CN103613082B - A kind of method preparing Dawson heteropolyphosphatotungstate - Google Patents
A kind of method preparing Dawson heteropolyphosphatotungstate Download PDFInfo
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Abstract
The invention discloses a kind of method preparing Dawson heteropolyphosphatotungstate, comprise the following steps: (1) makes tungstate solution contact with inorganic acid solution, obtains reactive intermediate；(2) continue to contact with phosphoric acid solution by above-mentioned solution, obtain Salkowski's solution；(3) above-mentioned solution is transferred in autoclave, high-temperature high-voltage reaction；(4) adding inorganic salt precipitant in gained Salkowski's solution, salting-out crystallization obtains phosphotungstate.Filter, purification, dry, obtain Dawson heteropolyphosphatotungstate.Compared with prior art, present invention process flow process is simple, and reaction time is short；Productivity and purity are all significantly high, and cost is low；Avoiding strong acid acidifying and ether extraction that traditional method uses, the safety of preparation process is greatly improved simultaneously.
Description
Technical field
The invention belongs to heteropoly acid preparing technical field, be specifically related to a kind of method preparing high-purity Dawson heteropolyphosphatotungstate.
Background technology
Dawson heteropolyphosphatotungstate formula is:
X6[Y2Z18O62]·nH2O
Wherein:
X is Dawson type phosphorus heteropoly tungstic acid gegenion, such as H+、K+、Na+、NH4 +Deng；
Y represents hetero atom or central atom, such as P, Si, Ge etc.；
Z represents polyatom or joins atom, such as Mo, W, V etc.；
N is water of crystallization number, is generally the positive integer of 0～30.
Dawson type phosphorus tungsten heteropoly compound is one of most typical structure in heteropoly acid, is with P for hetero atom, W for joining atom, P and W atomic ratio 2:18, there is Dawson space structure.Owing to having structure and the character of uniqueness, 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, has extensive use at numerous areas such as antitumor, clinical analysis, Radwastes treatment, analytical chemistry, electrochemistry (electrode material), gas sensor, POM film, dye for fabrics, electrooptics, collosol and gel doping agent, ion-exchanger, Food Chemistries.
Since nineteen twenty Wu et al. first time successfully synthesizes and isolates Dawson heteropolyphosphatotungstate, Dawson type phosphorus tungsten heteropoly compound is deepened continuously research, has more than 90 year history so far, referring to document: Wu, H.J.Biol.Chem.1920,43, and 189-220.The seminar such as Souchay, Droege, R.Contant, Nadjo has constantly updated the synthetic method of Dawson heteropolyphosphatotungstate therebetween, referring to document: Souchay, and P.IonsMin é rauxCondens é s;Masson:Paris,1969;p106；Droege, M.W.Ph.D.Dissertation, UniversityofOregon；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 phosphotungstic acid synthetic method is ether acidizing extraction method, is usually with excessive strong phosphoric acid or concentrated hydrochloric acid acidifying tungstates, extracts with ether, make ether volatilize by heating, finally obtain product after backflow a couple of days.The method uses excessive concentrated acid acidifying link to there is also the problem of wastage of material and equipment corrosion, uses inflammable and explosive ether to make extractant simultaneously, there is safety and environment hidden danger.At present, patent report about synthesis Dawson heteropolyphosphatotungstate is few both at home and abroad, CN1231943A discloses the synthetic method of a kind of Dawson heteropolyphosphatotungstate, saltout by refluxing after a large amount of strong phosphoric acid acidifying tungstate solutions, obtain product, avoid ether to extract, but use the problem of excessive strong phosphoric acid acidifying also unresolved.EP1113877A1, WO2007080067A1 are related to the method introduction of synthesis Dawson heteropolyphosphatotungstate, the method refluxes after adopting a small amount of strong phosphoric acid and a large amount of concentrated hydrochloric acid acidifying and saltouts, finally product being obtained by extraction with ether, the use problem of strong acid acidifying and ether is still without the solution obtained.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of with tungstates for raw material, realize low concentration first mineral acid acidified, low concentration phosphoric acid, hydro-thermal activates, last inorganic salt precipitated crystal, the method for preparation high-purity Dawson heteropolyphosphatotungstate.
A kind of method preparing Dawson heteropolyphosphatotungstate, comprises the following steps:
(1) adding inorganic acid solution to pH value in tungstate solution is 6.0～8.0, it is preferable that 6.5～7.5；
(2) continue up state solution add phosphoric acid solution to pH value be 0.1～2.0, stirring；
(3) above-mentioned solution is gone in autoclave, react under High Temperature High Pressure;
(4) above-mentioned solution is cooled to room temperature, adds inorganic salt precipitant and make phosphorus heteropoly tungstic acid salt out, filter, purification, dry, obtain highly purified Dawson heteropolyphosphatotungstate.
Mineral acid described in step (1) is one or more in hydrochloric acid, sulphuric acid or nitric acid.
