CN103613082A - Method for preparing Dawson heteropolyphosphatotungstate - Google Patents
Method for preparing Dawson heteropolyphosphatotungstate Download PDFInfo
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- CN103613082A CN103613082A CN201310572072.9A CN201310572072A CN103613082A CN 103613082 A CN103613082 A CN 103613082A CN 201310572072 A CN201310572072 A CN 201310572072A CN 103613082 A CN103613082 A CN 103613082A
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Abstract
The invention discloses a method for preparing Dawson heteropolyphosphatotungstate. The method comprises the following steps: (1) enabling a tungstate solution to come into contact with an inorganic acid solution, so as to obtain a reactive intermediate; (2) continuously enabling the solution to come into contact with a phosphoric acid solution, so as to obtain a phosphotungstic acid solution; (3) transferring the phosphotungstic acid solution to a high-pressure reactor, and carrying out high-temperature and high-pressure reaction; (4) adding an inorganic salt precipitant to the obtained phosphotungstic acid solution, carrying out salting-out crystallization to obtain phosphotungstate, filtering, purifying and drying, so as to obtain the Dawson heteropolyphosphatotungstate. Compared with the prior art, the method is simple in technological process, short in reaction cycle, high in yield and product purity, and low in cost; meanwhile, strong acid acidification and diethyl ether extraction used in the traditional method are avoided; the safety of the preparation process is greatly improved.
Description
Technical field
The invention belongs to heteropolyacid preparing technical field, be specifically related to a kind of method of preparing high purity Dawson type phospho heteropoly tungstate.
Background technology
Dawson type phospho heteropoly tungstate general formula is:
X
6[Y
2Z
18O
62]·nH
2O
Wherein:
X is Dawson type phosphorus heteropoly tungstic acid gegenion, as H
+, K
+, Na
+, NH
4 +deng;
Y represents heteroatoms or central atom, as P, Si, Ge etc.;
Z represents polyatom or joins atom, as Mo, W, V etc.;
N is crystal water number, is generally 0～30 positive integer.
Dawson type phosphorus tungsten heteropoly compound is one of most typical structure in heteropolyacid, is to take P as heteroatoms, and W is for joining atom, and P and W atomic ratio 2:18, have Dawson space structure.Owing to thering is unique structure and character, Dawson type phosphorus tungsten heteropoly compound is widely used in the focus of the interdisciplinary researchs such as chemistry, materialogy, biology and electronics at present, at numerous areas such as antitumor, clinical analysis, radwaste processing, analytical chemistry, electrochemistry (electrode materials), gas sensor, POM film, dye for fabrics, electrooptics, collosol and gel doping agent, ion-exchanger, food chemistries, has extensive use.
Since the people such as nineteen twenty Wu successfully synthesize for the first time and isolate Dawson type phospho heteropoly tungstate, the research that deepened continuously of Dawson type phosphorus tungsten heteropoly compound, so far existing more than 90 year history, referring to document: Wu, H.J.Biol.Chem.1920,43,189-220.The seminar such as Souchay, Droege, R.Contant, Nadjo has constantly updated the synthetic method of Dawson type phospho heteropoly tungstate therebetween, referring to document: Souchay, and P.IonsMin é raux Condens é s; Masson:Paris, 1969; P106; Droege, M.W.Ph.D.Dissertation, University of Oregon; 1984.Contant, R.Inorg.Synth.1990,27,104 – 111; Mbomekalle, I.M.; Lu, Y.W.; Keita, B.; Nadjo, L.Inorg.Chem.Commun.2004,7,86 – 90.
Traditional phospho-wolframic acid synthetic method is ether acidizing extraction method, is generally with excessive strong phosphoric acid or concentrated hydrochloric acid acidifying tungstate, after a couple of days of refluxing, by extracted with diethyl ether, by heating, ether is volatilized, and finally obtains product.The method is used excessive concentrated acid acidifying link also to exist the problem of wastage of material and equipment corrosion, uses inflammable and explosive ether to make extraction agent simultaneously, exists safety and environment hidden danger.At present, few about the patent report of synthetic Dawson type phospho heteropoly tungstate both at home and abroad, CN1231943A discloses a kind of synthetic method of Dawson type phospho heteropoly tungstate, by refluxing and saltout after a large amount of strong phosphoric acid acidifying tungstate solutions, obtain product, avoid extracted with diethyl ether, but used the problem of excessive strong phosphoric acid acidifying also unresolved.EP1113877A1, WO2007080067A1 are relevant for the method introduction of synthetic Dawson type phospho heteropoly tungstate, the method refluxes and saltouts after adopting a small amount of strong phosphoric acid and a large amount of concentrated hydrochloric acid acidifying, finally by extracted with diethyl ether, obtain product, the solution that the use problem of strong acid acidifying and ether does not still obtain.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, provide a kind of and take tungstate as raw material, realize first the acidifying of lower concentration mineral acid, the acidifying of lower concentration phosphoric acid, hydro-thermal activation, last inorganic salt precipitated crystal, prepares the method for high purity Dawson type phospho heteropoly tungstate.
