CN100460318C - Method for preparing phosphotungstic acid using ammonium paratungstate as raw material - Google Patents
Method for preparing phosphotungstic acid using ammonium paratungstate as raw material Download PDFInfo
- Publication number
- CN100460318C CN100460318C CNB2005101351735A CN200510135173A CN100460318C CN 100460318 C CN100460318 C CN 100460318C CN B2005101351735 A CNB2005101351735 A CN B2005101351735A CN 200510135173 A CN200510135173 A CN 200510135173A CN 100460318 C CN100460318 C CN 100460318C
- Authority
- CN
- China
- Prior art keywords
- acid
- accordance
- ammonium paratungstate
- solution
- phospho
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing phosphotungstic acid by taking ammonium paratungstate as raw material. It comprises following steps: (1) mixing ammonium paratungstate with inorganic acid at 0-60 Deg. C and getting active tungstate, and the molar ratio between inorganic acid and ammonium paratungstate is 10: 1 -100: 1; (2) mixing active tungstate and phosphoric acid at 20-90 Deg. C and getting phosphotungstic acid solution; and the molar ratio between phosphoric acid which accounts as H3PO4 and ammonium paratungstate is 1.1: 1- 50: 1; (3) making phosphotungstic acid precipitate from solution, drying, crystallizing and getting crystal phosphotungstic acid. By adding inorganic acid precipitant to precipitate phosphotungstic acid, then crying and crystallizing, it can increase its purity further. The invention is characterized by simple process, non use of high concentration of strong acid and flammable organic extractant, low content of phosphate radical in product and suitility for being uses as catalyst.
Description
Technical field
The present invention relates to a kind of method for preparing heteropoly acid containing tungsten, more particularly, the present invention relates to a kind of is the method for feedstock production high-purity phosphotungsticacid with the ammonium paratungstate.
Background technology
The heteropolyacid of Keggin (triumphant gold) structure is general to be made a general reference by the expressed mineral compound of following chemical general formula:
H
KYZ
12O
40·nH
2O
Wherein:
Y: atoms such as expression P, Si are called central atom or heteroatoms.
Z: atoms such as expression Mo, W are called polyatom.
K: be 3 or 4
N: be 0～30 positive integer
The heteropolyacid of Keggin (triumphant gold) structure is the class acid that, condensation acidified by two or more inorganic oxygen-containing acid ion, dehydration obtain having cagelike structure and duct, the existing strongly-acid of the heteropolyacid of this class formation, has oxidation-reduction quality again, therefore, it can be used as acid catalyst, also can be used as redox catalyst.Heteropolyacid has been applied in many organic chemical industry's reactions, as olefin hydration, formoxy-reaction, etherification reaction etc. as catalyzer.Phospho-wolframic acid H
3PW
12O
40NH
2O is most widely used in heteropolyacid, and is also the most representative.
People such as H.S.Booth have just reported the synthetic method of phospho-wolframic acid as far back as nineteen thirty-nine, are called as the prior synthesizing method of phospho-wolframic acid.This method is an ether acidizing extraction method.At first sodium tungstate solution is mixed with disodium phosphate soln, under heating and acidic conditions, generate the mixing solutions of phospho-wolframic acid and Tungstophosphoric acid, sodium salt.For phospho-wolframic acid is separated, adopt the method that adds the ether complexometric extraction from solution.Ether only forms a kind of complex compound of ether-phospho-wolframic acid with phospho-wolframic acid, form organic phase.A large amount of sodium ions are stayed aqueous phase.To contain the organic phase and the aqueous phase separation of ether-phosphotungstic acid complex, and add less water in the organic phase after separation, and heating makes ether volatilization, obtain the phospho-wolframic acid crystal behind the condensing crystal.This is the method for topmost synthetic phospho-wolframic acid in the at present domestic and international industrial production.This traditional method has used lower boiling organism compound-ether as complexing extractant.The boiling point of ether is 34.5 ℃, highly volatile.The defective that has safety and contaminate environment in the process of traditional synthetic phospho-wolframic acid.
