CN104974028A - Preparation method of solid vanadyl oxalate - Google Patents
Preparation method of solid vanadyl oxalate Download PDFInfo
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- CN104974028A CN104974028A CN201510349530.1A CN201510349530A CN104974028A CN 104974028 A CN104974028 A CN 104974028A CN 201510349530 A CN201510349530 A CN 201510349530A CN 104974028 A CN104974028 A CN 104974028A
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- oxalic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention relates to a preparation method of solid vanadyl oxalate, and belongs to the field of chemical engineering. The technical problem solved by the invention is to provide a solid preparation method of the solid vanadyl oxalate. The method is simple in operation, and direct solid synthesis of product can be realized under relatively low temperature. The method comprises the following steps: mixing V2O5 with oxalic acid, reacting for 30-60 min at the temperature of 100-200 DEG C so as to obtain a wet vanadyl oxalate solid; and drying the wet vanadyl oxalate solid so as to obtain a solid vanadyl oxalate product. According to the method disclosed by the invention, direct solid synthesis of the product is realized under relatively low temperature, the investment is saved, the technological process is short, the desired result is produced quickly, the direct utilization rate of vanadium is high, and no waste water is generated. the production cost of waste gas is low, and the method is beneficial for realizing large-scale production.
Description
Technical field
The present invention relates to the preparation method of solid oxalic acid vanadyl, belong to chemical field.
Background technology
Vanadyl oxalate (Vanadyl oxalate), chemical formula: VOC
2o
4nH
2o, comes into one's own day by day as a kind of fine chemical product, is widely used in chemical reagent, nano material, glaze, plated material, the synthesis of Organic chemical products, the producing and the preparation of high tension battery material lithium vanadium phosphate of high purity vanadium compound.At present, the production and selling of vanadyl oxalate controls in the thunder Bach (TCW) as special in Austria of fewer companies abroad hand, and its product composition is in table 1.Domesticly also be in conceptual phase, substantially without the production technology of scale manufacturer and industrialization.
The Austrian special thunder Bach liquid vanadyl oxalate composition/% of table 1
| Composition | V | Fe | Na | K | Si | Cr | P | S |
| Content | 7.0±0.2 | 0.01 | 0.03 | 0.06 | 0.008 | 0.014 | 0.002 | 0.025 |
The content of table 1 is amounted to into solid oxalic acid vanadyl, and its content is as table 2.
The Austrian special thunder Bach vanadyl oxalate (VOC of table 2
2o
4nH
2o) composition/%
| n | V | Fe | Na | K | Si | Cr | P | S |
| 0 | 32.551 | 0.047 | 0.140 | 0.279 | 0.037 | 0.065 | 0.009 | 0.116 |
| 0.5 | 30.783 | 0.044 | 0.132 | 0.264 | 0.035 | 0.062 | 0.009 | 0.110 |
| 1.0 | 29.197 | 0.042 | 0.125 | 0.250 | 0.033 | 0.058 | 0.008 | 0.104 |
| 1.5 | 27.766 | 0.040 | 0.119 | 0.238 | 0.032 | 0.056 | 0.008 | 0.099 |
| 2.0 | 26.469 | 0.038 | 0.113 | 0.227 | 0.030 | 0.053 | 0.008 | 0.095 |
Vanadyl oxalate Chang Zuowei prepares V
2o
4precursor, patent CN103319326A essentially discloses a kind of preparation method of vanadyl oxalate, the method comprises the following steps: the raw material containing Vanadium Pentoxide in FLAKES, under the existence of aqueous sulfuric acid, contacts with reductive agent by (1), obtains tetravalence vanadium solution; (2) tetravalence vanadium solution step (1) obtained contacts with alkali-metal oxyhydroxide and carries out precipitin reaction, and carries out solid-liquid separation, obtains solid product; (3) solid product that step (2) obtains is contacted with oxalic acid, obtain vanadyl oxalate.Its reduction process of the method is separated with salification process, there is Production Flow Chart length, reagent consumption amount is large, the problem that production cost is high.