A method of preparing Dawson type phospho heteropoly tungstate, comprises the following steps:
(1) to adding inorganic acid solution to pH value in tungstate solution, be 6.0～8.0, preferably 6.5～7.5;
(2) continuing to add phosphoric acid solution to pH value to above-mentioned solution is 0.1～2.0, stirs;
(3) above-mentioned solution is gone in autoclave, under High Temperature High Pressure, react;
(4) above-mentioned solution is cooled to normal temperature, adds inorganic salt precipitation agent that phosphorus heteropoly tungstic acid is salted out, filter, purifying, dry, obtain highly purified Dawson type phospho heteropoly tungstate.
Mineral acid described in step (1) is one or more in hydrochloric acid, sulfuric acid or nitric acid.
Tungstate described in step (1) is one or more in sodium wolframate, potassium wolframate, lithium tungstate, ammonium tungstate.
Tungstate solution concentration described in step (1) is 1～10mol/L.
The temperature of step (1) and (2) is 10～100 ℃; Preferably 10～40 ℃.
The reaction process adopting in step (3) is hydrothermal method, and temperature of reaction is 80～200 ℃, preferably 100～140 ℃; Soak time is 4～20 hours, preferably 6～12 hours.
In step (4), described inorganic salt are ammonium salt, basic metal or alkaline-earth metal strong acid salt, or their mixture.
In the building-up process of Dawson type phospho-wolframic acid of the present invention, the acidifying of the first step mineral acid is [WO
4]
2-to heptamer para-tungstic acid root [W
7o
24]
6-the process transforming, second step acidifying is that heptamer para-tungstic acid root is to polymkeric substance [PW
9o
31(OH)
3]
3-the process transforming; Again by [PW
9o
31(OH)
3]
3-hydrothermal conversion is [P
2w
18o
62]
6-; Due to [P
2w
18o
62]
6-be a kind of more stable polymkeric substance, make [PW
9o
31(OH)
3]
3-to [P
2w
18o
62]
6-transform, and hydrothermal condition is to obtain the most effectively piling up for crystal growth in reaction system, thereby has accelerated this process.When we open hydrothermal reaction kettle, can obviously observe bottom has alabastrine crystal accumulation, and this is a kind of nonequilibrium state crystallization process, can make product more stably separate out.
The present invention finds and is verified without strong acid acidifying and also can be reached the object that generates Dawson type phospho heteropoly tungstate by lot of experiments, and found the appropriate pH value of reaction, adding inorganic acid solution to pH value is 6.0～8.0, and adding phosphoric acid solution to pH value is 0.1～2.0; And by the generation of hydro-thermal reaction accelerated reaction product, finally by saltouing, obtain high-purity Dawson type phospho heteropoly tungstate.
Compared with prior art, beneficial effect major embodiment of the present invention is in the following areas:
(1) simple to operate, reaction process shortens greatly;
(2) avoid using extracted with diethyl ether, reduced environmental pollution and potential safety hazard;
(3) conservation avoids using excessive strong acid acidifying simultaneously, has reduced equipment corrosion, greatly reduces cost;
(4), than traditional Dawson type phospho heteropoly tungstate synthetic method, productive rate and purity (the general 70-80% of traditional method productive rate) all improve a lot.
Accompanying drawing explanation
Fourier transform infrared spectroscopy (FT-IR) is the classical way of Analysis and Identification polyacid compounds structure, referring to document Nadjo, and L.Inorg.Chem.Commun.2004,7,86 – 90.
31p-NMR nmr analysis is a kind of classical way of identifying phospho-wolframic acid compound purity, referring to document Christopher R.Graham and Richard G.Finke*.Inorg.Chem.2008,47,36793686.The present invention adopts Fourier transform infrared spectroscopy to identify synthetic Dawson type phospho heteropoly tungstate structure, adopts
31p-NMR nmr analysis is identified synthetic Dawson type phosphorus heteropoly tungstic acid purity salt, adopts Atomic Emission Spectral Analysis (ICP) analyze in Dawson type phospho heteropoly tungstate gegenion, heteroatoms and join atom content.
