CN107626930B - The method for preparing nano-tungsten powder using ammonium tungstate - Google Patents
The method for preparing nano-tungsten powder using ammonium tungstate Download PDFInfo
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Abstract
The invention discloses the methods for preparing nano-tungsten powder using ammonium tungstate, comprising: takes production tungstic acid powder to be dissolved into weak aqua ammonia, to obtain ammonium tungstate solution；The ammonium tungstate solution is contacted and reacted in autoclave with zinc salt, to obtain Zinc Tungstate precipitating；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, nano-tungsten powder not only can effectively be prepared, but also the discharge amount 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 fields, in particular to the method for preparing nano-tungsten powder using ammonium tungstate.
Background technique
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).Currently, researcher to how to obtain this two
It plants solid product and how subsequent both substances of use comprehensively study extensively.However, from ammonium tungstate solution
To APT solid, the actually process of ammonia water and steam volatilization, which needs a large amount of energy, and the ammonia to volatilize is also
It will cause environmental pollution, recycling ammonia tail gas is also required to a large amount 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, however should
What method needed has high reaction activity Ar+NH3+H2Gaseous mixture has certain danger, and needs to fill using high-frequency plasma
It sets, production cost is higher, and production efficiency is also up for improving；In addition, there are also received using ammonium metatungstate (AMT) and citric acid preparation
Rice tungsten powder body, this method needs use citric acid to carry out complex reaction, while also ammonia being needed to nitrogenize, and to tungsten nitride powder
It is heat-treated, process flow is long, 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 need into one
Step research.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is the method for proposing to prepare nano-tungsten powder using ammonium tungstate.The present invention is by preparing tungsten powder using ammonium tungstate, side
Method is simple and at low cost, and nano-tungsten powder not only can effectively be prepared, but also the discharge amount 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 invention proposes a kind of method for preparing nano-tungsten powder using ammonium tungstate, packets
It includes:
Production tungstic acid powder is taken, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；
The ammonium tungstate solution is contacted and reacted in autoclave with zinc salt, to obtain Zinc Tungstate precipitating；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 ammonium tungstate body using ammonium tungstate
In system, by zinc salts precipitate method, ammonium tungstate system is converted to Zinc Tungstate system, obtains pure Zinc Tungstate precipitating, it is then sharp
Zinc Tungstate is restored with hydrogen, obtains required nano-tungsten powder.The present invention prepares nano-tungsten powder using ammonium tungstate as a result,
Method it is possible to prevente effectively from prepare Zinc Tungstate precipitating when introduce alkali metal impurity, obtain pure Zinc Tungstate, and then can keep away
Exempt from the phenomenon that tungsten powder coarse grains are led to 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, passing through directly benefit in the present invention
It is reacted with ammonium tungstate solution and zinc salt, eliminates the step of tune acid when preparing tungsten powder in correlative technology field, be greatly decreased
The discharge amount of waste water and the consumption of hydrochloric acid, not only reduce labour cost, but also solve pollution problem of the ammonia to environment.
In addition, the method according to the above embodiment of the present invention for preparing nano-tungsten powder using ammonium tungstate 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 be further improved the efficiency of preparation Zinc Tungstate precipitating.
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 increase the efficiency of preparation Zinc Tungstate precipitating.
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 react ammonium tungstate sufficiently with zinc salt.
In some embodiments of the invention, by ammonium tungstate solution and zinc salt in autoclave, in 25-200 DEG C
It is reacted 1-9 hours under conditions of temperature and 100-500r/min mixing speed, to obtain Zinc Tungstate precipitating.Thus, it is possible to make
Ammonium tungstate sufficiently reacts with zinc salt and Zinc Tungstate precipitating 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 supplying Zinc Tungstate precipitating 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 increase 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 which Zinc Tungstate precipitating is made 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.
Detailed description of the invention
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 using ammonium tungstate and the Zinc Tungstate precipitating of zinc salt reaction preparation
Figure.
Fig. 3 is the SEM according to an embodiment of the invention using ammonium tungstate and the Zinc Tungstate precipitating of zinc salt reaction preparation
Figure.
Fig. 4 is the another of the Zinc Tungstate precipitating according to an embodiment of the invention prepared using ammonium tungstate and zinc salt reaction
A SEM figure.