US 2,503, and 991, US 3,288,562, US 3,361,518 disclose in succession with after the Lin Wusuanyan dilution, prepares the method for phospho-wolframic acid again with H type Zeo-karb.This method has avoided the 12-Lin Wusuanyan is changed into the preparation technology of free 12-phospho-wolframic acid, does not use ether, but this method steps complexity will be evaporated a large amount of solution, and power consumption greatly.And when ion-exchange, have many phospho-wolframic acids to resolve into wolframic acid to separate out, and be adsorbed on the surface of ion exchange resin, and greatly reduce the service efficiency of ion-exchange on the one hand, also greatly reduce the yield of 12-phospho-wolframic acid on the other hand.
CN1,301,592A discloses a kind of method for preparing phospho-wolframic acid.This method is a raw material with the sodium wolframate, adds oxygenant H in sodium tungstate solution
2O
2And mineral acid, after-5 to 30 ℃ of reactions, add reductive agent again, as SO
2, obtain a kind of active tungstic acid.Obtain Salkowski's solution with active tungstic acid and dilute phosphoric acid reaction, the reconcentration crystallization just obtains the phospho-wolframic acid crystal.This method preparation process complexity contains a large amount of phosphate radicals in the phospho-wolframic acid that obtains.CN1,544,483A improves aforesaid method, has used organic solvent C
2-C
20Ether carries out complexometric extraction with the phosphate radical in the reduction phospho-wolframic acid, but the organic solvent amount is big, has reduced the security of large-scale commercial production.
In sum, preparing phospho-wolframic acid at present, mostly to adopt sodium wolframate be raw material, yet there are no and utilize ammonium paratungstate (NH
4)
10[W
12O
42H
2] 4H
2The report and the patent of O (being called for short APT) preparation phospho-wolframic acid.And in the smelting process of tungsten ore, ammonium paratungstate (NH
4)
10[W
12O
42H
2] 4H
2O is the main Chemicals that the tungsten ore processing obtains, and its mature production technology has been removed impurity such as the Fe in the tungsten ore, Mn, Mo effectively, and the product purity height is a basic raw material of producing other tungsten products such as high true yellow wolframic acid, Tungsten oxide 99.999, tungsten powder material.
Summary of the invention
The present invention is a raw material with the ammonium paratungstate first, and a kind of method for preparing phospho-wolframic acid is provided.
Characteristics of the present invention are with the ammonium paratungstate to be raw material, contact with mineral acid earlier, generate a kind of active tungstic acid precipitation, contact with phosphoric acid again, generate the aqueous solution of phospho-wolframic acid, and phospho-wolframic acid is separated out from solution, and crystallization just obtains the phospho-wolframic acid crystal.
The method that with the ammonium paratungstate is the feedstock production phospho-wolframic acid contains following steps:
(1) ammonium paratungstate contacts with inorganic acid solution, obtains the active tungstic acid precipitation, and contact wherein is that the ammonium paratungstate powder is added in the inorganic acid solution,
(2) the active tungstic acid precipitation contacts with excess phosphoric acid solution, obtains Salkowski's solution,
(3) phospho-wolframic acid is separated out from solution, dry, crystallization obtain the phospho-wolframic acid crystal.
By method provided by the invention, in ammonium paratungstate and the sedimentary step of inorganic acid solution contact preparation active tungstic acid, described mineral acid is hydrochloric acid, sulfuric acid or nitric acid etc., or the mixture of the arbitrary volume ratio of hydrochloric acid, sulfuric acid and nitric acid etc.The mineral acid consumption can be chosen wantonly, as long as can generate the active tungstic acid precipitation, generally can control mineral acid and ammonium paratungstate mol ratio is 10:1～100:1, preferred 20:1～80:1.The suitable concentration of inorganic acid solution is 0.2mol/L～6.0mol/L, relatively is convenient to operation in this concentration range.The reaction of ammonium paratungstate and inorganic acid solution can be carried out in very wide temperature range, and general 0～60 ℃ gets final product, and preferred temperature is 10～40 ℃.In 1～10 hour reaction times, preferred 2～5 hours, long reaction time helped to react completely, thereby obtained the active tungstic acid precipitation of q.s.Reaction is left standstill, filters, is washed after finishing, and obtains the active tungstic acid precipitation.
By method provided by the invention, in ammonium paratungstate and the sedimentary step of inorganic acid solution contact preparation active tungstic acid, condense in order to quicken the active tungstic acid precipitation, and make precipitation be easy to washing and filtration, after ammonium paratungstate and inorganic acid solution reaction, can also add accelerant to reaction system.Accelerant is an inorganic aluminate, as Al (NO
3)
3, Al
2(SO
4)
3Or AlCl
3Deng, or Al (NO
3)
3, Al
2(SO
4)
3And AlCl
3Deng the mixture of any mol ratio.The volumetric molar concentration of accelerant in reaction system is 0.005～0.05mol/L, and digestion time is generally and got final product in 0.1～24 hour.After ageing process finishes, filter, wash, obtain the active tungstic acid precipitation.
