CN107793322A - A kind of method of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt - Google Patents
A kind of method of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt Download PDFInfo
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- CN107793322A CN107793322A CN201710877525.7A CN201710877525A CN107793322A CN 107793322 A CN107793322 A CN 107793322A CN 201710877525 A CN201710877525 A CN 201710877525A CN 107793322 A CN107793322 A CN 107793322A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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Abstract
The invention discloses a kind of method of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt, it in hot desalinized water mainly by adding EDETATE SODIUM and calcium salt, then add after alcohol is stood to filter and Ethylenediaminetetraacetic Acid Calcium Salt product salt is made, the present invention produces Ethylenediaminetetraacetic Acid Calcium Salt salt without high temperature, high-pressure process using the above method, required equipment and technique are simple, and investment risk is small.Technique is compared obvious without concentration section, energy conservation and consumption reduction effects compared with traditional handicraft.Product is obtained using deposition method so that product granularity is uniform, first-class quality.Meanwhile the alcohol reclaimed using rectifying in the above method, recovery alcohol can be used as to do precipitation agent for experiment next time and used, remaining water component is used to test next time does solvent use, and whole technical process is high without waste discharge, environmental benefit.
Description
Technical field
The present invention relates to organic chemical synthesis field, and in particular to a kind of low boiling low molecule separating out alcohol method synthesizes Ethylenediaminetetraacetic Acid Calcium Salt
Salt process.
Background technology
Ethylenediaminetetraacetic Acid Calcium Salt salt is a kind of very conventional food additives.Calcium is one of necessary weight element of plant simultaneously,
In chemical fertilizer, Ethylenediaminetetraacetic Acid Calcium Salt salt can effectively avoid calcium ion and phosphate radical, sulfate radical plasma generation water-insoluble, can apply
In the high-end fertilizer production such as full Water soluble fertilizer, Liquid Fertilizer, there is good economical and practical value.
Shandong Light Ind College journal the 3rd phase of volume 5 discloses a kind of EDTA calcium complex disodium salt preparation technology route,
This method is reacted using high calcium shell and disodium EDTA, and calcio-disodium edetate is obtained by concentrating, drying
Salt, this method has the advantages of calcium source source is wide, cost is low, but there is also the shortcomings that high energy consumption.
This technique separates out the Ethylenediaminetetraacetic Acid Calcium Salt salt in solution using low boiling low mass molecule alcohol, eliminates concentration process, can be very well
Reduction energy consumption.Ethylenediaminetetraacetic Acid Calcium Salt salt is produced there is not yet publishing using this method.
The content of the invention
The technical advance of the present invention is to provide a kind of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt method, adopted
The method that Ethylenediaminetetraacetic Acid Calcium Salt salt is separated out with addition low boiling low mass molecule alcohol substitutes traditional method for concentrating hair and separating out Ethylenediaminetetraacetic Acid Calcium Salt salt, can
It is effective to reduce energy consumption, reduce production cost；
The present invention is implemented by the following technical programs：
A kind of method of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt, comprises the following steps：
（1）Desalted water is heated, then EDETATE SODIUM is separately added into again and calcium salt is reacted, until moisture is in solution
40%-80%；
（2）EDETATE SODIUM or calcium salt are used again, and regulation pH value of solution is 6.5-7.5；
（3）After solution is cooled to room temperature, alcohol is added, is stood after stirring；
（4）After standing 3-10 hours, there is whiteness precipitation in solution, filter；
（5）Solid matter after filtering is put in baking oven and is dried to constant weight, as Ethylenediaminetetraacetic Acid Calcium Salt product salt；
（6）The detection of chelating degree and calcium ion content measure are carried out to Ethylenediaminetetraacetic Acid Calcium Salt product salt；
（7）By step（4）Gained filtrate rectifying goes out alkoxide component and does precipitation agent use for experiment next time, and water component is used for next time
Solvent use is done in experiment.