Fig. 1 is the FT-IR collection of illustrative plates of Dawson type phospho heteropoly tungstate sample in embodiment 1.
Fig. 2 is Dawson type phospho heteropoly tungstate sample in embodiment 1
31p-NMR nuclear magnetic resonance spectrum.
In every 1g sample prepared by the embodiment 1 that table 1 is measured for ICP, the quality of K, P, W, calculates by relative atomic mass, and sample K, P, W atomic ratio approach 6:2:18.
K, P, W element ICP observed value in table 1.1g sample
| Element | Atomic mass (mg) | Atomic ratio |
| K | 49.72 | 1.28 |
| P | 13.10 | 0.42 |
| W | 696.87 | 3.79 |
Embodiment
Example below will be further described method provided by the invention, but the present invention is not therefore subject to any restriction.
In concrete embodiment, sodium wolframate is technical grade, and the mass concentration of concentrated hydrochloric acid is 36%, and the mass concentration of strong phosphoric acid is 85%, and Repone K is technical grade, and experimental water is distilled water.
Take 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 1mol/L, be 7.0; Continue with the phosphoric acid regulator solution of 1.5mol/L to pH be 1.0; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 10 hours at 100 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 23.1 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 94.3%.The FT-IR spectrogram of product is shown in Fig. 1, can find out, product is at 1090cm
-1, 963cm
-1, 918cm
-1, 783cm
-1there is obvious absorption peaks at place, in full accord with the FT-IR collection of illustrative plates of Dawson type phospho-wolframic acid potassium standard;
31p-NMR nuclear magnetic resonance spectrum is shown in Fig. 2, can find out, chemical shift δ is-12.51ppm, with Dawson type phospho-wolframic acid potassium standard
31p-NMR nuclear magnetic resonance map is in full accord.
Embodiment 2
Take 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 25ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 1mol/L, be 6.5; Continue with the phosphoric acid regulator solution of 5mol/L to pH be 1.0; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 10 hours at 120 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 22.6 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 92.2%, the FT-IR collection of illustrative plates of sample phospho-wolframic acid and
31p-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 3
Take 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 1mol/L, be 7.0; Continue with the phosphoric acid regulator solution of 10mol/L to pH be 0.5; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 4 hours at 120 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 21.9 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 89.4%, the FT-IR collection of illustrative plates of sample phospho-wolframic acid and
31p-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 4
Take 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 25ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 3mol/L, be 7.0; Continue with the phosphoric acid regulator solution of 10mol/L to pH be 0.5; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 4 hours at 140 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 23.4 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 95.5%, the FT-IR collection of illustrative plates of sample phospho-wolframic acid and
31p-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 5
Take 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 4mol/L, be 6.8; Continue with the phosphoric acid regulator solution of 4mol/L to pH be 1.5; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 12 hours at 180 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 20.3 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 82.9%, the FT-IR collection of illustrative plates of sample phospho-wolframic acid and
31p-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 6
Take 100 grams of Disodium tungstate (Na2WO4) dihydrates, add 100ml deionized water, be stirred to sodium wolframate and dissolve completely; With the hydrochloric acid conditioning solution pH of 10mol/L, be 6.0; Continue with the phosphoric acid regulator solution of 4mol/L to pH be 1.0; Stir and after 1 hour, proceed in 100ml band teflon-lined autoclave, heat 8 hours at 160 ℃; After naturally cooling, solution is proceeded in beaker, add Repone K to closely saturated, stir 1 hour; Purifying, filters, and is dried to constant weight, obtains 75.3 grams of light yellow products, by K
6[P
2w
18o
62] 14H
2o meter, productive rate is about 92.7%, the FT-IR collection of illustrative plates of sample phospho-wolframic acid and
31p-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Claims (7)
1. a method of preparing Dawson type phospho heteropoly tungstate, is characterized in that, comprises the following steps:
(1) to adding inorganic acid solution to pH value in tungstate solution, be 6.0～8.0;
(2) continuing to add phosphoric acid solution to pH value to above-mentioned solution is 0.1～2.0, stirs;
(3) above-mentioned solution is gone in autoclave, under High Temperature High Pressure, react;
(4) above-mentioned solution is cooled to normal temperature, adds inorganic salt precipitation agent that phosphorus heteropoly tungstic acid is salted out, filter, purifying, dry, obtain highly purified Dawson type phospho heteropoly tungstate.