Tungstates described in step (1) is one or more in sodium tungstate, potassium tungstate, tungstate lithium, ammonium tungstate.
Tungstate solution concentration described in step (1) is 1～10mol/L.
The temperature of step (1) and (2) is 10～100 DEG C；Preferably 10～40 DEG C.
The course of reaction adopted in step (3) is hydro-thermal method, and reaction temperature is 80～200 DEG C, it is preferable that 100～140 DEG C；Soak time is 4～20 hours, it is preferable that 6～12 hours.
In step (4), described inorganic salt is ammonium salt, alkali metal or alkaline-earth metal strong acid salt, or their mixture.
In the building-up process of Dawson type phosphotungstic acid of the present invention, the first step is mineral acid acidified is [WO4]2-To heptamer para-tungstic acid root [W7O24]6-The process converted, second step acidifying is then heptamer para-tungstic acid root to polymer [PW9O31(OH)3]3-The process converted；Again by [PW9O31(OH)3]3-Hydrothermal conversion is [P2W18O62]6-；Due to [P2W18O62]6-It is a kind of more stable polymer so that [PW9O31(OH)3]3-To [P2W18O62]6-Convert, and hydrothermal condition is in order to crystal growth obtains maximally effective accumulation in reaction system, thus accelerating this process.When we open hydrothermal reaction kettle, substantially observing that alabastrine crystal accumulation is arranged at bottom, this is a kind of nonequilibrium state crystallization process, it is possible to make product more stably to precipitate out.
Present invention discover that and pass through lot of experiments checking and also can reach to generate the purpose of Dawson heteropolyphosphatotungstate without strong acid acidifying, and have found the optimum pH 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 acceleration product, obtain high-purity Dawson heteropolyphosphatotungstate finally by saltouing.
Compared with prior art, the beneficial effects are mainly as follows following aspect:
(1) simple to operate, reaction process is greatly shortened；
(2) avoid using ether to extract, decrease environmental pollution and potential safety hazard；
(3) conservation, avoids using excessive strong acid acidifying simultaneously, decreases equipment corrosion, greatly reduce cost；
(4) compared to traditional Dawson heteropolyphosphatotungstate synthetic method, productivity and purity (the general 70-80% of traditional method productivity) all improve a lot.
Accompanying drawing explanation
Fourier transform infrared spectroscopy (FT-IR) is the classical way of Analysis and Identification many acid compounds structure, referring to document Nadjo, L.Inorg.Chem.Commun.2004,7, and 86 90.31P-NMR nmr analysis is a kind of classical way identifying phosphotungstic acid compound purity, referring to document ChristopherR.GrahamandRichardG.Finke*.Inorg.Chem.2008,47,36793686.The present invention adopts Fourier transform infrared spectroscopy to identify synthesis Dawson heteropolyphosphatotungstate structure, adopts31P-NMR nmr analysis identifies synthesis Dawson heteropolyphosphatotungstate purity, adopts Atomic Emission Spectral Analysis (ICP) analyze gegenion in Dawson heteropolyphosphatotungstate, hetero atom and join atom content.
Fig. 1 is the FT-IR collection of illustrative plates of Dawson heteropolyphosphatotungstate sample in embodiment 1.
Fig. 2 is Dawson heteropolyphosphatotungstate sample in embodiment 131P-NMR nuclear magnetic resoance spectrum.
The quality of K, P, W in every 1g sample that table 1 is prepared for the ICP embodiment 1 measured, calculates by relative atomic mass, and sample K, P, W atomic ratio is close to 6:2:18.
K, P, W element ICP measured 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 |
Detailed description of the invention
Method provided by the invention will be further described by example below, but the present invention is not therefore subject to any restriction.
Being embodied as in example sodium tungstate is technical grade, and the mass concentration of concentrated hydrochloric acid is 36%, and the mass concentration of strong phosphoric acid is 85%, and potassium chloride is technical grade, and experimental water is distilled water.
Embodiment 1
Weighing 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, stirring to sodium tungstate is completely dissolved；It is 7.0 with the hydrochloric acid conditioning solution pH of 1mol/L；The phosphorus acid-conditioning solution of continuation 1.5mol/L is 1.0 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 10 hours at 100 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 23.1 grams of light yellow product, by K6[P2W18O62]·14H2O counts, and productivity is about 94.3%.The FT-IR spectrogram of product is shown in Fig. 1, it can be seen that product is at 1090cm-1、963cm-1、918cm-1、783cm-1There is obvious absorption peaks at place, completely the same with the FT-IR collection of illustrative plates of Dawson type phosphotungstic acid potassium standard sample；31P-NMR nuclear magnetic resoance spectrum is shown in Fig. 2, it can be seen that chemical shift δ is-12.51ppm, with Dawson type phosphotungstic acid potassium standard sample31P-NMR nuclear magnetic resonance map is completely the same.
Embodiment 2
Weighing 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 25ml deionized water, stirring to sodium tungstate is completely dissolved；It is 6.5 with the hydrochloric acid conditioning solution pH of 1mol/L；The phosphorus acid-conditioning solution of continuation 5mol/L is 1.0 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 10 hours at 120 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 22.6 grams of light yellow product, by K6[P2W18O62]·14H2O count, productivity is about 92.2%, the FT-IR collection of illustrative plates of sample phosphotungstic acid and31P-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 3
Weighing 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, stirring to sodium tungstate is completely dissolved；It is 7.0 with the hydrochloric acid conditioning solution pH of 1mol/L；The phosphorus acid-conditioning solution of continuation 10mol/L is 0.5 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 4 hours at 120 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 21.9 grams of light yellow product, by K6[P2W18O62]·14H2O count, productivity is about 89.4%, the FT-IR collection of illustrative plates of sample phosphotungstic acid and31P-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 4
Weighing 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 25ml deionized water, stirring to sodium tungstate is completely dissolved；It is 7.0 with the hydrochloric acid conditioning solution pH of 3mol/L；The phosphorus acid-conditioning solution of continuation 10mol/L is 0.5 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 4 hours at 140 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 23.4 grams of light yellow product, by K6[P2W18O62]·14H2O count, productivity is about 95.5%, the FT-IR collection of illustrative plates of sample phosphotungstic acid and31P-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 5
Weighing 30 grams of Disodium tungstate (Na2WO4) dihydrates, add 50ml deionized water, stirring to sodium tungstate is completely dissolved；It is 6.8 with the hydrochloric acid conditioning solution pH of 4mol/L；The phosphorus acid-conditioning solution of continuation 4mol/L is 1.5 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 12 hours at 180 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 20.3 grams of light yellow product, by K6[P2W18O62]·14H2O count, productivity is about 82.9%, the FT-IR collection of illustrative plates of sample phosphotungstic acid and31P-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Embodiment 6
Weighing 100 grams of Disodium tungstate (Na2WO4) dihydrates, add 100ml deionized water, stirring to sodium tungstate is completely dissolved；It is 6.0 with the hydrochloric acid conditioning solution pH of 10mol/L；The phosphorus acid-conditioning solution of continuation 4mol/L is 1.0 to pH；Proceed in 100ml band teflon-lined autoclave after stirring 1 hour, heat 8 hours at 160 DEG C；After natural cooling, solution is proceeded in beaker, add potassium chloride to closely saturated, stir 1 hour；Purification, filters, is dried to constant weight, obtains 75.3 grams of light yellow product, by K6[P2W18O62]·14H2O count, productivity is about 92.7%, the FT-IR collection of illustrative plates of sample phosphotungstic acid and31P-NMR nuclear magnetic resonance map is similar to Fig. 1, Fig. 2 respectively.
Claims (6)
1. the method preparing Dawson heteropolyphosphatotungstate, it is characterised in that comprise the following steps:
(1) adding inorganic acid solution to pH value in tungstate solution is 6.0～8.0；
(2) continuing up and stating solution addition phosphoric acid solution to pH value is 0.1～2.0, stirring；
(3) going in autoclave by above-mentioned solution, react under High Temperature High Pressure, reaction temperature is 80～200 DEG C, and soak time is 4～20 hours；
(4) above-mentioned solution is cooled to room temperature, adds inorganic salt precipitant and make phosphorus heteropoly tungstic acid salt out, filter, purification, dry, obtain highly purified Dawson heteropolyphosphatotungstate.
2. the method for preparation Dawson heteropolyphosphatotungstate according to claim 1, it is characterised in that step (1) described in mineral acid be one or more in hydrochloric acid, sulphuric acid or nitric acid.
3. the method for preparation Dawson heteropolyphosphatotungstate according to claim 1, it is characterised in that step (1) described in tungstates be one or more in sodium tungstate, potassium tungstate, tungstate lithium, ammonium tungstate.
4. the method for the preparation Dawson heteropolyphosphatotungstate according to claim 1 or 3, it is characterised in that step (1) described in tungstate solution concentration be 1～10mol/L.
5. the method for preparation Dawson heteropolyphosphatotungstate according to claim 1, it is characterised in that the temperature of step (1) and (2) is 10～100 DEG C.
6. the method for preparation Dawson heteropolyphosphatotungstate according to claim 1, it is characterised in that step (4) in, described inorganic salt is ammonium salt, alkali metal or alkaline-earth metal strong acid salt, or their mixture.
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| CN104353476B (en) * | 2014-10-23 | 2016-08-17 | 吉林化工学院 | The preparation method of solid-carrying type phosphorus heteropoly tungstic acid |
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| CN106082343B (en) * | 2016-08-26 | 2017-07-14 | 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 |
| CN107910187B (en) * | 2017-08-31 | 2020-05-12 | 哈尔滨理工大学 | Preparation and application of polyacid-based crystalline supercapacitor electrode material |
| 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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