Further, the temperature of the heating desalted water is 50-100 DEG C.
Further, according to the molar ratio, the dosage of described EDETATE SODIUM and calcium salt is 1:1-1.5.
Further, the calcium salt is in calcium carbonate, calcium hydroxide, calcium oxide, calcium sulfate, calcium nitrate, calcium chloride
It is one or more.
Further, the step（3）Middle alcohol addition is 0.8-2.5 times of the solution quality.
Further, described alcohol is the one or more in methanol, ethanol, propyl alcohol, isopropanol etc..
Further, the step（5）Middle drying temperature control is at 80-100 DEG C.
Further, the step（7）Middle filtrate rectification temperature is 70-120 DEG C.
Further, the chelating degree detection described in following method has been carried out to Ethylenediaminetetraacetic Acid Calcium Salt product salt：By product configuration into
The solution of 1% concentration, add equimolar than potassium carbonate, stand 24 hours after without precipitation produce, both thought in product without free state
Calcium is present.
Further, the present invention is measured using atomic absorption spectrography (AAS) to calcium ion content.
The present invention produces Ethylenediaminetetraacetic Acid Calcium Salt salt without high temperature, high-pressure process using the above method, and required equipment and technique are simple, throw
It is small to provide risk.Technique is compared obvious without concentration section, energy conservation and consumption reduction effects compared with traditional handicraft.Product is obtained using deposition method, is made
Product granularity uniformly, first-class quality.Meanwhile the alcohol reclaimed using rectifying in the above method, under being used for as recovery alcohol
Precipitation agent use is done in secondary experiment, and remaining water component is used for experiment next time and does solvent use, and whole technical process is without waste discharge, ring
Protect high efficiency.
Technology provided by the present invention be applied to Ethylenediaminetetraacetic Acid Calcium Salt salt, EDTA zinc sodium salt, EDTA magnesium sodium salt, NaFeEDTA sodium salt,
The EDTA such as EDTA copper sodiums metal salt products synthesize, and have preferable Popularizing of A.
Embodiment
The present invention is described in further detail by following examples, following examples are explanation of the invention and this
Invention is not limited to following examples.
Embodiment 1
200g desalted waters are added into beaker, is put into electric heating cover and is heated to 80 DEG C；It is stirred with magnetic rotor, revolution is set
It is set to 360 revs/min；Then 40gEDTA disodiums are added into desalted water, after solids is completely dissolved in solution, then slowly
10g calcium oxide is added, is reacted 0.5 hour after material all adds, then it is 7.02 to adjust pH value of solution with EDETATE SODIUM；Then survey
It is 59.6% to obtain moisture in solution；After solution is cooled to room temperature, 200g methanol is added, sealing and standing filters after 4 hours,
The product filtered out is put in dried to constant weight in 90 DEG C of baking ovens after pack, produce Ethylenediaminetetraacetic Acid Calcium Salt product salt；Then filtrate is transferred to
Rectifying obtains methanol component 190g, aqueous composition 188g for 35 minutes under the conditions of 80 DEG C in flask.Through atomic absorption spectrography (AAS)
Detect, calcium content is 9.54% in Ethylenediaminetetraacetic Acid Calcium Salt product salt；By 1g, the product is dissolved in 99g water, adds 1g potassium carbonate, and dissolving is quiet
Put 24 hours, produced in solution without precipitation, illustrate that Ethylenediaminetetraacetic Acid Calcium Salt product salt chelating degree is good.
