the right, not only wastes reactant, and solution
In contain substantial amounts of zinc salt, cause subsequent extracted Zinc Tungstate precipitate when be difficult to clean, so as to influence that a nanometer tungsten is finally prepared
The particle diameter of powder.Thus, ammonium tungstate and zinc can not only be made by using the ammonium tungstate solution and zinc salt of said ratio in the present invention
Salt fully reacts, moreover it is possible to ensures the particle diameter of nano-tungsten powder being finally prepared.
According to a particular embodiment of the invention, can be by ammonium tungstate solution and zinc salt in autoclave, in 25-200
DEG C temperature and 100-500r/min mixing speeds under conditions of react 1-9 hours, so as to obtain Zinc Tungstate precipitation.In the present invention
By using above-mentioned reaction condition tungstate ion can be made fully to be contacted with zinc ion, accelerate reaction rate, be effectively prepared into
Precipitated to Zinc Tungstate.In addition, inventor also found, finally it is prepared into by controlling different reaction temperatures further to control
The particle diameter of the nano-tungsten powder arrived.Specifically, and when controlling reaction temperature is 25-100 DEG C, the Zinc Tungstate solid being prepared is
Amorphous, activity is stronger, and the particle diameter that tungsten powder when reduction treatment prepares nano-tungsten powder is carried out to amorphous Zinc Tungstate is relative
It is larger.When reaction temperature is 100-200 DEG C, the Zinc Tungstate solid being prepared is the Zinc Tungstate solid to the crystalline state of crystalline state
The particle diameter for carrying out the nano-tungsten powder that reduction treatment is prepared is thinner；Thus, can be by controlling ammonium tungstate solution in the present invention
The particle diameter of nano-tungsten powder is further controlled with the reaction temperature of zinc salt.
According to a particular embodiment of the invention, the pressure in autoclave can be 0.1-1.5Mpa.Thus, it is possible to have
Effect promotes Zinc Tungstate to precipitate the transformation from amorphous state to crystalline state, and then can obtain the thinner nano-tungsten powder of particle diameter.
According to an embodiment of the invention, Zinc Tungstate is precipitated and carries out reduction treatment, to obtain nano-tungsten powder.Wherein, hydrogen
The reaction of gas reduction Zinc Tungstate is as follows：
ZnWO4(s)+4H2(g)=Zn (g) ↑+W (s)+4H2O↑。
The fusing point (420 DEG C) and boiling point (907 DEG C) of zinc are relatively low, and also original place is carried out to Zinc Tungstate precipitation using hydrogen
Reason, not only can effectively be prepared nano-tungsten powder, zinc simple substance can also be collected into by suitable equipment.
According to a particular embodiment of the invention, can further include before reduction treatment is carried out：Zinc Tungstate is precipitated
Carry out washing drying and processing.Thus, it is possible to further improve the purity of Zinc Tungstate precipitation, and then it can further reduce impurity pair
The interference of nano-tungsten powder particle diameter.
According to a particular embodiment of the invention, reduction treatment can be supplied into tube furnace by the way that Zinc Tungstate is precipitated, and
Hydrogen progress is passed through into tube furnace, the flow velocity of hydrogen can be 40L/h.Thus, it is possible to further improve the effect of reduction treatment
Rate.
According to a particular embodiment of the invention, the temperature of reduction treatment can be 700-1000 degrees Celsius, and the time can be
1-6 hours.Thus, it is possible to Zinc Tungstate precipitation is set to be reduced sufficiently and obtain nano-tungsten powder.
According to a particular embodiment of the invention, by using the above-mentioned method that nano-tungsten powder is prepared using ammonium tungstate of the present invention
And condition, the nano-tungsten powder average grain diameter that can make finally to be prepared reach 20-200nm, so as to use it for preparing function
The ductility of material can be not only effectively improved when material and structural material and reduces the transition temperature of ductile-brittle, one can also be entered
Step increase grain boundary area, reduces density of the impurity in crystal boundary, and then significantly improve the intensity and toughness of material.
Embodiment 1
Study the influence that reaction temperature precipitates to preparing Zinc Tungstate.
300ml ammonium tungstate solutions are taken, are divided into 3 groups, numbering A, B, C；To 3 groups of experiments, carry out decomposing autoclave reaction,
Identical reaction time (2h), mixing speed (400r/min), zinc nitrate dosage (tungstic acid and zinc salt in ammonium tungstate solution
The mol ratio of middle zinc is 1：1.2), different reaction temperature：Room temperature, 120,180 DEG C.Detect wolframic acid under differential responses temperature conditionss
The rate of deposition of zinc, testing result are as shown in table 1.