By method provided by the invention, in the step that active tungstic acid precipitation and phosphoric acid solution react, phosphoric acid is excessive, and general consumption is with H
3PO
4Meter is 1.1:1～50:1 with the ammonium paratungstate mol ratio, preferred 2:1～10:1.The suitable concentration of phosphoric acid solution is 0.02～6.0mol/L, relatively is convenient to operation in this concentration range; Reaction can be carried out at normal temperatures, but under the situation of heating, can accelerated reaction, the temperature of reaction of recommendation is 20～90 ℃, preferred 30-60 ℃.General reaction is 2～5 hours in the said temperature scope, and reaction is carried out fully.
By method provided by the invention, phospho-wolframic acid is separated out from solution, dry, crystallization just obtain the phospho-wolframic acid crystal.The described phospho-wolframic acid that makes is separated out from solution, and what generally adopt is the method for evaporation concentration.
By method provided by the invention, the described phospho-wolframic acid that makes is separated out from solution, also can adopt the method that adds the mineral acid precipitation agent in Salkowski's solution, and phospho-wolframic acid is precipitated out from solution, carries out drying, crystallization again.Described mineral acid precipitation agent is hydrochloric acid, sulfuric acid or nitric acid etc., or the mixture of the arbitrary volume ratio of hydrochloric acid, sulfuric acid and nitric acid etc.The volumetric molar concentration of mineral acid precipitation agent in reaction system is 0.1～6mol/L, preferred 0.5～4mol/L.The reaction pair temperature requirement is not high, can carry out at-20～80 ℃, generally at room temperature carries out.The mineral acid precipitation agent can recycle.The phospho-wolframic acid crystal phosphoric acid radical content that obtains by the method that adds the mineral acid precipitation agent is low, the purity height.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
(1) the ammonium paratungstate raw material is easy to get;
(2) technology is simple, and the yield height helps reducing production costs;
(3) production process is not used the strong acid of a large amount of high densitys, and the corrodibility of equipment is significantly reduced;
(4) do not use inflammableness lower boiling organic extractant, the security of production operation obviously improves, suitability for mass industrialized production;
(5) phosphate content is low in the product, and the purity height can be used as acid catalyst.
Description of drawings
31The P-NMR nmr analysis is a kind of classical way of identifying the phospho-wolframic acid compound purity, referring to document: J.Inorg.Chem., and 1977,16 (11): 2916; The nuclear magnetic resonance spectrum of the phosphorus atom of different chemical environment has the characteristic peak of different chemical displacement, and patent of the present invention adopts
31P-NMR nucleus magnetic resonance spectral method is identified the purity of synthetic phospho-wolframic acid.
Fig. 1 is embodiment 4 phospho-wolframic acid samples
31The P-NMR nuclear magnetic resonance spectrum.
Fig. 2 is Comparative Examples 1 a phospho-wolframic acid sample
31The P-NMR nuclear magnetic resonance spectrum.
Embodiment
Following example will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Ammonium paratungstate is an analytical pure, and the chemical company limited of the huge energy in Tianjin produces; The weight concentration of concentrated hydrochloric acid is 36%, analytical pure, and the Beijing Chemical Plant produces; Phosphoric acid, sulfuric acid, nitric acid, aluminum nitrate, Tai-Ace S 150, aluminum chloride are analytical pure, and Beijing chemical reagents corporation produces.
Embodiment 1
Take by weighing 50 gram concentrated hydrochloric acids, being made into concentration is the hydrochloric acid soln 600mL of 0.8mol/L, this hydrochloric acid soln is poured in the glass beaker, under 15 ℃, in beaker, add 20 gram ammonium paratungstate powder (hydrochloric acid and ammonium paratungstate mol ratio are 75:1), stirring reaction generates the active tungstic acid precipitation after 2.0 hours, leave standstill, filter, washing.