Fig. 5 is the EDS according to an embodiment of the invention using ammonium tungstate and the Zinc Tungstate precipitating of zinc salt reaction preparation
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 diagram of the Zinc Tungstate of a comparative example according to the present invention.
Fig. 9 is the XRD diagram of the tungsten powder of a comparative example according to the present invention.
Figure 10 is the XRD diagram of the Zinc Tungstate of another comparative example according to the present invention.
Figure 11 is the XRD diagram of the tungsten powder of another comparative example according to the present invention.
Figure 12 is the tungsten powder SEM figure of a comparative example according to the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
According to an aspect of the present invention, the invention proposes a kind of method for preparing nano-tungsten powder using ammonium tungstate, packets
It includes: taking production tungstic acid powder, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；By ammonium tungstate solution and zinc salt in height
It contacts and reacts in pressure reaction kettle, to obtain Zinc Tungstate precipitating；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 ammonium tungstate body using ammonium tungstate
In system, by zinc salts precipitate method, ammonium tungstate system is converted to Zinc Tungstate system, obtains pure Zinc Tungstate precipitating, it is then sharp
Zinc Tungstate is restored with hydrogen, obtains required nano-tungsten powder.The present invention prepares nano-tungsten powder using ammonium tungstate as a result,
Method it is possible to prevente effectively from prepare Zinc Tungstate precipitating when introduce alkali metal impurity, obtain pure Zinc Tungstate, and then can keep away
Exempt from the phenomenon that tungsten powder coarse grains are led to 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, passing through directly benefit in the present invention
It is reacted with ammonium tungstate solution and zinc salt, eliminates the step of tune acid when preparing tungsten powder in correlative technology field, be greatly decreased
The discharge amount of waste water and the consumption of hydrochloric acid, not only reduce labour cost, but also solve pollution problem of the ammonia to environment.
In prior art, multi-purpose sodium tungstate solution and zinc salt reaction precipitate to prepare Zinc Tungstate.However, invention human hair
Existing, when being precipitated using sodium tungstate and zinc salt reaction preparation Zinc Tungstate, the alkali metal element sodium in Zinc Tungstate precipitating 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 element of band will cause tungsten powder coarse grains, it is difficult to obtain the lesser nano-tungsten powder of partial size.Inventors have found that by straight
It connects and reacts preparation Zinc Tungstate with zinc salt using the ammonium tungstate solution in production, it is possible to prevente effectively from introducing alkali metal impurity sodium, obtains
To pure Zinc Tungstate, and then can guarantee to obtain the partial size 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 compares, 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 amount of waste water and the consumption of hydrochloric acid is greatly decreased, not only reduces labour cost, but also solution
It has determined pollution problem of the ammonia to environment.
It is retouched in detail below with reference to the method that using ammonium tungstate prepares nano-tungsten powder of the Fig. 1 to the above embodiment of the present invention
It states.
According to an embodiment of the invention, ammonium tungstate solution is contacted and reacted in autoclave with zinc salt, so as to
It is precipitated to Zinc Tungstate.Wherein, ammonium tungstate solution is reacted with the leading ion that zinc salt occurs are as follows:
Zn2++WO4 2-=ZnWO4↓。
Reacted with zinc salt in the present invention using ammonium tungstate solution, tungsten can be directly extracted from ammonium tungstate solution, make tungsten with
The form of Zinc Tungstate precipitating exists, and can also avoid introducing impurity when extraction Zinc Tungstate precipitating, and then prevent 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 with zinc salt
To save the step for adjusting acid in correlative technology field, and then the discharge amount 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, weak aqua ammonia is dissolved into, 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 oxidation in the present invention
The ammonium tungstate solution of tungsten concentration can further promote Zn2++WO4 2-=ZnWO4↓ reaction is gone on smoothly, and raising prepares wolframic acid
The efficiency of zinc precipitating.
According to a particular embodiment of the invention, zinc salt can for selected from zinc chloride, zinc sulfate, zinc acetate and zinc nitrate extremely
Few one kind.Thus, it is possible to further increase the efficiency of preparation Zinc Tungstate precipitating.