Patent CN1693212A essentially discloses the preparation method of vanadium dioxide nano powder, and processing step is followed successively by the preparation of presoma and the thermolysis of presoma, and the preparation of presoma is with V
2o
5be raw material with oxalic acid, V
2o
5be 1:1 ~ 3 with the weight ratio of oxalic acid, by the V of described proportioning
2o
5put into reaction vessel with oxalic acid and add water normal pressure, 40 ~ 70 DEG C stir, until V
2o
5till completing with the reduction reaction of oxalic acid, the add-on of water is with V
2o
5flooded with oxalic acid and be advisable, after reduction reaction completes, namely obtained solution evaporate to dryness was obtained solid oxalic acid vanadyl presoma.These class methods prepare vanadyl oxalate; need using water as solvent; have that Production Flow Chart is long, reagent consumption amount is large, facility investment is large, production cost is high, crystallization and evaporation concentration (wastewater treatment), vanadium the series of problems such as direct utilization ratio is low, produce with being difficult to mass-producing.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of solid oxalic acid vanadyl, and the method is simple to operate, can realize the direct solid state synthesis of product at a lower temperature.
The preparation method of solid oxalic acid vanadyl of the present invention, comprises the steps:
A, by V
2o
5mix with oxalic acid, at 100 ~ 200 DEG C of reaction 30 ~ 60min, obtain the vanadyl oxalate solid soaked;
B, obtain solid oxalic acid vanadyl product by after wetting vanadyl oxalate solid drying.
In a step, preferably by V
2o
5mix with oxalic acid, at 120 DEG C of reaction 30min; Or preferably by V
2o
5mix with oxalic acid, at 200 DEG C of reaction 60min; Or preferably by V
2o
5mix with oxalic acid, at 150 DEG C of reaction 45min; Or preferably by V
2o
5mix with oxalic acid, at 100 DEG C of reaction 50min.
Further, in a step, in mass ratio, V
2o
5︰ oxalic acid=1 ︰ 2.1 ~ 2.5.
Further, the drying described in b step is preferably 60 ~ 120 DEG C of drying 1 ~ 2h.
Further, stir during preferred a step reaction, and to control mixing speed be 100 ~ 200 revs/min.
Further, described oxalic acid is preferably H
2c
2o
42H
2o.
Method of the present invention; take full advantage of the response characteristic of oxalic acid and Vanadium Pentoxide in FLAKES; utilize simple equipment, achieve the direct solid state synthesis of product at a lower temperature; reduced investment, short, instant effect, vanadium the direct utilization ratio of technical process are high; production cost is low, is conducive to the production realizing mass-producing.Method of the present invention is utilized to produce solid oxalic acid vanadyl, can create beneficial result 5000 yuan/more than t, filled up the technological gap that domestic and international solid oxalic acid vanadyl is produced, have industry promotional value, remarkable in economical benefits, the utilization ratio of vanadium is high, environmental friendliness.
Compared with prior art, the present invention has following beneficial effect: reduction and salify two processes are carried out by present method simultaneously, and adopts solid state reaction, under certain temperature of reaction, directly generate wetting vanadyl oxalate solid; Solid oxalic acid vanadyl product is obtained after drying.In whole preparation process, reaction process is short, less investment, production unit simple, does not have waste water, waste gas to produce; environmental friendliness, does not also evaporate, crystallization flow process, and reagent consumption is few, the direct utilization ratio of vanadium is close to 100%; production cost is low, easily accomplishes scale production.
Embodiment
The preparation method of solid oxalic acid vanadyl of the present invention, comprises the steps:
A, by V
2o
5mix with oxalic acid, at 100 ~ 200 DEG C of reaction 30 ~ 60min, obtain the vanadyl oxalate solid soaked;
B, obtain solid oxalic acid vanadyl product by after wetting vanadyl oxalate solid drying.
Reduction and salify two processes are carried out by the inventive method simultaneously, first utilize oxalic acid both as reductive agent also as salt forming agent, simplify the medicament kind of production, also ensure that quality product; Then join after Vanadium Pentoxide in FLAKES being mixed with oxalic acid in reactor, complete reduction and salt-forming reaction at a certain temperature, obtain the vanadyl oxalate solid soaked; Finally namely obtain solid oxalic acid vanadyl product by after wetting vanadyl oxalate solid drying.
