CN104130283A - Preparation method of high energy phosphoric acid compound - Google Patents
Preparation method of high energy phosphoric acid compound Download PDFInfo
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- CN104130283A CN104130283A CN201410310876.6A CN201410310876A CN104130283A CN 104130283 A CN104130283 A CN 104130283A CN 201410310876 A CN201410310876 A CN 201410310876A CN 104130283 A CN104130283 A CN 104130283A
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Abstract
The invention discloses a preparation method of a high energy phosphoric acid compound, which comprises the following steps: uniformly mixing phosphoric pentoxide and industrial phosphoric acid, slowly adding organic acid anhydride in a mixing system and stirring for reaction; after reacting, adding carbonate and/or a bicarbonate precipitating agent in a reaction solution, stirring and precipitating deposition, and filtering and then obtaining the high energy phosphoric acid compound with high yield. The method has the advantages of simple operation, high utilization rate of raw materials, low production cost, safety and environmental protection, and can satisfy industrialization production.
Description
Technical field
The present invention relates to a kind of preparation method of high-energy phosphate compound, belong to the synthetic field of chemical industry.
Background technology
High-energy phosphate compound is the phosphate cpd occurring in organism intracellular metabolite process, during hydrolysis, can discharge a large amount of free energys, makes organism can complete various physiological activities.The high-energy phosphate bond that high-energy phosphate compound generally all has can be transferred in other compound as ADP etc. under the effect of enzyme, thereby realizes the in-situ regeneration of expensive cofactor ATP, thereby is with a wide range of applications.
Jinan Wei Erkang biochemical pharmacy company discloses preparation and the assay (< < China biochemical drug magazine > > in 2003) of acetylphosphate dilithium salt, synthetic high-energy phosphate compound is acetylphosphate dilithium salt, is mainly used in measuring coenzyme A vigor.It is raw material that the method be take aceticanhydride and dipotassium hydrogen phosphate, generates acetyl phosphate in pyridine solution, through lithium hydroxide, further reacts and generates acetylphosphate dilithium salt, separates out after finally adding cold ethanol.In the method, because easily causing aceticanhydride, the water electrode in used pyridine solution is hydrolyzed to acetic acid, therefore reaction need make aceticanhydride consumption greatly excessive, the transformation efficiency of aceticanhydride is very low, below 50%, and excessive aceticanhydride not only makes product cost unprecedented soaring, it is excessive that a large amount of residual aceticanhydrides and acetic acid make sewage treatment equipment investment simultaneously; In addition, the use of dipotassium hydrogen phosphate causes the excessive use of lithium hydroxide, otherwise the acetylphosphate di-potassium forming is difficult to separate out, also need to introduce dehydrated alcohol or ether is separated out product, and the introducing of excessive lithium hydroxide and organic solvent must cause waste water extremely difficult from reaction system simultaneously.
U.S. Patent number 4701285 discloses take aceticanhydride, propionic anhydride and Acetyl Chloride 98Min. as raw material, and phosphate group aliment is potassiumphosphate or sodium phosphate, reacts, then carry out extract product with ester, alcohol or ketone in water.The method adopts water react, must consume acid anhydrides and generate acetic acid, causes acid anhydrides utilization ratio to decline to a great extent; And the acetic acid generating meeting and salt precipitation have affected product content and purity, also increased cost; And use organic solvent extracting, increase undoubtedly cost contaminate environment.
U.S. Patent number 4088675 is with ketene and phosphatase reaction, and reaction solvent is ester class, ethers or their mixture, and ethyl acetate is solvent, after reaction finishes, with short-chain alkyl alcohol, ester or ether, carries out extracting.Although the method adopts ethyl acetate organic phase to reduce to a certain extent the hydrolysis of the raw materials such as acid anhydrides, reaction process and subsequent disposal need adopt a large amount of organic solvents, and production cost is improved, serious to environmental disruption, are unfavorable for industrial production.
Summary of the invention
The series of problems such as the feed stock conversion that exists for the preparation method of high-energy phosphate compound in prior art is low, production cost is high, environmental pollution is serious, the object of the invention is to be to provide that a kind of raw material availability is high, production cost is low, safety and environmental protection, high yield is prepared the method for highly purified high-energy phosphate compound.
The invention provides a kind of preparation method of high-energy phosphate compound, the method is that Vanadium Pentoxide in FLAKES is joined to temperature is in the industrial phosphoric acid of 55～65 ℃, after mixing by the solid-liquid proportioning of 2～10g:100mL, mixed system is cooled to 0～30 ℃, in described mixed system, slowly drip the organic acid anhydride stirring reaction of phosphatase 11～1.5 times molar weight; After having reacted, in reaction solution, add carbonate and/or supercarbonate precipitation agent, stir, separate out precipitation, filter, obtain high-energy phosphate compound.