According to a particular embodiment of the invention, the molar 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 previously mentioned, from there through 1-1.5 times of zinc is added, i.e., addition is relative to WO4 2-It crosses
The zinc of amount can make WO4 2-Sufficiently precipitating, and then improve the recycling of tungsten and the yield of tungsten powder.Specific implementation according to the present invention
Example, if the molar ratio of zinc is lower than 1:1 in tungstic acid and zinc salt in ammonium tungstate solution, tungstate radicle can not be precipitated completely, be led
Cause tungstate radicle waste；If the molar ratio of zinc is greater than 1.5:1 in the tungstic acid and zinc salt in ammonium tungstate solution, due to tungstate radicle
It is sufficiently reacted with zinc salt, Zn can not be pushed2++WO4 2-=ZnWO4↓ reaction carries out to the right, not only wastes reactant, but also solution
In contain a large amount of zinc salt, cause subsequent extracted Zinc Tungstate to be difficult to clean when precipitating, to influence finally to be prepared a nanometer tungsten
The partial size of powder.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 as a result,
Salt sufficiently reacts, moreover it is possible to the partial size for the nano-tungsten powder for ensuring finally to be prepared.
It 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 speed under conditions of react 1-9 hours, so as to obtain Zinc Tungstate precipitating.In the present invention
Tungstate ion can be made to come into full contact with zinc ion by using above-mentioned reaction condition, accelerate reaction rate, be effectively prepared into
It is precipitated to Zinc Tungstate.In addition, inventor also found, it can also further be controlled by the reaction temperature for controlling different and be finally prepared into
The partial size 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 partial size for carrying out tungsten powder when reduction treatment prepares nano-tungsten powder to amorphous Zinc Tungstate is opposite
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 partial size for carrying out the nano-tungsten powder that reduction treatment is prepared is thinner；It as a result, can be by controlling ammonium tungstate solution in the present invention
The partial size 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 the nano-tungsten powder that available partial size is thinner.
Reduction treatment is carried out according to an embodiment of the invention, precipitating to Zinc Tungstate, to obtain nano-tungsten powder.Wherein, hydrogen
The reaction that gas restores 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, carry out also original place to Zinc Tungstate precipitating using hydrogen
Reason, not only can effectively be prepared nano-tungsten powder, can also be collected into zinc simple substance by suitable equipment.
According to a particular embodiment of the invention, it can further include before carrying out reduction treatment: Zinc Tungstate precipitated
Carry out washing drying and processing.Thus, it is possible to further increase the purity of Zinc Tungstate precipitating, and then impurity pair can be further reduced
The interference of nano-tungsten powder partial size.
According to a particular embodiment of the invention, reduction treatment can be supplied by precipitating Zinc Tungstate into tube furnace, and
Hydrogen progress is passed through into tube furnace, the flow velocity of hydrogen can be 40L/h.Thus, it is possible to further increase 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 which Zinc Tungstate precipitating is made to be reduced sufficiently and obtain nano-tungsten powder.
According to a particular embodiment of the invention, by using the above-mentioned method for preparing nano-tungsten powder using ammonium tungstate of the present invention
And condition, the nano-tungsten powder average grain diameter being finally prepared can be made to reach 20-200nm, to be used for preparation function
It can not only be effectively improved the ductility of material when material and structural material and reduce the transition temperature of ductile-brittle, it can also be into one
Step increases grain boundary area, reduces impurity in the density of crystal boundary, and then significantly improve the intensity and toughness of material.
Embodiment 1
Study influence of the reaction temperature to preparation Zinc Tungstate precipitating.
300ml ammonium tungstate solution is taken, is divided into 3 groups, number 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 molar ratio of middle zinc is 1:1.2), different reaction temperature: room temperature, 120,180 DEG C.Wolframic acid under the conditions of detection differential responses temperature
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 conditions of 1 differential responses temperature of table
| Number | Reaction temperature/DEG C | Rate of deposition (%) |
| A | Room temperature | 95.69 |
| B | 120 | 96.26 |
| C | 180 | 97.83 |
Embodiment 2
Study influence of the zinc salt to preparation Zinc Tungstate precipitating.