Conclusion：The reaction temperature of ammonium tungstate solution and zinc nitrate is higher, and the rate of deposition of Zinc Tungstate is higher.
The rate of deposition of Zinc Tungstate under the differential responses temperature conditionss of table 1
| Numbering | Reaction temperature/DEG C | Rate of deposition (%) |
| A | Room temperature | 95.69 |
| B | 120 | 96.26 |
| C | 180 | 97.83 |
Embodiment 2
Study the influence that zinc salt precipitates to preparing Zinc Tungstate.
The dense material of 300ml ammonium tungstates is taken, is divided into 3 groups, numbering A, B, C；To 3 groups of experiments, carry out decomposing autoclave reaction,
Identical reaction time (2h), mixing speed (400r/min), reaction temperature is 140 DEG C, the tungstic acid in ammonium tungstate solution
Mol ratio with zinc in zinc salt is respectively：1：1、1:1.2、1:1.4.The rate of deposition of Zinc Tungstate under different zinc nitrate dosages is detected,
Testing result is as shown in table 2.
Conclusion：The mol ratio of zinc is 1 in tungstic acid and zinc salt in ammonium tungstate solution：When in the range of (1-1.5), with
Zinc and the increase of tungstic acid mol ratio, the rate of deposition of Zinc Tungstate also become big.
Influence of the zinc salt of table 2 to the rate of deposition of Zinc Tungstate
| Sequence number | The mol ratio of tungstic acid and zinc | Rate of deposition % |
| A | 1 | 95.88 |
| B | 1.2 | 96.55 |
| C | 1.4 | 97.03 |
Embodiment 3
Study the influence that mixing speed precipitates to preparing Zinc Tungstate.
The dense material of 300ml ammonium tungstates is taken, is divided into 3 groups, numbering A, B, C, D, E；To 3 groups of experiments, decomposition autoclave is carried out
Reaction, identical reaction time (2h), reaction temperature are 140 DEG C, zinc nitrate dosage (tungstic acid and zinc in ammonium tungstate solution
The mol ratio of zinc is 1 in salt：1.2), mixing speed be respectively 100,300,500r/min.Detect wolframic acid under different mixing speeds
The rate of deposition of zinc, testing result are as shown in table 3.
Conclusion：Mixing speed is bigger when ammonium tungstate solution reacts with zinc nitrate, and the rate of deposition of Zinc Tungstate is higher.
The rate of deposition of Zinc Tungstate under the differential responses temperature conditionss of table 3
| Sequence number | Mixing speed/(r/min) | Rate of deposition % |
| A | 100 | 93.51 |
| B | 300 | 93.99 |
| C | 500 | 96.97 |
Embodiment 4
Study influence of the reaction time to preparation Zinc Tungstate precipitation.
The dense material of 300ml ammonium tungstates is taken, is divided into 3 groups, numbering A, B, C；To 3 groups of experiments, carry out decomposing autoclave reaction,
Reaction temperature is 140 DEG C, mixing speed (400r/min), the amount of zinc nitrate are (in the tungstic acid and zinc salt in ammonium tungstate solution
The mol ratio of zinc is 1：1.2), different reaction time (hour)：1、3、5.Detect the precipitation of Zinc Tungstate under the differential responses time
Rate, testing result are as shown in table 4.
Conclusion：Ammonium tungstate solution and zinc nitrate reaction time are longer, and the rate of deposition of Zinc Tungstate is higher.
The rate of deposition of Zinc Tungstate under the differential responses time of table 4
| Sequence number | Reaction time | Rate of deposition % |
| A | 1 | 93.51 |
| B | 3 | 96.82 |
| C | 5 | 96.97 |
Embodiment 5
Ammonium tungstate dope is produced (with tungstic acid densimeter, WO3Concentration be 266.42g/L) with zinc acetate (analysis pure)
Reacted in 1L decomposing pots, prepare Zinc Tungstate.The condition of reaction is：160 DEG C of temperature, time are 2.5 hours, mixing speed
For 450r/min, the mol ratio of zinc and tungstic acid is 1.1 in zinc acetate:1.After reaction terminates, the Zinc Tungstate of acquisition is through 100 DEG C
Drying, for detecting and sequential reduction experiment.The Zinc Tungstate solid obtained will be precipitated, weigh 1.6g, be put into tube furnace, controlled
Hydrogen flowing quantity is 40L/h, and reduction temperature is 900 DEG C, and the time is 3 hours, obtains nano-tungsten powder.