The preparation method of solid oxalic acid vanadyl of the present invention, without the need to adding extra solvent, directly carries out solid state synthesis reaction.Wherein, control the key that temperature of reaction and reaction times are this reactions, if temperature is too low, by do not reach Vanadium Pentoxide in FLAKES and oxalic acid reaction needed for energy, cannot ensure that reaction is carried out smoothly, and temperature is too high, oxalic acid easily volatilizees, carrying out smoothly of impact reaction, therefore, temperature of reaction of the present invention controls to be advisable at 100 ~ 200 DEG C.
Preferably, in a step, by V
2o
5mix with oxalic acid, at 120 DEG C of reaction 30min; Or by V
2o
5mix with oxalic acid, at 200 DEG C of reaction 60min; Or by V
2o
5mix with oxalic acid, at 150 DEG C of reaction 45min; Or by V
2o
5mix with oxalic acid, at 100 DEG C of reaction 50min.
Further, in a step, in mass ratio, V
2o
5︰ oxalic acid=1 ︰ 2.1 ~ 2.5.Oxalic acid of the present invention is the oxalic acid containing two crystal water, i.e. H
2c
2o
42H
2o.The mass ratio of Vanadium Pentoxide in FLAKES and oxalic acid is also the key factor of the direct utilization ratio affecting reaction efficiency and vanadium.Consumption of oxalic acid is too low, and reaction is incomplete, the utilization ratio affecting vanadium of meeting high degree; Consumption of oxalic acid is too high, also can affect the purity of the finished product while waste medicament.
Further, in order to improve drying efficiency, the drying described in b step is preferably 60 ~ 120 DEG C of drying 1 ~ 2h.
Further, in order to improve reaction efficiency, stir during preferred a step reaction, and to control mixing speed be 100 ~ 200 revs/min.
Method of the present invention; take full advantage of the response characteristic of oxalic acid and Vanadium Pentoxide in FLAKES; utilize simple equipment, achieve the direct solid state synthesis of product at a lower temperature; reduced investment, short, instant effect, vanadium the direct utilization ratio of technical process are high; production cost is low, is conducive to the production realizing mass-producing.Method of the present invention is utilized to produce solid oxalic acid vanadyl, can create beneficial result 5000 yuan/more than t, filled up the technological gap that domestic and international solid oxalic acid vanadyl is produced, have industry promotional value, remarkable in economical benefits, the utilization ratio of vanadium is high, environmental friendliness.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
In embodiment, V
2o
5for the high purity vanadic anhydride that Fan Ye company limited of Pan Gang group produces, its main component (in massfraction) is: V
2o
5>99.5%, Fe<0.010%, Mo<0.010%, Cr<0.010%, Si<0.010%, Na<0.010%, K<0.010%.
Embodiment 1
Get 500g V
2o
5, add 1050g H
2c
2o
4.2H
2after O mixes, join in pivotal reactor, controlling mixing speed is 200 revs/min, controls temperature of reaction to 120 DEG C, terminates, pour out reaction product after reaction 30min; Reaction product is obtained solid oxalic acid vanadyl product after 60 DEG C of dry 2h, and sample presentation analysed preparation composition is: 30.53%TV, Fe<0.010%, 0.032%Na, 0.013%K, 0.013%Si, Mo<0.010%, 0.011%Cl.The direct utilization ratio of vanadium is 99.95% as calculated.
Wherein, the method for calculation of the direct utilization ratio of vanadium are:
Embodiment 2
Get 500g V
2o
5, add 1250g H
2c
2o
4.2H
2after O mixes, join in ceramic crucible and be placed on electrical heater and keep stirring, controlling mixing speed is 100 revs/min, controls temperature of reaction to 200 DEG C, terminates, pour out reaction product after reaction 60min; Reaction product is obtained solid oxalic acid vanadyl product after 80 DEG C of dry 2h, and sample presentation analysed preparation composition is: 31.50%TV, Fe<0.010%, 0.033%Na, 0.014%K, 0.014%Si, Mo<0.010%, 0.012%Cl.The direct utilization ratio of vanadium is 99.90% as calculated.