The dense material of 300ml ammonium tungstate is taken, is divided into 3 groups, number A, B, C；To 3 groups of experiments, carry out decomposing autoclave reaction,
Identical reaction time (2h), mixing speed (400r/min), reaction temperature be 140 DEG C, the tungstic acid in ammonium tungstate solution
It is respectively as follows: 1:1,1:1.2,1:1.4 with the molar ratio of zinc in zinc salt.The rate of deposition of Zinc Tungstate under different zinc nitrate dosages is detected,
Testing result is as shown in table 2.
Conclusion: the molar ratio of zinc is in 1:(1-1.5 in the tungstic acid and zinc salt in ammonium tungstate solution) in range when, with
The rate of deposition of the increase of zinc and tungstic acid molar ratio, Zinc Tungstate also becomes larger.
Influence of 2 zinc salt of table to the rate of deposition of Zinc Tungstate
| Serial number | The molar 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 influence of the mixing speed to preparation Zinc Tungstate precipitating.
The dense material of 300ml ammonium tungstate is taken, is divided into 3 groups, number 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 molar ratio of zinc is 1:1.2 in salt), mixing speed is 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 is reacted with zinc nitrate, and the rate of deposition of Zinc Tungstate is higher.
The rate of deposition of Zinc Tungstate under the conditions of 3 differential responses temperature of table
| Serial 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 precipitating.
The dense material of 300ml ammonium tungstate is taken, is divided into 3 groups, number 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 molar ratio of zinc is 1:1.2), the different reaction time (hour): 1,3,5.Detect the precipitating 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 4 differential responses time of table
| Serial 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)
It is reacted in 1L decomposing pot, prepares Zinc Tungstate.The condition of reaction are as follows: 160 DEG C of temperature, the time is 2.5 hours, mixing speed
For 450r/min, the molar ratio of zinc and tungstic acid is 1.1:1 in zinc acetate.After reaction, the Zinc Tungstate of acquisition is through 100 DEG C
Drying, for detecting and sequential reduction experiment.The Zinc Tungstate solid that precipitating is obtained weighs 1.6g, is put into tube furnace, controls
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 precipitating being prepared is observed, and EDS constituent analysis, X-ray are done to Zinc Tungstate precipitating
Diffraction analysis, transmission and BET analysis.It observes the microscopic appearance for the nano-tungsten powder being prepared and it does BET analysis.
As a result with conclusion:
Table 5 be Zinc Tungstate precipitating composition analysis result, Fig. 2 be prepared Zinc Tungstate precipitating XRD diagram, Fig. 3 and
Fig. 4 is the SEM electron microscope for the Zinc Tungstate precipitating being prepared, and Fig. 5 is the EDS figure of Zinc Tungstate precipitating, wherein Fig. 5 is in Fig. 4
On the basis of obtain, Fig. 6 is the XRD diagram for the nano-tungsten powder being prepared, and Fig. 7 is the TEM figure of the nano-tungsten powder that is prepared.
As can be seen that the deposit that use above-mentioned preparation method to be prepared is pure and to be brilliant from table 5, Fig. 2 and Fig. 5
The complete Zinc Tungstate of type, and from figure 3, it can be seen that be prepared Zinc Tungstate precipitating partial size it is smaller, and be in short grained group
Aggressiveness, the BET result of Zinc Tungstate precipitating are 18m2/g.From fig. 6, it can be seen that the receiving in dispersion for the nano-tungsten powder being prepared
Rice grain, BET result are 8m2/ g, the partial size that conversion obtains nano-tungsten powder is 38.76nm.And from Fig. 7 it can also be seen that system
The partial size of standby obtained nano-tungsten powder is smaller.The method for preparing nano-tungsten powder using ammonium tungstate by using the present invention as a result, can
Partial size is prepared effectively as the nano-tungsten powder of 20-200nm.
The EDS composition analysis result of 5 Zinc Tungstate of table precipitating
Comparative example 1
The method for preparing tungsten powder using the dense feed liquid of sodium tungstate is as follows:
(1) use glacial acetic acid (acetic acid) by the dense feed liquid tune acid of sodium tungstate to pH=8-10.
(2) to adjust acid after the dense feed liquid of sodium tungstate in zinc acetate is added, heating water bath to 100 DEG C, the reaction time 5 hours,
The ingredient for detecting the tungstic acid and filter residue in filtrate, judges whether reaction terminates, and is such as not finished, continuously adds and reacted,
Zinc Tungstate precipitating 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 Tungstate in water-bath is restored, 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, carries out X-ray diffraction detection to tungsten powder
And fluorescence analysis, the x-ray diffraction pattern of tungsten powder are shown in that Fig. 9, fluorometric result are shown in Table 6.