The microscopic appearance for the Zinc Tungstate precipitation being prepared is observed, and EDS constituent analyses, X ray are done to Zinc Tungstate precipitation
Diffraction analysis, transmission and BET analyses.Observe the microscopic appearance for the nano-tungsten powder being prepared and it does BET analyses.
As a result with conclusion：
Table 5 be Zinc Tungstate precipitation composition analysis result, Fig. 2 be prepared Zinc Tungstate precipitation XRD, Fig. 3 and
Fig. 4 is the SEM electron microscopes for the Zinc Tungstate precipitation being prepared, and Fig. 5 is the EDS figures of Zinc Tungstate precipitation, wherein, Fig. 5 is in Fig. 4
On the basis of obtain, Fig. 6 is the XRD for the nano-tungsten powder being prepared, and Fig. 7 is the TEM figures of the nano-tungsten powder that is prepared.
As can be seen that the deposit for using above-mentioned preparation method to be prepared is pure and for crystalline substance from table 5, Fig. 2 and Fig. 5
The complete Zinc Tungstate of type, and and be in short grained group from figure 3, it can be seen that the particle diameter for the Zinc Tungstate precipitation being prepared is smaller
Aggressiveness, the BET results of Zinc Tungstate precipitation are 18m2/g.From fig. 6, it can be seen that the nano-tungsten powder being prepared is received in scattered
Rice grain, its BET result are 8m2/ g, the particle diameter that conversion obtains nano-tungsten powder is 38.76nm.And from Fig. 7 it can also be seen that system
The particle diameter of standby obtained nano-tungsten powder is smaller.Thus, the method for preparing nano-tungsten powder using ammonium tungstate by using the present invention, can
So that nano-tungsten powder of the particle diameter as 20-200nm is effectively prepared.
The EDS composition analysis results of the Zinc Tungstate of table 5 precipitation
Comparative example 1
The method that tungsten powder is prepared using the dense feed liquid of sodium tungstate is as follows：
(1) glacial acetic acid (acetic acid) is used by the dense feed liquid acid adjustment of sodium tungstate to pH=8-10.
(2) zinc acetate is added into the dense feed liquid of sodium tungstate after acid adjustment, heating water bath is to 100 DEG C, 5 hours reaction time,
The composition of the tungstic acid and filter residue in filtrate is detected, judges whether reaction terminates, is not terminated such as, is continuously added and reacted,
Zinc Tungstate precipitation 10g is obtained, X-ray diffraction detection is carried out to Zinc Tungstate, as a result sees Fig. 8.
(3) under the conditions of temperature is 950 DEG C, in a hydrogen atmosphere, the 10g Zinc Tungstates in water-bath are reduced, reaction 2 is small
When, tungsten powder is obtained, the color of tungsten powder is in grey black, and quality is loose, is weighed as 5.393g, and X-ray diffraction detection is carried out to tungsten powder
And fluorescence analysis, the x-ray diffraction pattern of tungsten powder are shown in Fig. 9, fluorometric result is shown in Table 6.
Conclusion：Can be seen that Zinc Tungstate and tungsten powder from Fig. 8 and Fig. 9 is amorphous state, and as can be seen from Table 6, wolframic acid
Contain impurity element in zinc.
The tungsten powder fluorometric result (qualitative) of table 6
| Sequence number | Element/component | Content/% | Sequence number | Element/component | Content/% |
| 1 | Na | 3.6064 | 8 | Si | 0.1896 |
| 2 | Mg | 0.0189 | 9 | Cl | 0.0454 |
| 3 | Al | 0.0792 | 10 | Fe | 0.0409 |
| 4 | P | 0.2788 | 11 | As | 0.0241 |
| 5 | S | 0.0708 | 12 | Mo | 0.0327 |
| 6 | K | 0.1589 | 13 | W | 95.3169 |
| 7 | Ca | 0.1373 |
Comparative example 2
The method that tungsten powder is prepared using the dense feed liquid of sodium tungstate is as follows：
(1) glacial acetic acid (acetic acid) is used by the dense feed liquid acid adjustment of sodium tungstate to pH=8-10.
