CN101955497A - Process technology for producing high content phosethyl-Al original drug - Google Patents
Process technology for producing high content phosethyl-Al original drug Download PDFInfo
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- CN101955497A CN101955497A CN2009101537821A CN200910153782A CN101955497A CN 101955497 A CN101955497 A CN 101955497A CN 2009101537821 A CN2009101537821 A CN 2009101537821A CN 200910153782 A CN200910153782 A CN 200910153782A CN 101955497 A CN101955497 A CN 101955497A
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- fosetylaluminium
- ammonia
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Abstract
The invention relates to a process technology for producing a high content phosethyl-Al original drug, comprising the following steps of taking ethanol and phosphorus trichloride as starting materials, and carrying out reactions of esterification, amination dropping with ammonia as well as synthesis, centrifugation, dehydration, drying and the like of amide and aluminum sulfate. The process technology for producing the high content phosethyl-Al original drug is characterized in that the ethanol is absolute alcohol; the concentration of the ammonia taking part in the reaction is 12 percent, the ammonia dropping speed (temperature) is the reaction temperature in the ammonia dropping process and is controlled at 45-50 DEG C, and the ammonia dropping quantity is excess i.e. a final pH value is controlled at 7.5-8; the aluminum sulfate inventory is 1.00-1.05 times of the theoretical quantity, the synthesis original drug discharge temperature is 90 DEG C, and the synthesis reaction time is 1.5-2.5h. The process technology ensures the content is no less than 96 percent and also ensures the yield of the product (not lower than the traditional process level).
Description
One, technical field:
The present invention relates to produce the former pharmaceutical worker's technology of high-content fosetylaluminium.
Two, background technology:
The former medicine of fosetylaluminium be a kind ofly can in plant materials, make progress simultaneously, two-way feasible organophosphorus systemic fungicide downwards, have low toxicity, to honeybee, Lagomorpha and wildlife safety, non-corrosiveness, nonflammable explosive characteristics to people and animals.Its sterilization effect is good, and crop is had protection and therapeutic action.Eqpidemic disease and oidium to Phycomycetes have preventive effect preferably, are applicable to the various oidium of control on the cash crop such as fruit tree, vegetables, flowers, cotton, tobacco, rubber, hops, potato, viruses such as eqpidemic disease.
Producing at present the former medicine of fosetylaluminium, to adopt 95% ethanol, phosphorus trichloride be starting raw material, makes through reaction such as esterification, amination, centrifugal, dehydration, oven dry and step.
The former medicine preparation feedback of fosetylaluminium equation:
(1)3C
2H
5OH+PCl
3→(C
2H
5O)
2POH+2HCl↑+C
2H
5Cl↑
The former medicine technological process of production of fosetylaluminium synoptic diagram:
See accompanying drawing
The key element of its content raising is more, difficulty is bigger owing to influence, the Technology of the former medicine of producing of fosetylaluminium falls behind at present, be that relevant starting material are used and processing condition do not reach better, thereby the content of the former medicine of fosetylaluminium is only between 87%-90%, the highest can only reaching in 95%.Because former medicine content is low, impurity is many, causes the water-dispersible granules of processing environment-friendly type and the quality of wettable powder to be had a strong impact on, drug effect is reduced, and polluted environment.
Owing to can not reach high-content (〉=96%, down together) by the existing former medicine of Technology fosetylaluminium, influence the former medicine of fosetylaluminium successfully to enter the world market, especially Mei Jia and European Union market.Should improve the purity of product, the content of the former medicine of fosetylaluminium be reached 〉=96% guarantee product yield again, must improve present processing method.
Three, summary of the invention:
The technical problem that this patent mainly solves provides the former pharmaceutical worker's technology of a kind of production high-content (〉=96%) fosetylaluminium, the feasible purity that should guarantee to reach product, make content 〉=more than 96%, guarantee the yield (being not less than original state of the art) of product again, realize energy-saving and emission-reduction.
Thinking: do not changing substantially under the prerequisite of original operational path, we grope and medium and small experimental control through long-term practice, carried out the critical process condition optimizing, it is starting raw material that the former medicine of high-content fosetylaluminium adopts dehydrated alcohol, phosphorus trichloride, make through reactions such as esterification, aminations, by providing synthesis technique promptly: 1. improve diethyl phosphite content improve the aminate quality, 2. improve the aminate quality, 3. adjust building-up reactions charge ratio, 4. synthetic former medicine drop temperature, thereby make the former medicine content of fosetylaluminium 〉=more than 96%.