Embodiment 3
Get 500g V
2o
5, add 1100g H
2c
2o
4.2H
2after O mixes, join in ceramic crucible and be placed on electrical heater and keep stirring, controlling mixing speed is 150 revs/min, controls temperature of reaction to 150 DEG C, terminates, pour out reaction product after reaction 45min; Reaction product is obtained solid oxalic acid vanadyl product after 100 DEG C of dry 1h, and sample presentation analysed preparation composition is: 30.97%TV, Fe<0.010%, 0.030%Na, 0.012%K, 0.012%Si, Mo<0.010%, 0.010%Cl.The direct utilization ratio of vanadium is 99.93% as calculated.
Embodiment 4
Get 500g V
2o
5, add 1150g H
2c
2o
4.2H
2after O mixes, join in ceramic crucible and be placed on electrical heater and keep stirring, controlling mixing speed is 180 revs/min, controls temperature of reaction to 100 DEG C, terminates, pour out reaction product after reaction 50min; Reaction product is obtained solid oxalic acid vanadyl product after 120 DEG C of dry 1h, and sample presentation analysed preparation composition is: 29.78%TV, Fe<0.010%, 0.034%Na, 0.011%K, 0.011%Si, Mo<0.010%, 0.013%Cl.The direct utilization ratio of vanadium is 99.87% as calculated.
Comparative example 1
Adopt method disclosed in CN1693212A to prepare solid oxalic acid vanadyl, its reaction process is as follows:
Get 500g V
2o
5, 1500g H
2c
2o
4.2H
2o, puts into reaction vessel and adds water logging and cross V
2o
5and oxalic acid, normal pressure, 70 DEG C stir 2h complete reaction, then by obtained solution after 90 DEG C of evaporates to dryness, drying obtains solid oxalic acid vanadyl product.Sample presentation analysed preparation composition is: 26.81%TV, Fe<0.010%, 0.035%Na, 0.011%K, 0.011%Si, Mo<0.010%, 0.013%Cl.As calculated, the direct utilization ratio of vanadium is 99.83%.
Visible, compared with the inventive method, adopt method disclosed in CN1693212A to prepare solid oxalic acid vanadyl, not only complicated process of preparation, need to carry out the steps such as solvent evaporate to dryness, and content of vanadium in the product adopting the method to obtain is lower.Vanadyl oxalate VOC
2o
4theoretical content of vanadium be 32.90%, in fact because vanadyl oxalate all contains certain crystal water more or less, therefore its content of vanadium often will lower than this numerical value.The height of its water content depends in solid oxalic acid vanadyl preparation process the number introducing the water yield, and that is, the water of introducing is more, then crystal water quantity is more, and the crystal water of vanadyl oxalate solid during cryodrying, can not be deviate from, therefore, adopt the content of vanadium in the product of the method gained lower.
Comparative example 2
Adopt method disclosed in CN103319326A to prepare solid oxalic acid vanadyl, its reaction process is as follows:
Get 500g V
2o
5, add the making beating of 1000ml deionized water, add 500g H
2c
2o
4.2H
2o, at 80 DEG C of stirring reaction 2h, adds sodium hydrate regulator solution pH to 5.0, stirring reaction 1h, obtains filter cake and (be equivalent to 400g V after filtration
2o
5); Reaction vessel put into by filter cake, adds 1000g H
2c
2o
4.2H
2o, and add water logging and cross V
2o
5and oxalic acid, normal pressure, 70 DEG C stir 2h complete reaction, then by obtained solution after 90 DEG C of evaporates to dryness, drying obtains solid oxalic acid vanadyl product.Sample presentation analysed preparation composition is: 25.78%TV, Fe<0.010%, 0.035%Na, 0.011%K, 0.011%Si, Mo<0.010%, 0.013%Cl.As calculated, the direct utilization ratio of vanadium is 79.58%.
Visible, adopt method disclosed in CN103319326A to prepare solid oxalic acid vanadyl, its reaction process is complicated, and content of vanadium in the product obtained is lower, and the direct utilization ratio of vanadium is not high yet.