The 18.5 gram active tungstic acid precipitations that obtain are joined (phosphoric acid and ammonium paratungstate mol ratio are 31:1) in the 100mL 2.0mol/L phosphate aqueous solution, be warming up to 60 ℃, constant temperature 2 hours obtains the clear Salkowski's solution.Evaporation, concentrated, dry, crystallization obtain the highly purified white phospho-wolframic acid of 16.24 grams, with H
3PW
12O
4029H
2The O meter, yield is 74.8%.
Embodiment 2
Take by weighing 50 gram concentrated hydrochloric acids, being made into concentration is the hydrochloric acid soln 600mL of 0.8mol/L, this hydrochloric acid soln is poured in the glass beaker, add 20 gram ammonium paratungstate powder (hydrochloric acid and ammonium paratungstate mol ratio are 75:1) under 5 ℃ in beaker, stirring reaction generates the active tungstic acid precipitation after 3.0 hours, adds 1.0 gram accelerant aluminum chloride (volumetric molar concentration is 0.01mol/L) then, 2 hours after-filtration of ageing, washing is left standstill, and filters washing.
The 19.8 gram active tungstic acid precipitations that obtain are joined (phosphoric acid and ammonium paratungstate mol ratio are 5:1) in the 500mL 0.06mol/L phosphate aqueous solution, be warming up to 55 ℃, constant temperature 2 hours obtains the clear Salkowski's solution.Evaporation, concentrated, dry, crystallization obtain the highly purified white phospho-wolframic acid of 16.55 grams, with H
3PW
12O
4029H
2The O meter, yield is 76.2%.
Embodiment 3
Take by weighing 50 gram concentrated hydrochloric acids, being made into concentration is the hydrochloric acid soln 600mL of 0.8mol/L, this hydrochloric acid soln is poured in the glass beaker, under 15 ℃, in beaker, add 20 gram ammonium paratungstate powder (hydrochloric acid and ammonium paratungstate mol ratio are 75:1), stirring reaction generates the active tungstic acid precipitation after 1.5 hours, leave standstill, filter, washing.
The 18.8 gram active tungstic acid precipitations that obtain are joined (phosphoric acid and ammonium paratungstate mol ratio are 5:1) in the 500mL 0.06mol/L phosphate aqueous solution, be warming up to 55 ℃, constant temperature 2 hours obtains the clear Salkowski's solution.Add weight concentration under 55 ℃ in this solution is 36% hydrochloric acid 10 grams (volumetric molar concentration is 0.2mol/L), generates white precipitate, filters, dry, crystallization, promptly obtains the highly purified white phospho-wolframic acid of 16.42 grams, with H
3PW
12O
4029H
2The O meter, yield is 75.6%.
Embodiment 4
Take by weighing 8 gram concentrated hydrochloric acids, being made into concentration is the hydrochloric acid soln 160mL of 0.5mol/L, this hydrochloric acid soln is poured in the glass beaker, under 45 ℃, in beaker, add 20 gram ammonium paratungstate powder (hydrochloric acid and ammonium paratungstate mol ratio are 12:1), stirring reaction generates the active tungstic acid precipitation after 8 hours, add 0.4 gram accelerant aluminum chloride (volumetric molar concentration is 0.017mol/L) then, 0.5 hour after-filtration of ageing, washing.
The 20.2 gram active tungstic acid precipitations that obtain are joined in the 500mL 0.6mol/L phosphate aqueous solution (mol ratio of phosphoric acid and ammonium paratungstate is 46:1), be warming up to 70 ℃, constant temperature 3 hours obtains the clear Salkowski's solution.Be cooled under 15 ℃ in this solution, to add weight concentration and be 36% hydrochloric acid 25 grams (volumetric molar concentration is 0.5mol/L), generate white precipitate, filter, dry, crystallization, promptly obtain the highly purified white phospho-wolframic acid of 17.12 grams, with H
3PW
12O
4029H
2The O meter, yield is 78.8%.The sample phospho-wolframic acid
31The P-NMR nuclear magnetic resonance spectrum is seen Fig. 1.Be phosphorus atom in the phospho-wolframic acid at the peak at chemical shift-14.879 place among Fig. 1
31The P-NMR nuclear magnetic resonance peak is a phosphorus atom in the phosphate radical at the peak at chemical shift 0.327 place
31The P-NMR nuclear magnetic resonance peak.As can be seen from Figure 1, sample does not almost have phosphate radical impurity.