Embodiment 2
Aqueous composition 188g and 20g the desalination water mixed liquid obtained by the rectifying of embodiment 1 is added into beaker, is put into electric heating cover
In be heated to 80 DEG C；It is stirred with magnetic rotor, revolution is arranged to 360 revs/min；Then added into mixed liquor
30gEDTA disodiums, after solids is completely dissolved in solution, 7g calcium oxide is slow added into, is reacted after material all adds
0.5 hour, then it is 7.16 to adjust pH value of solution with calcium oxide；It is 53.2% to measure moisture in solution；Solution is cooled to room temperature
Afterwards, methanol component 190g and the 10g methanol obtained by the rectifying of embodiment 1 is added, sealing and standing filters after 4 hours, the production filtered out
Product are put in dried to constant weight in 90 DEG C of baking ovens after pack, produce Ethylenediaminetetraacetic Acid Calcium Salt product salt；Then filtrate is transferred in flask 80
Rectifying obtains methanol component 198g, aqueous composition 150g for 40 minutes under the conditions of DEG C.Detected through atomic absorption spectrography (AAS), EDTA calcium
Calcium content is 9.58% in sodium salt product；By 1g, the product is dissolved in 99g water, is added 1g potassium carbonate, dissolving, is stood 24 hours, molten
Produced in liquid without precipitation, illustrate that Ethylenediaminetetraacetic Acid Calcium Salt product salt chelating degree is good.
Embodiment 3
Aqueous composition 150g and 60g the desalination water mixed liquid obtained by the rectifying of embodiment 2 is added into beaker, is put into electric heating cover
In be heated to 85 DEG C；It is stirred with magnetic rotor, revolution is arranged to 360 revs/min；Then added into mixed liquor
30gEDTA disodiums, after solids is completely dissolved in solution, 8g calcium oxide is slow added into, is reacted after material all adds
0.5 hour, then it is 6.91 to adjust pH value of solution with EDETATE SODIUM；It is 52.8% to measure moisture in solution；Solution is cooled to room temperature
Afterwards, methanol component 198g and the 5g methanol obtained by the rectifying of embodiment 2 is added, sealing and standing filters after 5 hours, the product filtered out
It is put in after being dried to constant weight in 90 DEG C of baking ovens and packs, produces Ethylenediaminetetraacetic Acid Calcium Salt product salt；Then filtrate is transferred in flask at 80 DEG C
Under the conditions of rectifying obtain within 40 minutes methanol component 194g, aqueous composition 161g.Detected through atomic absorption spectrography (AAS), calcium in product
Content is 9.51%；By 1g, the product is dissolved in 99g water, is added 1g potassium carbonate, dissolving, is stood 24 hours, is produced in solution without precipitation
It is raw, illustrate that Ethylenediaminetetraacetic Acid Calcium Salt product salt chelating degree is good.
Embodiment 4
Aqueous composition 161g and 50g the desalination water mixed liquid obtained by the rectifying of embodiment 3 is added into beaker, is put into electric heating cover
In be heated to 90 DEG C；It is stirred with magnetic rotor, revolution is arranged to 400 revs/min；30gEDTA bis- is added into mixed liquor
Sodium, after solids is completely dissolved in solution, 8g calcium oxide is slow added into, is reacted 0.3 hour after material all adds, then
It is 7.04 with EDETATE SODIUM regulation pH value of solution；It is 54.6% to measure moisture in solution；After solution is cooled to room temperature, add real
Methanol component 194g and the 10g methanol obtained by the rectifying of example 3 is applied, sealing and standing filters after 5 hours, and the product filtered out is put in 90 DEG C
Packed after being dried to constant weight in baking oven, produce Ethylenediaminetetraacetic Acid Calcium Salt product salt；Filtrate is transferred in flask the rectifying 40 under the conditions of 80 DEG C and divided
Clock obtains methanol component 201g, aqueous composition 158g.Detected through atomic absorption spectrography (AAS), calcium content is 9.55% in product；Will
The 1g products are dissolved in 99g water, are added 1g potassium carbonate, dissolving, are stood 24 hours, are produced in solution without precipitation, illustrate EDTA calcium
Sodium salt product chelating degree is good.