Technical solution of the present invention is: produce the former pharmaceutical worker's technology of high-content fosetylaluminium, with ethanol, phosphorus trichloride is starting raw material, reactions such as synthetic, centrifugal, the dehydration of amination, aminate and the Tai-Ace S 150 that drips through esterification, ammoniacal liquor, oven dry, it is characterized in that: described ethanol is raw spirit; The ammonia concn of participating in amination reaction is 12%, and the temperature of reaction when ammoniacal liquor rate of addition (temperature) drips for ammoniacal liquor is controlled at 45-50 ℃, and the ammoniacal liquor dripping quantity is suitably excessive, i.e. endpoint pH control 7.5-8; The Tai-Ace S 150 charging capacity is 1.00～1.05 times of theoretical amount, and synthetic former medicine drop temperature is 90 ℃, and synthesising reacting time was at 1.5-2.5 hour.Above-mentioned raw spirit is 99% dehydrated alcohol, and terminal point p H value optimum control is 8, and synthesising reacting time the best is 2 hours.
The former pharmaceutical worker's technology of above-mentioned production high-content fosetylaluminium makes its content 〉=more than 96%, guaranteed the yield (being not less than original state of the art) of product again, has realized energy-saving and emission-reduction.
Four, description of drawings
Accompanying drawing is the former medicine technological process of production of a fosetylaluminium synoptic diagram
Five, embodiment:
Embodiment: produce the former pharmaceutical worker's technology of high-content fosetylaluminium, with ethanol, phosphorus trichloride is starting raw material, reactions such as synthetic, centrifugal, the dehydration of amination, aminate and the Tai-Ace S 150 that drips through esterification, ammoniacal liquor, oven dry, it is characterized in that: described ethanol is 99% raw spirit; The ammonia concn of participating in amination reaction is 12%, and the temperature of reaction when ammoniacal liquor rate of addition (temperature) drips for ammoniacal liquor is controlled at 45-50 ℃, and the ammoniacal liquor dripping quantity is suitably excessive, i.e. terminal point p H value control 8; The Tai-Ace S 150 charging capacity is 1.00～1.05 times of theoretical amount, and synthetic former medicine drop temperature is 90 ℃, and synthesising reacting time was at 2 hours.
The former pharmaceutical worker's technology of above-mentioned production high-content fosetylaluminium makes its content 〉=more than 96%, guaranteed the yield (being not less than original state of the art) of product again, has realized energy-saving and emission-reduction.Relevant test situation is as follows:
1. improve the test of diethyl phosphite content
The diethyl phosphite production technique is to generate diethyl phosphite and monochloroethane and hydrogenchloride by ethanol and phosphorus trichloride generation esterification.Reaction equation is as follows:
Main reaction: 3C
2H
5OH+PCl
3→ (C
2H
5O)
2POH+2HCl ↑+C
2H
5Cl ↑
Side reaction: 3C
2H
5OH+PCl
3→ 3C
2H
5Cl+H
3PO
3
The production of diethyl phosphite is a thermopositive reaction, there is being the high condition subordinate of water, acidity and temperature easily to decompose, therefore shift reaction heat and drain the sour gas such as hydrogenchloride of generation as early as possible in process of production prevents the decomposition of diethyl phosphite, to improve its content.
At above-mentioned processing requirement, in production test, raw material selected for use and done some adjustment.Main raw material alcohol in the original production process uses 95% industrial spirit always, contains the moisture about 5% in 95% industrial spirit, certainly will cause the part phosphorus trichloride to decompose and generate hydrogenchloride and phosphorous acid.Because the existence of water and acidic substance impels the decomposition of diethyl phosphite easily.According to this specific character, we change 95% industrial spirit of former usefulness into 99% raw spirit, and have carried out synthetic test.This test is carried out in production equipment.(see Table 1, table 2)
Table 199% raw spirit test-results
Table 295% industrial spirit test-results
Can find out that from table 1, table 2 the diethyl phosphite quality of making the raw material production gained with raw spirit will get well, its content exceeds 15.6% than the product of making raw material production with 95% industrial spirit, and acidity reduces by 3.78%.