Comparative Examples 1
According to patent CN1,301, the disclosed preparation method of 592A, the synthetic phospho-wolframic acid sample that obtains.The phospho-wolframic acid sample
31The P-NMR nuclear magnetic resonance spectrum is seen Fig. 2, can clearly be seen that from Fig. 2, and is very high at the resonance peak at chemical shift 0.378 place, illustrate by patent CN1, and 301, the content of phosphate radical is very high in the phospho-wolframic acid that the disclosed preparation method of 592A obtains.
Take by weighing weight concentration and be 65% concentrated nitric acid 20 grams, being made into concentration is the salpeter solution 80mL of 2.5mol/L, this salpeter solution is poured in the glass beaker, add 20 gram ammonium paratungstate powder (nitric acid and ammonium paratungstate mol ratio are 31:1) under 8 ℃ in beaker, stirring reaction generates the active tungstic acid precipitation after 6 hours.Add 0.4 gram accelerant aluminum nitrate (volumetric molar concentration is about 0.01mol/L) then, 8 hours after-filtration of ageing, washing.The 20.9 gram active tungstic acid precipitations that obtain are added in the 50mL 5.0mol/L phosphate aqueous solution (mol ratio of phosphoric acid and ammonium paratungstate is 39:1), are warming up to 85 ℃, be incubated 5 hours again, obtain the clear Salkowski's solution; In this solution, add 35 gram weight concentration when being cooled to-10 ℃ and be 80% sulfuric acid (volumetric molar concentration is 3.3mol/L), generate white precipitate, filter, dry, crystallization, promptly obtain the highly purified white phospho-wolframic acid of 17.15 grams, with H
3PW
12O
4029H
2The O meter, yield is 79.0%, the sample phospho-wolframic acid
31The P-NMR nuclear magnetic resonance spectrum is similar to Fig. 1.
Embodiment 6
Take by weighing 60 gram mixing acid (nitric acid: hydrochloric acid=1:1, volume ratio) is made into the mixed acid solution 120mL that concentration is 5.0mol/L (mixing acid and ammonium paratungstate mol ratio are 94:1), mixed acid solution is poured in the glass beaker, add 20 gram ammonium paratungstate powder under 25 ℃ in cup, stirring reaction generates the active tungstic acid precipitation after 3 hours.Add 2.0 gram weight then than being the aluminum nitrate of 1:1 and Tai-Ace S 150 mixture accelerant (volumetric molar concentration is 0.03mol/L), 4 hours after-filtration of ageing, washing.The 19.5 gram active tungstic acid precipitations that obtain are added in the 100mL 0.1ml/L phosphate aqueous solution (mol ratio of phosphoric acid and ammonium paratungstate is 1.6:1), are warming up to 30 ℃, constant temperature 4 hours obtains the clear Salkowski's solution; In this solution, add 50 gram weight concentration when being warmed up to 74 ℃ and be 80% the vitriol oil (volumetric molar concentration is 2.7mol/L), generate white precipitate, filter, dry, crystallization, promptly obtain the highly purified white phospho-wolframic acid of 16.90 grams, with H
3PW
12O
4029H
2The O meter, yield 77.8%, the sample phospho-wolframic acid
31The P-NMR nuclear magnetic resonance spectrum is similar to Fig. 1.
Embodiment 7
Take by weighing 38 gram concentrated hydrochloric acids, being made into concentration is the hydrochloric acid soln 470mL (hydrochloric acid and ammonium paratungstate mol ratio are 60:1) of 0.8mol/L, this hydrochloric acid soln is poured in the glass beaker, under 20 ℃, in beaker, add 20 gram ammonium paratungstate powder, stirring reaction generates the active tungstic acid precipitation after 2 hours, add 1.0 gram accelerant aluminum nitrates (the accelerant volumetric molar concentration is 0.006mol/L) then, 20 hours after-filtration of ageing, washing.The 19.9 gram active tungstic acid precipitations that obtain are joined in the 100mL 1.0mol/L phosphate aqueous solution (mol ratio of phosphoric acid and ammonium paratungstate is 15:1), be warming up to 55 ℃, constant temperature 2 hours obtains the clear Salkowski's solution.Add weight concentration under 30 ℃ in this solution is 36% hydrochloric acid 100 grams (volumetric molar concentration is 5mol/L), generates white precipitate, filters, dry, crystallization, promptly obtains the highly purified white phospho-wolframic acid of 17.08 grams, with H
3PW
12O
4029H
2The O meter, yield is 78.6%.The sample phospho-wolframic acid
31The P-NMR nuclear magnetic resonance spectrum is similar to Fig. 1.