The preparation method of high-energy phosphate compound of the present invention also comprises following preferred version:
In preferred scheme, organic acid anhydride add-on is 1～1.2 times of phosphoric acid molar weight.
In preferred scheme, the time of stirring reaction is 1～3h.
In preferred scheme, organic acid anhydride is propionic anhydride, butyryl oxide, sym-dichloroacetic anhydride or diacetyl oxide.
In preferred scheme, carbonate is MgCO
3and/or CaCO
3.
In preferred scheme, supercarbonate is Mg (HCO
3)
2and/or Ca (HCO
3)
2.
In preferred scheme, the add-on of carbonate and/or supercarbonate precipitation agent is 1～1.5 times of phosphoric acid molar weight; Most preferably be 1～1.2 times.
The commercially available phosphoric acid that described industrial phosphoric acid mass concentration is 85%.
Most preferred preparation method is that Vanadium Pentoxide in FLAKES is joined to temperature is in the industrial phosphoric acid of 55～65 ℃, by the solid-liquid proportioning of 2～10g:100mL, is uniformly mixed after 0.5～1.5h; Mixed system is cooled to 0～25 ℃, in described mixed system, slowly drip the organic acid anhydride stirring reaction 1～3h of phosphatase 11～1.2 times molar weight; After having reacted, in reaction solution, add carbonate and/or the supercarbonate precipitation agent of phosphatase 11～1.2 times molar weight, stir 1.5～2.5h, separate out precipitation, filter, obtain high-energy phosphate compound.
The preparation method of high-energy phosphate compound of the present invention, comprises following concrete steps:
Step 1: get industrial phosphoric acid and be placed in reaction vessel, reaction vessel is placed in to 55～60 ℃ of environment, then add Vanadium Pentoxide in FLAKES powder in reaction vessel, stir 0.5～1.5 hour, obtain mixed solution; Wherein, the solid-liquid additional proportion of Vanadium Pentoxide in FLAKES and industrial phosphoric acid is 2～10g:100mL;
Step 2: the mixed solution of step 1 is cooled to 0～30 ℃ of propionic anhydride, butyryl oxide, sym-dichloroacetic anhydride or diacetyl oxide of getting phosphatase 11～1.5 times molar weight, slowly drop in the mixed solution of step 1 gained, stirring reaction, reacts and continue 1～3 hour simultaneously;
Step 3: add carbonate and/or the supercarbonate precipitation agent of phosphatase 11～1.5 times molar weight in the reaction solution after step 2 has been reacted, stir 1.5～2.5 hours, separate out solid granular precipitation; Described carbonate is MgCO
3and/or CaCO
3; Supercarbonate is Mg (HCO
3)
2and/or Ca (HCO
3)
2;
Step 4: filtration step 3 is collected above-mentioned particulate state throw out, suction filtration sediment separate out and liquid, collecting precipitation thing vacuum-drying and get final product.
Useful technique effect of the present invention: it is raw material that phosphoric acid and acid anhydrides are take in the present invention first, under Vanadium Pentoxide in FLAKES effect, directly acidylate obtains the high-energy phosphate compound of high yield.Advantage of the present invention is: 1, adopt appropriate Vanadium Pentoxide in FLAKES, under suitable temperature condition, join in Phosphoric Acid, remove on the one hand a small amount of moisture in industrial phosphoric acid, effectively prevent the hydrolysis of follow-up acid anhydrides, catalysed promoted acylation reaction on the other hand, improves the transformation efficiency of raw material effectively, wherein, acid anhydrides transformation efficiency is more than 90%, and phosphoric acid transformation efficiency reaches 98%, and purity content is greater than 90%; Overcome and greatly increased the defect that acid anhydrides consumption reaches increase phosphoric acid transformation efficiency in the past, effectively prevented that excessive acid anhydrides from being used the environmental pollution bringing, the negative impact that cost raises.2,, without adopting other organic solvent, be conducive to further reduce product cost and reduced the destruction of organic solvent to environment.3, the carbonate that precipitation process adopts or bicarbonate salts precipitation agent, also without excessive in a large number, have further improved the purity of product.In sum, technique of the present invention is simple, raw material is cheap and easy to get, and the compound preparing has the feature of high purity, high yield, is applicable to suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is the infrared spectrogram of the propionyl trimagnesium phosphate product of embodiment 1 preparation.
[Fig. 2] is the infrared spectrogram of the acetylphosphate calcium product of embodiment 3 preparations.