2. improve the test of aminate quality
The amination production technique is that diethyl phosphite and ammonium hydroxide reaction generate aminate, deviates from ethanol simultaneously.Reaction equation is as follows:
Diethyl phosphite is having decomposition easily under water and the acidic conditions, for this reason, cross the long control that contacts and be convenient to speed of response in order to take precautions against in diethyl phosphite and the ammoniacal liquor moisture, be earlier diethyl phosphite to be thrown in the amination pot in actual production, dropping ammonia under the situation of cooling and stirring, reaction process are exothermic process.Key in this process is to control the definite of ammonia concn, rate of addition (temperature) and dropping terminal point well.This test is carried out in the 1000mL four-hole boiling flask, and band stirs, and adopts the water-bath cooling, and the used diethyl phosphite content of the every batch of test is all identical with charging capacity, and its batch charging capacity is 400g, and content is 92.4%.(see Table 3, table 4, table 5)
Table 3 ammonia concn control test
From test situation, the ammonia concn of participating in reaction is to the content of synthetic former medicine and yield considerable influence all.As can be seen from Table 3, under equal conditions, the ammonia concn of selection 12% is comparatively favourable to preparing former medicine raising content and yield.
Table 4 ammoniacal liquor rate of addition (temperature) test
Under equal conditions, ammoniacal liquor rate of addition (temperature) has certain influence to the content of former medicine.Temperature of reaction when ammoniacal liquor drips as can be seen from Table 4 is controlled at 45-50 ℃ and is advisable.
Table 5 terminal point p H value control test
It is exactly to control ammonia volume that control ammoniacal liquor drips terminal point actual, and the ammoniacal liquor dripping quantity can be suitably excessive as can be seen from Table 5, and promptly terminal point p H value is controlled at 7.5-8, is preferably 8, and is favourable to improving former medicine content, but excessive too many former medicine content can descend again.
3. adjust the test of building-up reactions charge ratio
Building-up reactions claims replacement(metathesis)reaction again, and aminate and reacting aluminum sulfate generate fosetylaluminium, generate by product ammonium sulfate simultaneously.Reaction equation is as follows:
+3(NH
4)
2SO
4+18H
2O
React completely for guaranteeing in actual production, the Tai-Ace S 150 proportioning is suitably excessive.Accumulate in easily in the former medicine too much but Tai-Ace S 150 is excessive, former medicine content is reduced.How much Tai-Ace S 150 is excessive is advisable, and is the emphasis of test.This test is carried out in production equipment.(seeing Table 6)
The test of table 6 Tai-Ace S 150 charge ratio
Annotate: diethyl phosphite (diethyl ester amount+mono ethyl ester amount) charging capacity/Tai-Ace S 150 content conversion is pressed in the calculating of the charging capacity of Tai-Ace S 150.
Situation from test, the control of Tai-Ace S 150 charging capacity has considerable influence to the content of synthetic former medicine, as can be seen from Table 6, in order to guarantee to react completely, consider that simultaneously Tai-Ace S 150 accumulates less in synthetic former medicine, general Tai-Ace S 150 charging capacity is advisable with theoretical amount, promptly press the theoretical charging capacity of the Tai-Ace S 150 of diethyl phosphite (diethyl ester amount+mono ethyl ester amount) charging capacity conversion, must not surpass 5% at most, promptly the Tai-Ace S 150 charging capacity feeds intake by 1.00～1.05 of theoretical amount.
4. synthetic former medicine drop temperature is handled the influence test to quality product
Building-up reactions leaves by product ammonium sulfate and excessive Tai-Ace S 150 after finishing in the former medicine, former medicine is slightly soluble in water, and ammonium sulfate and Tai-Ace S 150 are all water-soluble.In order to improve former medicine quality product, the drop temperature that synthesizes former medicine in the process control of former medicine separating and dehydrating all has bigger influence with the control of setting up washing amount in the filter cake washing step to former medicine quality and recovery rate.In what temperature bottom discharge centrifuge dehydration, how much water yield control of centrifugal back filter cake (finished product) water flushing is advisable and has also been carried out corresponding test.(seeing Table 7)
The influence test of table 7 drop temperature
As seen, drop temperature with 90 ℃ for well.