Embodiment 8
According to the synthetic phospho-wolframic acid of the condition of embodiment 4, difference is that the Acid precipitation agent that adds is mixture 50 grams (volumetric molar concentration is 0.9mol/L) of hydrochloric acid and nitric acid, replaces the hydrochloric acid that adds among the embodiment 4 in the phospho-wolframic acid mother liquor.Obtain the highly purified white phospho-wolframic acid of 16.97 grams at last, with H
3PW
12O
4029H
2The O meter, yield 78.2%, the sample phospho-wolframic acid
31The P-NMR nuclear magnetic resonance spectrum is similar to Fig. 1.
Claims (19)
1. one kind is the method for feedstock production phospho-wolframic acid with the ammonium paratungstate, contains following steps:
(1) ammonium paratungstate contacts with inorganic acid solution, obtains the active tungstic acid precipitation, and contact wherein is that the ammonium paratungstate powder is added in the inorganic acid solution, and described mineral acid is hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio,
(2) the active tungstic acid precipitation contacts with excess phosphoric acid solution, obtains Salkowski's solution,
(3) phospho-wolframic acid is separated out from solution, dry, crystallization obtain the phospho-wolframic acid crystal.
2. in accordance with the method for claim 1, it is characterized in that mineral acid and ammonium paratungstate mol ratio are 10:1-100:1.
3. in accordance with the method for claim 2, it is characterized in that mineral acid and ammonium paratungstate mol ratio are 20:1～80:1.
4. in accordance with the method for claim 1, it is characterized in that ammonium paratungstate contacts under 0～60 ℃ with inorganic acid solution.
5. in accordance with the method for claim 4, it is characterized in that ammonium paratungstate contacts under 10～40 ℃ with inorganic acid solution.
6. in accordance with the method for claim 1, it is characterized in that, in reaction system, add the inorganic aluminate accelerant afterwards in step (1).
7. in accordance with the method for claim 6, it is characterized in that described inorganic aluminate accelerant is Al (NO
3)
3, Al
2(SO
4)
3Or AlCl
3, or Al (NO
3)
3, Al
2(SO
4)
3And AlCl
3The mixture of any mol ratio.
8. in accordance with the method for claim 6, it is characterized in that the volumetric molar concentration of described inorganic aluminate accelerant in reaction system is 0.005～0.05mol/L.
9. according to the described method of one of claim 6-8, it is characterized in that digestion time is 0.1～24 hour.
10. in accordance with the method for claim 1, it is characterized in that described phosphoric acid consumption is with H
3PO
4Meter is 1.1:1～50:1 with the ammonium paratungstate mol ratio.
11. in accordance with the method for claim 10, it is characterized in that described phosphoric acid consumption is with H
3PO
4Meter is 2:1～10:1 with the ammonium paratungstate mol ratio.
12. in accordance with the method for claim 1, it is characterized in that the active tungstic acid precipitation contacts at 20～90 ℃ with phosphoric acid solution.
13. in accordance with the method for claim 12, it is characterized in that the active tungstic acid precipitation contacts at 30-60 ℃ with phosphoric acid solution.
14. in accordance with the method for claim 1, it is characterized in that the described phospho-wolframic acid that makes of step (3) is separated out from solution, the method for employing is evaporation, concentrates.
15. in accordance with the method for claim 1, it is characterized in that the described phospho-wolframic acid that makes of step (3) is separated out from solution, the method for employing is to add the mineral acid precipitation agent in solution, make the phospho-wolframic acid precipitation, the volumetric molar concentration of mineral acid precipitation agent in reaction system is 0.1～6mol/L.
16. in accordance with the method for claim 15, it is characterized in that described mineral acid precipitation agent is hydrochloric acid, sulfuric acid or nitric acid, or the mixture of the arbitrary volume of hydrochloric acid, sulfuric acid and nitric acid ratio.
17. in accordance with the method for claim 15, it is characterized in that the volumetric molar concentration of described mineral acid precipitation agent in reaction system is 0.5～4mol/L.
18. in accordance with the method for claim 15, it is characterized in that the temperature when adding the mineral acid precipitation agent is-20～80 ℃.