Embodiment 5
Aqueous composition 158g and 50g the desalination water mixed liquid obtained by the rectifying of embodiment 4 is added into beaker, is put into electric heating cover
In be heated to 90 DEG C；It is stirred with magnetic rotor, revolution is arranged to 400 revs/min；30gEDTA is added into mixed liquor, is treated
After solids is completely dissolved in solution, 8g calcium oxide is slow added into, is reacted 0.3 hour after material all adds, then use
EDETATE SODIUM regulation pH value of solution is 7.06；It is 54.0% to measure moisture in solution；After solution is cooled to room temperature, adds and implement
Methanol component 201g obtained by the rectifying of example 4, sealing and standing filter after 5 hours, and the product filtered out is put in 90 DEG C of baking ovens and is dried to
Packed after constant weight, produce Ethylenediaminetetraacetic Acid Calcium Salt product salt；Filtrate is transferred in flask the rectifying under the conditions of 80 DEG C and obtains methanol in 40 minutes
Component 192g, aqueous composition 155g.Detected through atomic absorption spectrography (AAS), calcium content is 9.55% in product；By 1g, the product is molten
In 99g water, 1g potassium carbonate is added, dissolving, stands 24 hours, is produced in solution without precipitation, illustrates Ethylenediaminetetraacetic Acid Calcium Salt product salt chela
It is right good.
Embodiment 6
Aqueous composition 155g and 50g the desalination water mixed liquid obtained by the rectifying of embodiment 5 is added into beaker, is put into electric heating cover
In be heated to 90 DEG C；It is stirred with magnetic rotor, revolution is arranged to 400 revs/min；30gEDTA bis- is added into mixed liquor
Sodium, after solids is completely dissolved in solution, 8g calcium oxide is slow added into, is reacted 0.3 hour after material all adds, then
It is 7.07 with EDETATE SODIUM regulation pH value of solution；It is 53.4% to measure moisture in solution；After solution is cooled to room temperature, add real
The methanol component 192g and methanol 5g obtained by the rectifying of example 5 are applied, sealing and standing filters after 5 hours, and the product filtered out is put in 90 DEG C
Packed after being dried to constant weight in baking oven, produce Ethylenediaminetetraacetic Acid Calcium Salt product salt；Filtrate is transferred in flask the rectifying 40 under the conditions of 80 DEG C and divided
Clock obtains methanol component 190g, aqueous composition 152g.Detected through atomic absorption spectrography (AAS), calcium content is 9.54% in product；Will
The 1g products are dissolved in 99g water, are added 1g potassium carbonate, dissolving, are stood 24 hours, are produced in solution without precipitation, illustrate EDTA calcium
Sodium salt product chelating degree is good.
Claims (10)
- A kind of 1. method of low boiling low molecule separating out alcohol method synthesis Ethylenediaminetetraacetic Acid Calcium Salt salt, it is characterised in that this method includes following step Suddenly：（1）Desalted water is heated, then EDETATE SODIUM is separately added into again and calcium salt is reacted, until moisture is in solution 40%-80%；（2）EDETATE SODIUM or calcium salt are used again, and regulation pH value of solution is 6.5-7.5；（3）After solution is cooled to room temperature, alcohol is added, is stood after stirring；（4）After standing 3-10 hours, there is whiteness precipitation in solution, filter；（5）Solid matter after filtering is put in baking oven and is dried to constant weight, as Ethylenediaminetetraacetic Acid Calcium Salt product salt；（6）The detection of chelating degree and calcium ion content measure are carried out to Ethylenediaminetetraacetic Acid Calcium Salt product salt；（7）By step（4）Gained filtrate rectifying goes out alkoxide component and does precipitation agent use for experiment next time, and water component is used for next time Solvent use is done in experiment.
- 2. according to the method described in claims 1, it is characterised in that：The temperature of the heating desalted water is 50-100 DEG C.
- 3. according to the method described in claims 1, it is characterised in that：According to the molar ratio, described EDETATE SODIUM and calcium salt Dosage is 1:1-1.5.