Economic benefit and social benefit after the project implementation of employing present technique
1, technical target of the product is reached advanced world standards comprehensively after the project implementation:
Measured result: be that Zhejiang Province agriculture chemical examination administrative institute measures report number 2008DJ339.
2, economic benefit
Estimate 2,000 ten thousand yuan of year newly-increased sales revenue after this project implementation, 4,000,000 yuan of newly-increased profits taxes, 2,500,000 dollars of newly-increased foreign exchange earnings.
3, social benefit
After this project implementation, at one stroke broken through the REACH of European Union rules, made my company's quality product exceed the requirement of China's industry standard all sidedly, reached advanced international standard the limiting of the former medicine quality index of fosetylaluminium.It will advance the upgrading of China's Pesticidal products industry standard, advance improving constantly of pesticide intermediate quality.The invention enterprise of the former medicine of fosetylaluminium-Bayer crop science company limited represents: after good magnificent product is up to standard, just advance to purchase the product that uses Jia Hua company specially.The said firm took charge of to me and has into purchased 600 tons of former medicines in 2008.This is just for continuing and lay a good foundation in expand export EU countries and market, America, for positive contribution has been made in the production development that promotes China's chemical industry.
Claims (4)
1. produce the former pharmaceutical worker's technology of high-content fosetylaluminium for one kind, with ethanol, phosphorus trichloride is starting raw material, reactions such as synthetic, centrifugal, the dehydration of amination, aminate and the Tai-Ace S 150 that drips through esterification, ammoniacal liquor, oven dry, it is characterized in that: described ethanol is raw spirit; The ammonia concn of participating in amination reaction is 12%, and the temperature of reaction when the ammoniacal liquor rate of addition is the ammoniacal liquor dropping is controlled at 45-50 ℃, and the ammoniacal liquor dripping quantity is controlled at endpoint pH 7.5-8; The Tai-Ace S 150 charging capacity is 1.00～1.05 times of theoretical amount, and synthetic former medicine drop temperature is 90 ℃, and synthesising reacting time was at 1.5-2.5 hour.
2. the former pharmaceutical worker's technology of production high-content fosetylaluminium according to claim 1, it is characterized in that: described raw spirit is 99% dehydrated alcohol.
3. the former pharmaceutical worker's technology of production high-content fosetylaluminium according to claim 1, it is characterized in that: described endpoint pH is controlled to be 8.
4. the former pharmaceutical worker's technology of production high-content fosetylaluminium according to claim 1, it is characterized in that: described synthesising reacting time is 2 hours.
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|---|---|---|---|
| CN2009101537821A CN101955497A (en) | 2009-11-09 | 2009-11-09 | Process technology for producing high content phosethyl-Al original drug |
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|---|---|---|---|
| CN2009101537821A CN101955497A (en) | 2009-11-09 | 2009-11-09 | Process technology for producing high content phosethyl-Al original drug |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268033A (en) * | 2011-06-16 | 2011-12-07 | 浙江嘉华化工有限公司 | Production method of sodium O-ethyl phosphate |
| CN102766157A (en) * | 2012-09-05 | 2012-11-07 | 利民化工股份有限公司 | Method for producing technical-grade fosetyl-aluminum |
| CN106543219A (en) * | 2015-09-22 | 2017-03-29 | 浙江嘉华化工有限公司 | A kind of method for preparing high-load technical-grade fosetyl-aluminum |
-
2009
- 2009-11-09 CN CN2009101537821A patent/CN101955497A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268033A (en) * | 2011-06-16 | 2011-12-07 | 浙江嘉华化工有限公司 | Production method of sodium O-ethyl phosphate |
| CN102766157A (en) * | 2012-09-05 | 2012-11-07 | 利民化工股份有限公司 | Method for producing technical-grade fosetyl-aluminum |
| CN102766157B (en) * | 2012-09-05 | 2015-11-11 | 利民化工股份有限公司 | A kind of method of producing technical-grade fosetyl-aluminum |
| CN106543219A (en) * | 2015-09-22 | 2017-03-29 | 浙江嘉华化工有限公司 | A kind of method for preparing high-load technical-grade fosetyl-aluminum |
| CN106543219B (en) * | 2015-09-22 | 2018-07-27 | 浙江嘉华化工有限公司 | A method of preparing high-content technical-grade fosetyl-aluminum |
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Application publication date: 20110126 |