Embodiment
Following examples are intended to further illustrate content of the present invention, rather than limit the scope of the invention.Embodiment 1
1, get 85% phosphoric acid 200mL in glass beaker, add 16.0g Vanadium Pentoxide in FLAKES powder, 55 ℃ of stirred in water bath 1 hour;
2, the mixture of step 1 is cooled to 25 ℃, get the propionic anhydride of 1.1 times of phosphoric acid mole numbers, be slowly added drop-wise in phosphate mixture, process continues 1.5 hours;
3, add 274.0g magnesiumcarbonate, ice bath stirs 2 hours, obtains solid granular precipitation;
4, filter and collect above-mentioned particulate state throw out, vacuum filtration is dried to obtain propionyl trimagnesium phosphate 564.5g, and purity is 90.2%, and the transformation efficiency of phosphoric acid is 98.7%, and the transformation efficiency of propionic anhydride is 90.9%.
Embodiment 2
1, get 85% phosphatase 11 20mL in glass beaker, add 7.8g Vanadium Pentoxide in FLAKES powder, 60 ℃ of stirred in water bath 1.5 hours;
2, the mixture of step 1 is cooled to 15 ℃, get the propionic anhydride of 1.05 times of phosphoric acid mole numbers, be added drop-wise in phosphate mixture, stirring and evenly mixing continues 2.5 hours;
3, add 163.3g Calcium hydrogen carbonate, ice bath stirs 2 hours, is precipitated thing;
4, filter collecting precipitation thing, vacuum filtration dry propionyl calcium phosphate 347.6g, purity 94.96%, phosphoric acid transformation efficiency 98.5%, the propionic anhydride transformation efficiency 95.2% of obtaining.
Embodiment 3
1, get 85% phosphoric acid 300mL in glass beaker, add 15.6g Vanadium Pentoxide in FLAKES powder, 65 ℃ of stirred in water bath 1 hour;
2, the mixture of step 1 is cooled to 3 ℃, get the diacetyl oxide of 1.1 times of mole numbers, be slowly added drop-wise in phosphate mixture, stirring reaction, process continues 1.5 hours;
3, add calcium carbonate 440.6g, ice bath stirs 2.5 hours, obtains solid granular precipitation;
4, filter and collect above-mentioned particulate state throw out, vacuum filtration is also dry, obtains acetylphosphate calcium 829.3g, purity 93.19%.Phosphoric acid transformation efficiency is 98.6%, and diacetyl oxide transformation efficiency is 90.6%.
Embodiment 4
1, get 85% phosphatase 11 00mL in glass beaker, add 2.5g Vanadium Pentoxide in FLAKES powder, 55 ℃ of stirred in water bath 1 hour;
2, the mixture of step 1 is cooled to 10 ℃, get the diacetyl oxide of 1.1 times of mole numbers, in the phosphate mixture being slowly added drop-wise to, stirring reaction, process continues 1.5 hours;
3, add Calcium hydrogen carbonate 236.5g, ice bath stirs 2.5 hours, obtains solid granular precipitation;
4, filter and collect above-mentioned particulate state throw out, vacuum filtration is also dry, obtains acetylphosphate calcium 276.9g, purity 93.19%.Phosphoric acid transformation efficiency is 98.1%, and diacetyl oxide transformation efficiency is 90.2%.
Comparative example 1
1, get 85% phosphoric acid 200mL in glass beaker, get the diacetyl oxide of 1.1 times of phosphoric acid mole numbers, at 25 ℃ of temperature, be slowly added drop-wise in phosphoric acid, process continues 1.5 hours;
2, add 274.0g magnesiumcarbonate, ice bath stirs 2 hours, obtains solid granular precipitation;
3, filter and collect above-mentioned particulate state throw out, vacuum filtration is dried to obtain acetylphosphate magnesium 388.2g, and purity is 60.1%, and the transformation efficiency of phosphoric acid is 44.6%, and the transformation efficiency of diacetyl oxide is 40.9%.
Comparative example 2
1, get 85% phosphoric acid 200mL in glass beaker, the propionic anhydride of getting 1.2 times of phosphoric acid mole numbers is slowly added drop-wise in phosphoric acid at 25 ℃ of temperature, and process continues 1.5 hours;
2, add 274.0g magnesiumcarbonate, ice bath stirs 2 hours, obtains solid granular precipitation;
3, filter and collect above-mentioned particulate state throw out, vacuum filtration is dried to obtain propionyl trimagnesium phosphate 422.6g, and purity is 52.9%, and the transformation efficiency of phosphoric acid is 43.0%, and the transformation efficiency of propionic anhydride is 38.8%.
Comparative example 3
1, get 85% phosphoric acid 200mL in glass beaker, add 16.0g Vanadium Pentoxide in FLAKES powder, 25 ℃ of stirred in water bath 1 hour;
2, holding temperature is 25 ℃, gets the propionic anhydride of 1.1 times of phosphoric acid mole numbers, is slowly added drop-wise in phosphate mixture, and process continues 1.5 hours;
3, add 274.0g magnesiumcarbonate, ice bath stirs 2 hours, obtains solid granular precipitation;
4, filter and collect above-mentioned particulate state throw out, vacuum filtration is dried to obtain propionyl trimagnesium phosphate 396.5g, and purity is 51.3%, and the transformation efficiency of phosphoric acid is 39.5%, and the transformation efficiency of propionic anhydride is 38.2%.