- 4. according to the method described in claims 1, it is characterised in that：The calcium salt is selected from calcium carbonate, calcium hydroxide, oxidation One or more in calcium, calcium sulfate, calcium nitrate, calcium chloride.
- 5. according to the method described in claims 1, it is characterised in that：The step（3）Middle alcohol addition is the solution quality 0.8-2.5 times.
- 6. the method according to claims 1 or 5, it is characterised in that：Described alcohol is selected from methanol, ethanol, propyl alcohol, different One or more in propyl alcohol etc..
- 7. according to the method described in claims 1, it is characterised in that：The step（5）Middle drying temperature control is in 80-100 ℃。
- 8. according to the method described in claims 1, it is characterised in that：The step（7）Middle filtrate rectification temperature is 70-120 ℃。
- 9. according to the method described in claims 1, it is characterised in that：Ethylenediaminetetraacetic Acid Calcium Salt product salt has been carried out described in following method Chelating degree detection：Solution by product configuration into 1% concentration, add equimolar than potassium carbonate, stand 24 hours after without precipitation Produce, both thought exist in product without free state calcium.
- 10. according to the method described in claims 1, it is characterised in that：Calcium ion content is entered using atomic absorption spectrography (AAS) Row measure.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3681416A (en) * | 1968-10-29 | 1972-08-01 | Ciba Geigy Corp | Process for the production of metal chelates |
| CN102311358A (en) * | 2010-07-02 | 2012-01-11 | 天津金耀集团有限公司 | Calcium disodium edetate sterile raw material medicine and production process thereof |
| CN103172532A (en) * | 2011-12-02 | 2013-06-26 | 扬子江药业集团江苏海慈生物药业有限公司 | Preparation method of ethylenediaminetetraacetic acid calcium disodium salt |
| CN104230453A (en) * | 2013-06-08 | 2014-12-24 | 武邑县华风感光材料有限责任公司 | Production method for EDTA chelate efficient foliar fertilizer |
| CN106084570A (en) * | 2016-08-08 | 2016-11-09 | 陶如意 | A kind of heat conduction low free chlorine PVC pipeline and preparation method thereof |
| CN106636667A (en) * | 2016-12-23 | 2017-05-10 | 中南大学 | Method for recycling manganese and silver from manganese-silver ores |
-
2017
- 2017-09-26 CN CN201710877525.7A patent/CN107793322A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3681416A (en) * | 1968-10-29 | 1972-08-01 | Ciba Geigy Corp | Process for the production of metal chelates |
| CN102311358A (en) * | 2010-07-02 | 2012-01-11 | 天津金耀集团有限公司 | Calcium disodium edetate sterile raw material medicine and production process thereof |
| CN103172532A (en) * | 2011-12-02 | 2013-06-26 | 扬子江药业集团江苏海慈生物药业有限公司 | Preparation method of ethylenediaminetetraacetic acid calcium disodium salt |
| CN103172532B (en) * | 2011-12-02 | 2016-10-12 | 扬子江药业集团江苏海慈生物药业有限公司 | A kind of preparation method of ethylenediaminetetraacidic acidic calcium disodium salt |
| CN104230453A (en) * | 2013-06-08 | 2014-12-24 | 武邑县华风感光材料有限责任公司 | Production method for EDTA chelate efficient foliar fertilizer |
| CN106084570A (en) * | 2016-08-08 | 2016-11-09 | 陶如意 | A kind of heat conduction low free chlorine PVC pipeline and preparation method thereof |
| CN106636667A (en) * | 2016-12-23 | 2017-05-10 | 中南大学 | Method for recycling manganese and silver from manganese-silver ores |
Non-Patent Citations (2)
| Title |
|---|
| ANKUR GUPTA ETAL: "A General Route for Nanoemulsion Synthesis using Low Energy Methods at Constant Temperature", 《LANGMUIR》 * |
| 张天秀: "食品抗氧化剂EDTA钙钠盐制备工艺新探", 《食品科技》 * |
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