To sum up; can find out; method of the present invention is in whole preparation process, and reaction process is short, less investment, production unit simple, does not have waste water, waste gas to produce; environmental friendliness; also do not evaporate, crystallization flow process, reagent consumption is few, content of vanadium in product is high, and the direct utilization ratio of vanadium is close to 100%; production cost is low, easily accomplishes scale production.
Claims (9)
1. the preparation method of solid oxalic acid vanadyl, is characterized in that, comprises the steps:
A, by V
2o
5mix with oxalic acid, at 100 ~ 200 DEG C of reaction 30 ~ 60min, obtain the vanadyl oxalate solid soaked;
B, obtain solid oxalic acid vanadyl product by after wetting vanadyl oxalate solid drying.
2. the preparation method of solid oxalic acid vanadyl according to claim 1, is characterized in that: in a step, by V
2o
5mix with oxalic acid, at 120 DEG C of reaction 30min.
3. the preparation method of solid oxalic acid vanadyl according to claim 1, is characterized in that: in a step, by V
2o
5mix with oxalic acid, at 200 DEG C of reaction 60min.
4. the preparation method of solid oxalic acid vanadyl according to claim 1, is characterized in that: in a step, by V
2o
5mix with oxalic acid, at 150 DEG C of reaction 45min.
5. the preparation method of solid oxalic acid vanadyl according to claim 1, is characterized in that: in a step, by V
2o
5mix with oxalic acid, at 100 DEG C of reaction 50min.
6. the preparation method of the solid oxalic acid vanadyl according to any one of Claims 1 to 5, is characterized in that: in a step, in mass ratio, V
2o
5︰ oxalic acid=1 ︰ 2.1 ~ 2.5.
7. the preparation method of the solid oxalic acid vanadyl according to any one of claim 1 ~ 6, is characterized in that: the drying described in b step is 60 ~ 120 DEG C of drying 1 ~ 2h.
8. the preparation method of the solid oxalic acid vanadyl according to any one of claim 1 ~ 7, is characterized in that: stir during a step reaction, and to control mixing speed be 100 ~ 200 revs/min.
9. the preparation method of the solid oxalic acid vanadyl according to any one of claim 1 ~ 8, is characterized in that: described oxalic acid is H
2c
2o
42H
2o.
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| CN201510349530.1A CN104974028A (en) | 2015-06-23 | 2015-06-23 | Preparation method of solid vanadyl oxalate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056604A (en) * | 2017-05-15 | 2017-08-18 | 天津市风船化学试剂科技有限公司 | A kind of preparation method of high-purity oxalic acid vanadyl solid product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689515A (en) * | 1971-06-04 | 1972-09-05 | Foote Mineral Co | Vanadyl oxalate compounds and process for producing same |
| CN1693212A (en) * | 2005-04-25 | 2005-11-09 | 四川大学 | Process for preparing vanadium dioxide nano powder |
| CN101077772A (en) * | 2007-06-27 | 2007-11-28 | 四川大学 | Process for producing nano vanadium nitride powder-body |
-
2015
- 2015-06-23 CN CN201510349530.1A patent/CN104974028A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689515A (en) * | 1971-06-04 | 1972-09-05 | Foote Mineral Co | Vanadyl oxalate compounds and process for producing same |
| CN1693212A (en) * | 2005-04-25 | 2005-11-09 | 四川大学 | Process for preparing vanadium dioxide nano powder |
| CN101077772A (en) * | 2007-06-27 | 2007-11-28 | 四川大学 | Process for producing nano vanadium nitride powder-body |
Non-Patent Citations (2)
| Title |
|---|
| D. N. SATHYANARAYANA ET AL.: "STUDIES ON OXOVANADIUM (IV) OXALATE HYDRATES", 《J.INORG.NUCL.CHEM.》 * |
| 陈寿椿: "《重要无机化学反应》", 30 April 1994 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056604A (en) * | 2017-05-15 | 2017-08-18 | 天津市风船化学试剂科技有限公司 | A kind of preparation method of high-purity oxalic acid vanadyl solid product |
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