Claims (9)
1. the preparation method of a high-energy phosphate compound, it is characterized in that, it is in the industrial phosphoric acid of 55～65 ℃ that Vanadium Pentoxide in FLAKES is joined to temperature, after mixing by the solid-liquid proportioning of 2～10g:100mL, mixed system is cooled to 0～30 ℃, in described mixed system, slowly drip the organic acid anhydride stirring reaction of phosphatase 11～1.5 times molar weight; After having reacted, in reaction solution, add carbonate and/or supercarbonate precipitation agent, stir, separate out precipitation, filter, obtain high-energy phosphate compound.
2. preparation method according to claim 1, is characterized in that, described organic acid anhydride add-on is 1～1.2 times of phosphoric acid molar weight.
3. preparation method according to claim 1, is characterized in that, the time of stirring reaction is 1～3h.
4. preparation method according to claim 1, is characterized in that, described organic acid anhydride is propionic anhydride, butyryl oxide, sym-dichloroacetic anhydride or diacetyl oxide.
5. preparation method according to claim 1, is characterized in that, described carbonate is MgCO
3and/or CaCO
3.
6. preparation method according to claim 1, is characterized in that, described supercarbonate is Mg (HCO
3)
2and/or Ca (HCO
3)
2.
7. preparation method according to claim 1, is characterized in that, the add-on of described carbonate and/or supercarbonate precipitation agent is 1～1.5 times of phosphoric acid molar weight.
8. preparation method according to claim 7, is characterized in that, the add-on of described carbonate and/or supercarbonate precipitation agent is 1～1.2 times of phosphoric acid molar weight.
9. according to the preparation method described in claim 1～8 any one, it is characterized in that, it is in the industrial phosphoric acid of 55～65 ℃ that Vanadium Pentoxide in FLAKES is joined to temperature, by the solid-liquid proportioning of 2～10g:100mL, is uniformly mixed after 0.5～1.5h; Mixed system is cooled to 0～25 ℃, in described mixed system, slowly drip the organic acid anhydride stirring reaction 1～3h of phosphatase 11～1.2 times molar weight; After having reacted, in reaction solution, add carbonate and/or the supercarbonate precipitation agent of phosphatase 11～1.2 times molar weight, stir 1.5～2.5h, separate out precipitation, filter, obtain high-energy phosphate compound.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3387024A (en) * | 1965-03-30 | 1968-06-04 | Procter & Gamble | Class of organo-phosphorous compounds and process for preparing members thereof |
| US4088675A (en) * | 1976-03-15 | 1978-05-09 | Massachusetts Institute Of Technology | Production of acyl phosphate salts |
| EP0153571A1 (en) * | 1984-02-01 | 1985-09-04 | Daicel Chemical Industries, Ltd. | Process for preparing solid acetyl phosphate salt |
| US4701285A (en) * | 1984-03-19 | 1987-10-20 | Massachusetts Institute Of Technology | Acyl phosphate salts and their use |
| CN1930176A (en) * | 2004-03-08 | 2007-03-14 | 西巴特殊化学品控股有限公司 | Phosphoric acid esters and their use as wetting and dispersing agent |
-
2014
- 2014-07-01 CN CN201410310876.6A patent/CN104130283A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3387024A (en) * | 1965-03-30 | 1968-06-04 | Procter & Gamble | Class of organo-phosphorous compounds and process for preparing members thereof |
| US4088675A (en) * | 1976-03-15 | 1978-05-09 | Massachusetts Institute Of Technology | Production of acyl phosphate salts |
| EP0153571A1 (en) * | 1984-02-01 | 1985-09-04 | Daicel Chemical Industries, Ltd. | Process for preparing solid acetyl phosphate salt |
| US4701285A (en) * | 1984-03-19 | 1987-10-20 | Massachusetts Institute Of Technology | Acyl phosphate salts and their use |
| CN1930176A (en) * | 2004-03-08 | 2007-03-14 | 西巴特殊化学品控股有限公司 | Phosphoric acid esters and their use as wetting and dispersing agent |
Non-Patent Citations (2)
| Title |
|---|
| GEORGE M. WHITESIDES,ET AL.: ""Large-Scale Synthesis of Diammonium Acetyl Phosphate"", 《J. ORG. CHEM.》 * |
| 殷磬 等: ""乙酰磷酸二锂盐的制备及含量测定"", 《中国生化药物杂志》 * |
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Application publication date: 20141105 |