Conclusion: can be seen that Zinc Tungstate from Fig. 8 and Fig. 9 and tungsten powder is amorphous state, and as can be seen from Table 6, wolframic acid
Contain impurity element in zinc.
6 tungsten powder fluorometric result (qualitative) of table
| Serial number | Element/component | Content/% | Serial 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 for preparing tungsten powder using the dense feed liquid of sodium tungstate is as follows:
(1) use glacial acetic acid (acetic acid) by the dense feed liquid tune acid of sodium tungstate to pH=8-10.
(2) to adjust acid after the dense feed liquid of sodium tungstate in zinc acetate is added, heating water bath to 180 DEG C, the reaction time 5 hours,
The ingredient for detecting the tungstic acid and filter residue in filtrate, judges whether reaction terminates, and is such as not finished, continuously adds and reacted,
Zinc Tungstate precipitating 10g is obtained, X-ray diffraction detection and sem analysis, the result is shown in Figure 10 are carried out to Zinc Tungstate.
(3) under the conditions of temperature is 950 DEG C, in a hydrogen atmosphere, the 10g Zinc Tungstate in water-bath is restored, 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, carries out X-ray diffraction inspection to tungsten powder
It surveys, sem analysis and fluorescence analysis, the x-ray diffraction pattern of tungsten powder are shown in that Figure 11, the SEM figure of tungsten powder are shown in Figure 12, fluorometric result
It is shown in Table 7.
Conclusion: can be seen that Zinc Tungstate from Figure 10 and Figure 11 and tungsten powder is amorphous state, it can be recognized from fig. 12 that system
Standby obtained Tungsten Powder Size is larger, and as can be seen from Table 7, impurity element is contained in Zinc Tungstate.
7 tungsten powder fluorometric result (qualitative) of table
| Serial number | Element/component | Content/% | Serial 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 conclusion by embodiment 5 and comparative example 1-2 it can be found that being prepared by using the present invention using ammonium tungstate
The complete Zinc Tungstate precipitating of pure and crystal form can be prepared in the method for nano-tungsten powder, and obtaining partial size is 103-155nm's
Nano-tungsten powder.And contain impurity in the tungsten powder that comparative example 1-2 it can be seen from table 6-7, Fig. 8-9 and Figure 10-12 is prepared
Ingredient, and the tungsten powder obtained is coarseer.
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 spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. a kind of method for preparing nano-tungsten powder using ammonium tungstate characterized by comprising
Production tungstic acid powder is taken, weak aqua ammonia is dissolved into, to obtain ammonium tungstate solution；
The ammonium tungstate solution is contacted and reacted in autoclave with zinc salt, to obtain Zinc Tungstate precipitating；And
The Zinc Tungstate is precipitated and carries out reduction treatment, to obtain the nano-tungsten powder.
2. the method according to claim 1 for preparing nano-tungsten powder using ammonium tungstate, which is characterized 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 for preparing nano-tungsten powder using ammonium tungstate, which is characterized 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 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that in the zinc salt
The molar ratio of tungstic acid is (1-1.5) in zinc and the ammonium tungstate solution: 1.
5. the method according to claim 1 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that by the ammonium tungstate
Solution and zinc salt react 1- under conditions of 25-200 DEG C of temperature and 100-500r/min mixing speed in autoclave
9 hours, to obtain Zinc Tungstate precipitating.
6. the method according to claim 1 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that the reaction under high pressure
Pressure in kettle is 0.1-1.5Mpa.
7. the method according to claim 1 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that the reduction treatment
It is the hydrogen by the way that Zinc Tungstate precipitating supply is passed through what hydrogen carried out into tube furnace, and into the tube furnace
Flow velocity be 40L/h.
8. the method according to claim 7 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that the reduction treatment
Temperature be 700-1000 degrees Celsius, the time be 1-6 hours.
9. the method according to claim 1 for preparing nano-tungsten powder using ammonium tungstate, which is characterized in that the nano-tungsten powder
Average grain diameter is 20-200nm.
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