19. in accordance with the method for claim 18, it is characterized in that the temperature when adding the mineral acid precipitation agent is a room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101351735A CN100460318C (en) | 2005-12-29 | 2005-12-29 | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101351735A CN100460318C (en) | 2005-12-29 | 2005-12-29 | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1990387A CN1990387A (en) | 2007-07-04 |
| CN100460318C true CN100460318C (en) | 2009-02-11 |
Family
ID=38212969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101351735A Active CN100460318C (en) | 2005-12-29 | 2005-12-29 | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100460318C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100918990B1 (en) * | 2007-10-22 | 2009-09-25 | 주식회사 효성 | Method of preparing phosphotungstic acid |
| CN101975691A (en) * | 2010-08-28 | 2011-02-16 | 绍兴文理学院 | Production method of phosphotungstic acid staining liquid for electron microscope experiment |
| JP6802582B2 (en) | 2016-08-26 | 2020-12-16 | 中南大学 | How to prepare phosphotungstic acid |
| CN106824274B (en) * | 2016-12-23 | 2019-03-19 | 盐城工学院 | A method of the fabricated in situ Keggin-type phosphotungstic acid in Y type molecular sieve |
| CN109988923A (en) * | 2019-03-29 | 2019-07-09 | 厦门钨业股份有限公司 | A kind of tungsten separation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63179008A (en) * | 1987-01-20 | 1988-07-23 | Daido Steel Co Ltd | Production of high purity tungsten powder |
| CN1301592A (en) * | 1999-12-24 | 2001-07-04 | 中国科学院感光化学研究所 | Method for preparing 12-tungstophosphoric acid |
-
2005
- 2005-12-29 CN CNB2005101351735A patent/CN100460318C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63179008A (en) * | 1987-01-20 | 1988-07-23 | Daido Steel Co Ltd | Production of high purity tungsten powder |
| CN1301592A (en) * | 1999-12-24 | 2001-07-04 | 中国科学院感光化学研究所 | Method for preparing 12-tungstophosphoric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1990387A (en) | 2007-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1978327B (en) | Method for preparing high-purity phosphotungsticacid | |
| CN101310857B (en) | Method for preparing high-purity heteropoly acid of Keggin structure | |
| CN100460318C (en) | Method for preparing phosphotungstic acid using ammonium paratungstate as raw material | |
| CN102659181B (en) | Method for preparing phosphotungstic heteropoly acid with Keggin structure | |
| US11214495B2 (en) | Preparation method of phosphotungstic acid | |
| CN106277060B (en) | A kind of preparation method of phosphotungstic acid | |
| Flynn Jr et al. | Tungstovanadate heteropoly complexes. I. Vanadium (V) complexes with the constitution M6O19n-and vanadium: tungsten. leq. 1: 2 | |
| CN106335928A (en) | Method of preparing phosphotungstic acid from sodium tungstate as raw material | |
| CN1126600C (en) | Method for preparing 12-tungstophosphoric acid | |
| CN101704823B (en) | Method for preparing bicyclopentadiene dioxide by catalysis through emulsion method | |
| Tsang | Synthesis of lower-valent molybdenum oxides in aqueous solutions by reducing Na 2 MoO 4 with NaBH 4 | |
| CN106082343A (en) | A kind of purification process of phosphotungstic acid crystal | |
| CN107587195B (en) | Tantalum-based rare earth polyacid and preparation method of nanocrystalline thereof | |
| CN103055860B (en) | Composited crystal solid alkali supporter catalyst and preparation method | |
| CN102744088A (en) | Preparation method of silicotungstic heteropoly acid | |
| CN103361488A (en) | Recycling method of scandium in titanium white waste water | |
| CN1978328A (en) | Method for preparing heteropoly acid containing tungsten from tunsten powder | |
| CN113106271A (en) | Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid | |
| US3446577A (en) | Process for producing heteropoly metal acids | |
| CN107737601B (en) | ɑ-AgVO3Graphene oxide/Ag3PO4Composite material and preparation method and application thereof | |
| US3428415A (en) | Preparation of heteropolytungstic and heteropolymolybdic acids | |
| CN113717222B (en) | Preparation method of high-purity dioctyl phosphate | |
| US3425794A (en) | Method of preparing heteropoly compounds | |
| CN102731314B (en) | Method for preparing quaternary ammonium base from quaternary ammonium salt | |
| CN109651239A (en) | A kind of multidentate ligand terpyridyl diacetic acid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |