CN106745267A - Wells Dawson type phosphotungstic acids and preparation method thereof - Google Patents
Wells Dawson type phosphotungstic acids and preparation method thereof Download PDFInfo
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- CN106745267A CN106745267A CN201611018470.6A CN201611018470A CN106745267A CN 106745267 A CN106745267 A CN 106745267A CN 201611018470 A CN201611018470 A CN 201611018470A CN 106745267 A CN106745267 A CN 106745267A
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- 239000002253 acid Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 150000007513 acids Chemical class 0.000 title claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 83
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 51
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012259 ether extract Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of Wells Dawson type phosphotungstic acids and preparation method thereof, belong to phosphotungstic acid preparation field.The preparation method of the Wells Dawson type phosphotungstic acids is comprised the following steps：Tungsten trioxide powder is added in 60 80 DEG C of phosphoric acid, and reaction obtains Salkowski's solution for 12 24 hours at 120 180 DEG C, wherein phosphoric acid and the mol ratio of tungstic acid is 12 18:1；Ether extract and separate is used after Salkowski's solution is acidified.The preparation method of the Wells Dawson type phosphotungstic acids uses tungstic acid to replace sodium tungstate as raw material, avoid to Na ions are introduced in product, improve the yield and purity of phosphotungstic acid finished product, and the preparation method process is simple, it is easy to operate, it is adapted to industrialization use of large-scale production.The invention also discloses the Wells Dawson type phosphotungstic acids prepared using above-mentioned preparation method.
Description
Technical field
The present invention relates to phosphotungstic acid preparation field, and more particularly to a kind of Wells-Dawson types phosphotungstic acid and its preparation side
Method.
Background technology
Heteropoly acid (Polyoxometalates) is hetero atom (such as P, Si, Co) oxyacid and polyatom (such as Mo, W, V
Deng) by certain structure condensation, the oxygen-containing polyacid of a class of dehydration composition, it had both had highly acid to oxyacid, and with oxidation also
Originality, is widely used in catalyst field.Phosphotungstic acid is a kind of conventional heteropoly acid, and it has stronger acid, excellent
Electric conductivity and strong oxidation performance, be widely used in photocatalytic degradation organic wastewater field.Common phosphotungstic acid tool
There are two kinds of structures：Keggin-type ([XM12O40]n-) and Wells-Dawson types ([X2M18O62]n-), wherein, Keggin-type phosphorus tungsten
Acid is widely used, and related research paper and patent is also more, and the research of Wells-Dawson type phosphotungstic acids is relatively fewer, but
Wells-Dawson types phosphotungstic acid has more horn of plenty compared to Keggin-type phosphotungstic acidIt is sour and more preferable thermally-stabilised
Property, it is for someThe catalytic reaction of acid also has more preferable catalytic performance.
R.G.Finke(Inorg.Chem.26(1987)3886-3896)、C.R.Graham(Inorg.Chem.47
(2008) 3679-3686), C.H.M.Hu (J.Catal.143 (1993) 437-448) etc. reports on Wells- per capita
The preparation method of Dawson type phosphotungstic acids, it is using sodium tungstate as raw material, the Wells-Dawson type phosphorus tungsten for preparing
The content of the impurity such as the sodium phosphotungstate or sodium ion that are remained in acid is higher, reduces the purity of final products.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Wells-Dawson types phosphotungstic acid, the method can be avoided
To Na ions are introduced in the phosphotungstic acid for preparing, the purity of finished product, and the method high income, process is simple, operation are improve
It is convenient.
Another object of the present invention is to provide the Wells-Dawson type phosphorus tungsten that a kind of above-mentioned preparation method is prepared
Acid, it has purity high, the few advantage of impurity.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of preparation method of Wells-Dawson types phosphotungstic acid, comprises the following steps：
Tungsten trioxide powder is added in 60-80 DEG C of phosphoric acid and stirred, and 12-24 is reacted at 120-180 DEG C
Hour obtains Salkowski's solution, and phosphoric acid is 12-18 with the mol ratio of tungstic acid:1；
Ether extract and separate is used after Salkowski's solution is acidified.
Further, in present pre-ferred embodiments, the granularity of tungsten trioxide powder is 30-60 μm.
Further, in present pre-ferred embodiments, tungsten trioxide powder was dividedly in some parts phosphoric acid in 6-10 hours
In.
Further, in present pre-ferred embodiments, tungsten trioxide powder is divided into 9-12 parts and is dividedly in some parts in phosphoric acid.
Further, in present pre-ferred embodiments, tungsten trioxide powder is added to phosphoric acid after being heated to 60-80 DEG C
In.
Further, in present pre-ferred embodiments, tungstic acid is anti-at 160-170 DEG C after being stirred with phosphoric acid
Answer 12-16 hours and obtain Salkowski's solution.
Further, in present pre-ferred embodiments, tungsten trioxide powder uses water-bath or microwave after mixing with phosphoric acid
Reacted at being heated to 120-180 DEG C.
Further, in present pre-ferred embodiments, the method for acidifying is：Salkowski's solution is mixed with inorganic acid and is put
Put 3-5 hours.
Further, in present pre-ferred embodiments, the method for ether extract and separate is：Phosphotungstic acid after acidifying is molten
Liquid is extracted 5-8 times using ether, and the subnatant of collection is dried 6-12 hours at 100-120 DEG C.
Present invention also offers a kind of Wells-Dawson type phosphotungstic acids prepared using above-mentioned preparation method.
The beneficial effect of the Wells-Dawson type phosphotungstic acids of the embodiment of the present invention and preparation method thereof is：The present invention is provided
Method be that tungsten trioxide powder is added in 60-80 DEG C of phosphoric acid, and reacted at 120-180 DEG C and obtain for 12-24 hours
Salkowski's solution, phosphotungstic acid is obtained after then Salkowski's solution is acidified using ether extract and separate, and the method uses three oxidations
Tungsten replaces sodium tungstate as raw material, it is to avoid to Na ions are introduced in product, improve the yield and purity of phosphotungstic acid finished product, and
The preparation method process is simple, it is easy to operate, it is adapted to industrialization use of large-scale production.Present invention also offers a kind of above-mentioned system
The Wells-Dawson type phosphotungstic acids that Preparation Method is prepared, it has purity high, the few advantage of impurity.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the XRD of the Wells-Dawson type phosphotungstic acids that the embodiment of the present invention 1 is prepared；
Fig. 2 is the infrared spectrogram of the Wells-Dawson type phosphotungstic acids that the embodiment of the present invention 1 is prepared；
Fig. 3 is the ultraviolet spectrogram of the Wells-Dawson type phosphotungstic acids that the embodiment of the present invention 1 is prepared.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional product that can be obtained by commercially available purchase
Product.
The preparation method to the Wells-Dawson type phosphotungstic acids of the embodiment of the present invention is specifically described below.
The preparation method of the Wells-Dawson type phosphotungstic acids that the present embodiment is provided, comprises the following steps：
Tungsten trioxide powder is divided into 9-12 parts, and is mixed in being dividedly in some parts 60-80 DEG C of phosphoric acid in 6-10 hours
Uniformly, subsequent water-bath or heating using microwave obtains Salkowski's solution, phosphoric acid and three oxidations for 12-24 hours to reaction at 120-180 DEG C
The mol ratio of tungsten is 12-18:1；Preferably, the granularity of tungsten trioxide powder is 30-60 μm, and tungsten trioxide powder is heated to
It is added in phosphoric acid after 60-80 DEG C, tungsten trioxide powder reacts 12-16 hours after being well mixed with phosphoric acid at 160-170 DEG C
Obtain Salkowski's solution.
Salkowski's solution is mixed into placement with inorganic acid to be acidified within 3-5 hours, is then extracted 5-8 times using ether, will collected
Subnatant dried at 100-120 DEG C 6-12 hours and obtain phosphotungstic acid.Wherein, inorganic acid include hydrochloric acid, sulfuric acid at least
It is a kind of.
The preparation method of the Wells-Dawson type phosphotungstic acids that the present invention is provided replaces sodium tungstate conduct using tungstic acid
Raw material, can effectively avoid that Na ions are incorporated into reaction the purity and yield for reducing finished product phosphotungstic acid.The method is first
The reaction critical-temperature that phosphoric acid is heated to 60-80 DEG C is kept into activity, and be would be heated to 60-80 DEG C of tungstic acid and be dissolved in heating
In phosphoric acid afterwards；Specifically, being dividedly in some parts 60-80 DEG C by what tungstic acid was divided into after 9-12 parts in 6-10 hours interval
It is well mixed in phosphoric acid, tungstic acid molecule is well mixed with phosphoric acid molecules and keep dispersity, then at 120-180 DEG C
Lower reaction obtains Salkowski's solution in 12-24 hours, and tungstic acid molecule is formed with phosphoric acid molecules dehydration, condensation during the course of the reaction
P：W=2:18 Wells-Dawson type phosphotungstic acids；Phosphoric acid is 12-18 with the mol ratio of wolframic acid:When 1, excessive phosphoric acid can
Guarantee is sufficiently reacted with tungstic acid；Tungsten trioxide powder reacts 12-16 hours energy after mixing with phosphoric acid at 160-170 DEG C
Enough reduce the reaction time, improve reaction efficiency；Can make heated tungstic acid molecule and phosphoric acid molecules using heating using microwave
High frequency motion is produced, heat is produced inside tungstic acid molecule and phosphoric acid molecules and is made to be heated temperature of charge rising, heating
Speed they heat quickly and evenly so that tungstic acid molecule and phosphoric acid molecules fully react condensation generation Wells-Dawson type phosphorus
Wolframic acid molecule, is extracted after finally Salkowski's solution is acidified using ether, is dried at 100-120 DEG C after separating and collecting subnatant
6-12 hours, the structure of phosphotungstic acid can be avoided damage to, obtain the phosphotungstic acid solid of Wells-Dawson type structures.
Present invention also offers a kind of Wells-Dawson type phosphotungstic acids prepared using above-mentioned preparation method, its tool
There is purity high, impurity is few, the strong advantage of catalytic performance.
In the medicament that the embodiment of the present invention is used：Tungstic acid (WO3), mass fraction is 99.995%；Phosphoric acid (H3PO4),
Mass fraction is 85%；Hydrochloric acid (HCl), mass fraction is 38%；Sulfuric acid (H2SO4)；Ether (C4H10O), chromatographically pure；Above-mentioned medicine
Agent is bought in sigma-Aldrich companies.
Embodiment 1
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 40mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 60 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 10 equal portions, are dividedly in some parts to the four-hole boiling flask that well mixed to obtain reaction molten in 6 hours
, then be put into for four-hole boiling flask at being heated to 120 DEG C in Hydrothermal Synthesiss kettle and react 12 hours by liquid, is cooled to room temperature and obtains phosphotungstic acid
Solution, is acidified for 3 hours to adding the hydrochloric acid of 10mL to place in Salkowski's solution, then pours into the Salkowski's solution of acidifying
Separatory funnel, the ether for adding 50mL to separatory funnel carries out 5 extracting operations, collects subnatant after extraction obtain phosphorus every time
Wolframic acid ether mixtures, dry 6 hours remaining solid after finally reclaiming ether using revolving equipment at 100 DEG C, obtain
The light yellow Wells-Dawson types phosphotungstic acid of 11.5g, with H6P2W18O62·24H2O is calculated, and yield is 86.8%.
Embodiment 2
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 60mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 80 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 10 equal portions after being heated to 80 DEG C, mixing was dividedly in some parts to the four-hole boiling flask in 8 hours equal
Even to obtain reaction solution, heating using microwave was cooled to room to reaction at 160 DEG C 18 hours during four-hole boiling flask then is put into synthesis reactor
Temperature obtains Salkowski's solution, is acidified within 5 hours to adding the hydrochloric acid of 20mL to place in Salkowski's solution, the phosphorus that then will be acidified
Tungstic acid pours into separatory funnel, and the ether for adding 80mL to separatory funnel carries out 8 extracting operations, every time by lower floor after extraction
Liquid is collected and obtains phosphotungstic acid ether mixtures, and remaining solid is done at 110 DEG C after finally reclaiming ether using revolving equipment
Dry 12 hours, the light yellow Wells-Dawson types phosphotungstic acid of 12.6g is obtained, with H6P2W18O62·24H2O is calculated, and yield is
94.7%.
Embodiment 3
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 50mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 60 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 11 equal portions, and well mixed reaction was dividedly in some parts to the four-hole boiling flask in 11 hours
, then be put into for four-hole boiling flask at being heated to 180 DEG C in Hydrothermal Synthesiss kettle and react 12 hours by solution, is cooled to room temperature and obtains phosphorus tungsten
Acid solution, is acidified for 3 hours to adding the hydrochloric acid of 15mL to place in Salkowski's solution, then falls the Salkowski's solution of acidifying
Enter separatory funnel, the ether for adding 60mL to separatory funnel carries out 8 extracting operations, subnatant is collected after extraction obtain every time
Phosphotungstic acid ether mixtures, dry 6 hours remaining solid after finally reclaiming ether using revolving equipment at 120 DEG C, obtain
To the buff Wells-Dawson type phosphotungstic acids of 11.8g, with H6P2W18O62·24H2O is calculated, and yield is 88.7%.
Embodiment 4
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 45mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 70 DEG C are heated with stirring to；Will
The tungsten trioxide powder that 11.6g is heated to 70 DEG C is divided into 10 equal portions, and is dividedly in some parts in 10 hours to the four-hole boiling flask mixed
Conjunction uniformly obtains reaction solution, and heating using microwave was cooled down to reaction at 170 DEG C 14 hours during four-hole boiling flask then is put into synthesis reactor
Salkowski's solution is obtained to room temperature, is acidified within 3 hours to adding the hydrochloric acid of 25mL to place in Salkowski's solution, then will acidifying
Salkowski's solution pour into separatory funnel, to separatory funnel add 60mL ether carry out 6 extracting operations, every time extraction after will
Subnatant is collected and obtains phosphotungstic acid ether mixtures, is finally reclaimed remaining solid after ether at 120 DEG C using revolving equipment
Lower drying 6 hours, obtains the buff Wells-Dawson type phosphotungstic acids of 12.1g, with H6P2W18O62·24H2O is calculated, yield
It is 91.1%.
Embodiment 5
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 44mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 65 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 9 equal portions, are dividedly in some parts to the four-hole boiling flask that well mixed to obtain reaction molten in 6 hours
, then be put into for four-hole boiling flask at being heated to 165 DEG C in Hydrothermal Synthesiss kettle and react 12 hours by liquid, is cooled to room temperature and obtains phosphotungstic acid
Solution, is acidified for 3 hours to adding the hydrochloric acid of 30mL to place in Salkowski's solution, then pours into the Salkowski's solution of acidifying
Separatory funnel, the ether for adding 65mL to separatory funnel carries out 6 extracting operations, collects subnatant after extraction obtain phosphorus every time
Wolframic acid ether mixtures, dry 6.5 hours remaining solid after finally reclaiming ether using revolving equipment at 105 DEG C, obtain
To the light yellow Wells-Dawson types phosphotungstic acid of 12.0g, with H6P2W18O62·24H2O is calculated, and yield is 90.4%.
Embodiment 6
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 48mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 75 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 10 equal portions, are dividedly in some parts to the four-hole boiling flask that well mixed to obtain reaction molten in 7 hours
, then be put into for four-hole boiling flask at being heated to 175 DEG C in Hydrothermal Synthesiss kettle and react 10 hours by liquid, is cooled to room temperature and obtains phosphotungstic acid
Solution, is acidified for 3 hours to adding the hydrochloric acid of 35mL to place in Salkowski's solution, then pours into the Salkowski's solution of acidifying
Separatory funnel, the ether for adding 60mL to separatory funnel carries out 7 extracting operations, collects subnatant after extraction obtain phosphorus every time
Wolframic acid ether mixtures, dry 12 hours remaining solid after finally reclaiming ether using revolving equipment at 110 DEG C, obtain
The light yellow Wells-Dawson types phosphotungstic acid of 11.7g, with H6P2W18O62·24H2O is calculated, and yield is 88.0%.
Embodiment 7
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 54mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 68 DEG C are heated with stirring to；Will
11.6g tungsten trioxide powders are divided into 12 equal portions, and well mixed reaction was dividedly in some parts to the four-hole boiling flask in 12 hours
, then be put into for four-hole boiling flask at being heated to 170 DEG C in Hydrothermal Synthesiss kettle and react 10 hours by solution, is cooled to room temperature and obtains phosphorus tungsten
Acid solution, is acidified for 3 hours to adding the sulfuric acid of 30mL to place in Salkowski's solution, then falls the Salkowski's solution of acidifying
Enter separatory funnel, the ether for adding 60mL to separatory funnel carries out 6 extracting operations, subnatant is collected after extraction obtain every time
Phosphotungstic acid ether mixtures, dry 6 hours remaining solid after finally reclaiming ether using revolving equipment at 120 DEG C, obtain
To the buff Wells-Dawson type phosphotungstic acids of 11.9g, with H6P2W18O62·24H2O is calculated, and yield is 89.5%.
Embodiment 8
A kind of preparation method of Wells-Dawson types phosphotungstic acid is present embodiments provided, is comprised the following steps：
The phosphoric acid of 58mL is added in the 100mL four-hole boiling flasks with cooling and reflux device, 70 DEG C are heated with stirring to；Will
The tungsten trioxide powder that 11.6g is heated to 70 DEG C is divided into 9 equal portions, and mixing was dividedly in some parts to the four-hole boiling flask in 9 hours
Reaction solution uniformly is obtained, heating using microwave was cooled to reaction at 145 DEG C 18 hours during four-hole boiling flask then is put into synthesis reactor
Room temperature obtains Salkowski's solution, is acidified within 5 hours to adding the hydrochloric acid of 40mL to place in Salkowski's solution, then by acidifying
Salkowski's solution pours into separatory funnel, and the ether for adding 55mL to separatory funnel carries out 6 extracting operations, every time after extraction by under
Layer liquid is collected and obtains phosphotungstic acid ether mixtures, is finally reclaimed remaining solid after ether at 112 DEG C using revolving equipment
Dry 6 hours, the light yellow Wells-Dawson types phosphotungstic acid of 12.1g is obtained, with H6P2W18O62·24H2O is calculated, and yield is
91.1%.
The Wells-Dawson type phosphotungstic acids prepared to embodiment 1 detect, as a result as shown in Figure 1, Figure 2 and with 3 institutes
Show, the Wells-Dawson type phosphotungstic acids that embodiment 2 to embodiment 8 is prepared are detected respectively, as a result with Fig. 1, Fig. 2
It is similar with Fig. 3.
Wherein, Fig. 1 is the XRD of the Wells-Dawson type phosphotungstic acids that embodiment 1 is prepared, can from Fig. 1
To phosphotungstic acid (H6P2W18O62·24H2O whole characteristic peaks), it is 17-22 ° in 2 θ, 25-30 °, is had in the range of 31-38 °
Stronger absworption peak.
Fig. 2 is the infrared spectrogram of the Wells-Dawson type phosphotungstic acids that embodiment 1 is prepared, can from Fig. 2
Arrive, in 3425cm-1Place can see the stretching vibration of H-O keys in hydrone, in 1091cm-1, 963cm-1, 914cm-1With
782cm-1Place can be respectively seen P-O keys, W=O keys, W-Ob- W keys and W-OcThe stretching vibration of-W keys.
Fig. 3 is the ultraviolet spectrogram of the Wells-Dawson type phosphotungstic acids that embodiment 1 is prepared, and can be seen by Fig. 3
Arrive, the weak absorbing bands of a spectrum at strong absorption band and 320nm at 205nm have two obvious characteristic absorption peaks, wherein
Absworption peak at 205nm corresponds to Od→ W lotuses move transition, and the absworption peak at 320nm corresponds to Ob(c)→ W lotuses move transition.
The molecular structure that can be seen that the phosphotungstic acid that the present embodiment is prepared by Fig. 1, Fig. 2 and Fig. 3 is Wells-
Dawson types.
In sum, the preparation method of Wells-Dawson types phosphotungstic acid provided in an embodiment of the present invention can be prepared
Purity Wells-Dawson type phosphotungstic acids higher, and the method process is simple, easy to operate, high income.The Wells-
Dawson type phosphotungstic acids have that purity is high, impurity is few, the strong advantage of catalytic performance.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of Wells-Dawson types phosphotungstic acid, it is characterised in that comprise the following steps：
Tungsten trioxide powder is added in 60-80 DEG C of phosphoric acid and stirred, and reacted 12-24 hours at 120-180 DEG C
Salkowski's solution is obtained, the phosphoric acid is 12-18 with the mol ratio of the tungstic acid:1；
Ether extract and separate is used after the Salkowski's solution is acidified.
2. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
The granularity of tungsten powder is 30-60 μm.
3. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
During tungsten powder was dividedly in some parts the phosphoric acid in 6-10 hours.
4. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
Tungsten powder is divided into 9-12 parts and is dividedly in some parts in the phosphoric acid.
5. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
Tungsten powder is added in the phosphoric acid after being heated to 60-80 DEG C.
6. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
Tungsten reacts at 160-170 DEG C after being stirred with the phosphoric acid and obtains the Salkowski's solution in 12-16 hours.
7. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that three oxidation
Tungsten powder uses water-bath or heating using microwave to reaction at 120-180 DEG C after mixing with the phosphoric acid.
8. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that the acidifying
Method is：The Salkowski's solution is mixed into placement 3-5 hours with inorganic acid.
9. the preparation method of Wells-Dawson types phosphotungstic acid according to claim 1, it is characterised in that the ether extraction
Taking the method for separation is：The Salkowski's solution after by acidifying is extracted 5-8 times using ether, and the subnatant that will be collected is in 100-
Dried at 120 DEG C 6-12 hours.
10. a kind of Wells-Dawson types phosphotungstic acid, it is characterised in that：It is as any one of claim 1 to 9
The preparation method of Wells-Dawson type phosphotungstic acids is prepared.
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