(2) zinc acetate is added into the dense feed liquid of sodium tungstate after acid adjustment, heating water bath is to 180 DEG C, 5 hours reaction time,
The composition of the tungstic acid and filter residue in filtrate is detected, judges whether reaction terminates, is not terminated such as, is continuously added and reacted,
Zinc Tungstate precipitation 10g is obtained, X-ray diffraction detection and sem analysis are carried out to Zinc Tungstate, as a result see Figure 10.
(3) under the conditions of temperature is 950 DEG C, in a hydrogen atmosphere, the 10g Zinc Tungstates in water-bath are reduced, reaction 2 is small
When, tungsten powder is obtained, the color of tungsten powder is in grey black, and quality is loose, is weighed as 5.492g, and X-ray diffraction inspection is carried out to tungsten powder
Survey, sem analysis and fluorescence analysis, the x-ray diffraction pattern of tungsten powder are shown in Figure 11, and the SEM figures of tungsten powder are shown in Figure 12, fluorometric result
It is shown in Table 7.
Conclusion：Can be seen that Zinc Tungstate and tungsten powder from Figure 10 and Figure 11 is amorphous state, it can be recognized from fig. 12 that system
It is larger for obtained Tungsten Powder Size, and as can be seen from Table 7, impurity element is contained in Zinc Tungstate.
The tungsten powder fluorometric result (qualitative) of table 7
| Sequence number | Element/component | Content/% | Sequence number | Element/component | Content/% |
| 1 | Na | 0.6917 | 8 | Mn | 0.0354 |
| 2 | Mg | 0.0048 | 9 | Fe | 0.110 |
| 3 | Al | 0.0812 | 10 | Zn | 0.1061 |
| 4 | P | 0.0454 | 11 | As | 0.0447 |
| 5 | S | 0.1348 | 12 | Mo | 0.0557 |
| 6 | K | 0.0192 | 13 | W | 98.5771 |
| 7 | Ca | 0.0929 |
In summary, by embodiment 5 and comparative example 1-2 it can be found that being prepared by using the present invention using ammonium tungstate
The method of nano-tungsten powder, the complete Zinc Tungstate precipitation of pure and crystal formation can be prepared, and it is 103-155nm's to obtain particle diameter
Nano-tungsten powder.And contain impurity in the tungsten powder being prepared by comparative example 1-2 it can be seen from table 6-7, Fig. 8-9 and Figure 10-12
Composition, and the tungsten powder obtained is thicker.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be any
Combined in an appropriate manner in individual or multiple embodiments or example.In addition, in the case of not conflicting, the technology of this area
Different embodiments or example and the feature of different embodiments or example described in this specification can be combined by personnel
And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (9)
- A kind of 1. method that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that including：Production tungstic acid powder is taken, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；The ammonium tungstate solution in autoclave is contacted and reacted with zinc salt, to obtain Zinc Tungstate precipitation；AndThe Zinc Tungstate is precipitated and carries out reduction treatment, to obtain the nano-tungsten powder.
- 2. the method according to claim 1 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the ammonium tungstate is molten The concentration of tungstic acid is 50-500g/L in liquid.
- 3. the method according to claim 2 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the zinc salt is choosing From at least one of zinc chloride, zinc sulfate, zinc acetate and zinc nitrate.
- 4. the method according to claim 3 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that in the zinc salt The mol ratio of zinc and tungstic acid in the ammonium tungstate solution is (1-1.5)：1.
- 5. the method according to claim 1 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that by the ammonium tungstate Solution in autoclave, reacts 1- with zinc salt under conditions of 25-200 DEG C of temperature and 100-500r/min mixing speeds 9 hours, to obtain Zinc Tungstate precipitation.
- 6. the method according to claim 1 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the reaction under high pressure Pressure in kettle is 0.1-1.5Mpa.
- 7. the method according to claim 1 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the reduction treatment It is to be supplied by the way that the Zinc Tungstate is precipitated into tube furnace, and hydrogen progress, the hydrogen is passed through into the tube furnace Flow velocity be 40L/h.
- 8. the method according to claim 7 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the reduction treatment Temperature be 700-1000 degrees Celsius, the time is 1-6 hours.
- 9. the method according to claim 1 that nano-tungsten powder is prepared using ammonium tungstate, it is characterised in that the nano-tungsten powder Average grain diameter is 20-200nm.
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