2. the method for preparing Dawson type phospho heteropoly tungstate according to claim 1, is characterized in that, the mineral acid described in step (1) is one or more in hydrochloric acid, sulfuric acid or nitric acid.
3. the method for preparing Dawson type phospho heteropoly tungstate according to claim 1, is characterized in that, the tungstate described in step (1) is one or more in sodium wolframate, potassium wolframate, lithium tungstate, ammonium tungstate.
4. according to the method for preparing Dawson type phospho heteropoly tungstate described in claim 1 or 3, it is characterized in that, the tungstate solution concentration described in step (1) is 1～10mol/L.
5. the method for preparing Dawson type phospho heteropoly tungstate according to claim 1, is characterized in that, the temperature of step (1) and (2) is 10～100 ℃.
6. the method for preparing Dawson type phospho heteropoly tungstate according to claim 1, is characterized in that, the reaction process adopting in step (3) is hydrothermal method, and temperature of reaction is 80～200 ℃, and soak time is 4～20 hours.
7. the method for preparing Dawson type phospho heteropoly tungstate according to claim 1, is characterized in that, in step (4), described inorganic salt are ammonium salt, basic metal or alkaline-earth metal strong acid salt, or their mixture.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353476A (en) * | 2014-10-23 | 2015-02-18 | 吉林化工学院 | Preparation method of solid-supported phosphotungstic heteropoly acid |
| CN105129759A (en) * | 2015-07-21 | 2015-12-09 | 渤海大学 | Preparation method of silver phosphotungstate rhombic dodecahedron microcrystal |
| CN105645372A (en) * | 2016-04-01 | 2016-06-08 | 云南铁坦新材料科技股份有限公司 | Preparation method of negative thermal expansion material zirconium phosphotungstate |
| CN106082343A (en) * | 2016-08-26 | 2016-11-09 | 中南大学 | A kind of purification process of phosphotungstic acid crystal |
| CN106698374A (en) * | 2016-11-21 | 2017-05-24 | 扬州大学 | Rhombic hollow dodecahedron potassium phosphate noncrystal and synthesis method thereof |
| CN107910187A (en) * | 2017-08-31 | 2018-04-13 | 哈尔滨理工大学 | A kind of preparation and application of more acidic group crystalline state electrode material for super capacitor |
| CN110937995A (en) * | 2019-12-06 | 2020-03-31 | 西安石油大学 | Dawson type phosphotungstic heteropoly acid salt constructed by mixed valence tetracarboxylic acid binuclear ruthenium and synthetic method thereof |
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Cited By (9)
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|---|---|---|---|---|
| CN104353476A (en) * | 2014-10-23 | 2015-02-18 | 吉林化工学院 | Preparation method of solid-supported phosphotungstic heteropoly acid |
| CN105129759A (en) * | 2015-07-21 | 2015-12-09 | 渤海大学 | Preparation method of silver phosphotungstate rhombic dodecahedron microcrystal |
| CN105129759B (en) * | 2015-07-21 | 2017-07-11 | 渤海大学 | A kind of preparation method of silver phosphotungstate granatohedron crystallite |
| CN105645372A (en) * | 2016-04-01 | 2016-06-08 | 云南铁坦新材料科技股份有限公司 | Preparation method of negative thermal expansion material zirconium phosphotungstate |
| CN106082343A (en) * | 2016-08-26 | 2016-11-09 | 中南大学 | A kind of purification process of phosphotungstic acid crystal |
| CN106698374A (en) * | 2016-11-21 | 2017-05-24 | 扬州大学 | Rhombic hollow dodecahedron potassium phosphate noncrystal and synthesis method thereof |
| CN107910187A (en) * | 2017-08-31 | 2018-04-13 | 哈尔滨理工大学 | A kind of preparation and application of more acidic group crystalline state electrode material for super capacitor |
| CN110937995A (en) * | 2019-12-06 | 2020-03-31 | 西安石油大学 | Dawson type phosphotungstic heteropoly acid salt constructed by mixed valence tetracarboxylic acid binuclear ruthenium and synthetic method thereof |
| CN110937995B (en) * | 2019-12-06 | 2022-01-04 | 西安石油大学 | Dawson type phosphotungstic heteropoly acid salt constructed by mixed valence tetracarboxylic acid binuclear ruthenium and synthetic method thereof |
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