CN102766157B - A kind of method of producing technical-grade fosetyl-aluminum - Google Patents
A kind of method of producing technical-grade fosetyl-aluminum Download PDFInfo
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Abstract
The invention discloses a kind of method of producing technical-grade fosetyl-aluminum, in the method, phosphorus trichloride and ethanol are mixed continuously and carries out esterification generation phosphorous acid ester feed liquid; Described phosphorous acid ester feed liquid and mineral alkali are carried out saponification reaction continuously and generates ammonium phosphite feed liquid; Described ammonium phosphite feed liquid and water-soluble aluminum salt are carried out replacement(metathesis)reaction continuously and generates fosetylaluminium soup compound; Described fosetylaluminium soup compound carried out precipitate, be continuously separated, successive drying, obtain that fosetylaluminium content reaches 98%, total recovery reach 95%(in phosphorus trichloride) product.Production technique of the present invention is simple, easy to implement, speed of response is fast, side reaction is few, site environment is good, has significant economic benefit.
Description
Technical field
The present invention relates to field of pesticide preparation, specifically, relate to a kind of method of producing bactericide original drug.
Background technology
Fosetylaluminium is the former medicine of a kind of high-efficiency low-toxicity systemic fungicide developed by French Luo Na-Pu Langmai company, outward appearance is white solid powder, soluble in water, is insoluble in organic solution, volatility is little, meet soda acid easily to decompose, non-corrosiveness, nonflammable, non-explosive, the wet easily caking of wet, storage period is 3 years, belongs to low toxicity sterilant.Former powder rat acute LD50 of passing through mouth is 5800 mgs/kg, acute painting skin LD50 ﹥ 3200 mgs/kg.
The foreign patent documents of US4139616 such as, describe fosetylaluminium preparation technology, it take diethyl phosphite as raw material, and synthetic method is interrupter method, and plant factor is low, is economically not suitable for scale operation; The operational path that domestic current production adopts is for main raw material with phosphorus trichloride, dehydrated alcohol, 20% ammoniacal liquor, Solid aluminum sulfate, through esterification, saponification reaction, replacement(metathesis)reaction, total recovery is about 80%, and former medicine content is about 95%, and outward appearance is white powder.
Following shortcoming is there is: (1) adopts dehydrated alcohol, and cost is high in the method for the production fosetylaluminium of current domestic employing; (2) saponification and neutralization reaction adopt the dropping mode that ammoniacal liquor drips in phosphorous acid ester, and by product is many, yield is low; (3) replacement(metathesis)reaction employing Solid aluminum sulfate is directly fed in saponification reaction liquid and reacts, and long reaction time, by product are many, yield is low; (4) replacement(metathesis)reaction adopts Solid aluminum sulfate dosing method, and labor strength is large, site environment is poor, not easy to operate; (5) synthesis adopts interrupter method, and plant factor is low, efficiency is low, cost is high.
Summary of the invention
In order to shortcomings such as the cost solving prior art existence is high, yield is low, by product is many, long reaction time, not easy to operate, site environment is poor, the invention provides a kind of method of producing technical-grade fosetyl-aluminum, product yield and content are improved, and improve site environment, reduce labor strength.
The present invention relates to a kind of method of producing technical-grade fosetyl-aluminum, be achieved through the following technical solutions:
Produce a method for technical-grade fosetyl-aluminum, comprise the following steps:
Phosphorus trichloride and ethanol are mixed continuously and carries out esterification generation phosphorous acid ester feed liquid;
Described phosphorous acid ester feed liquid and mineral alkali are carried out saponification reaction continuously and generates ammonium phosphite feed liquid;
Described ammonium phosphite feed liquid and water-soluble aluminum salt are carried out replacement(metathesis)reaction continuously and generates fosetylaluminium soup compound;
Described fosetylaluminium soup compound carried out precipitate, be continuously separated, successive drying, obtain technical-grade fosetyl-aluminum.
Described esterification uses canned-motor pump to make phosphorus trichloride and ethanol after static mixing reactor mixes continuously by under meter, and enter esterifying kettle and carry out esterification, the reaction formula of esterification is as follows:
。
Described ethanol is 90% ethanolic soln by mass percentage.
Described saponification reaction is joined by inorganic alkali solution in reactor to carry out stirring, cooling, and drip phosphorous acid ester continuously, the reaction formula of saponification reaction is as follows:
。
Described mineral alkali adopts mass percent to be the ammonia soln of 10%.
Described replacement(metathesis)reaction is: be 80-85 DEG C in temperature, and in replacement(metathesis)reaction still, add ammonium phosphite feed liquid and water-soluble aluminum salt continuously, the reaction formula of replacement(metathesis)reaction is as follows simultaneously:
。
Described water-soluble aluminum salt adopts mass percent to be the alum liquor of 40%.
Compared with prior art, the present invention has the following advantages:
1, the present invention adopt mass percent be 90% ethanol, ethanol consumption can be reduced, reduce production cost, easy to operate;
2, the present invention adopts the mode that phosphorous acid ester drips in ammoniacal liquor, reduces phosphorous acid ester and decomposes in water, makes reaction yield improve about 10%;
3, the present invention is in metathesis process, adopts 40% alum liquor and saponification liquor to drip mode continuous synthesis simultaneously, and speed of response is fast, and side reaction is few, improves reaction yield and content, and improves the automatization level of operation;
4, the present invention adopts 40% liquid aluminium sulfate to participate in reaction in metathesis process, reduces site environment and pollutes, reduce labour intensity, improve equipment automatization level;
5, produce at present in the method for fosetylaluminium, mass content is about 95%, and total recovery is at 80%(phosphorus trichloride meter) left and right, mass content of the present invention reaches 98%, and total recovery reaches 95%(in phosphorus trichloride).
Accompanying drawing explanation
Fig. 1 is production technique circuit figure of the present invention.
Embodiment
In order to explain the present invention better, below in conjunction with Fig. 1, the present invention will be further described.In the examples below that, if no special instructions, " % " representation quality percentage ratio.
Embodiment 1
Phosphorus trichloride and ethanol are mixed continuously and carries out esterification.Concrete steps are: use canned-motor pump with the speed of 600Kg/ hour, the phosphorus trichloride of 600Kg99% and the ethanol of 600Kg90% to be mixed by under meter continuously through static mixing reactor (SV3.5/32), enter esterifying kettle, esterification temperature is 50-60 DEG C, vacuum tightness is 0.08MPa-0.09MPa, generate 680Kg phosphorous acid ester, wherein phosphorous acid ester by mass percentage content about 85%, produce byproduct hydrogen chloride and monochloroethane simultaneously, hydrogenchloride anhydrates absorption, and monochloroethane removes pressure recovery.
According to above-mentioned steps, dehydrated alcohol and concentration are that three groups of parallel reactor results of the ethanol of 90% illustrate in Table 1.
the ethanol synthesis experimental result of table 1 different concns
| Lot number | Ethanol charging capacity (Kg) | Alcohol concn (%) | Phosphorous acid ester (Kg) | Phosphorous acid ester content (%) | Phosphorous acid ester yield (%, in phosphorus trichloride) |
| 1 | 600 | Anhydrous | 680 | 84.9 | 96.3 |
| 2 | 600 | Anhydrous | 680 | 85.1 | 96.5 |
| 3 | 600 | Anhydrous | 680 | 84.9 | 96.2 |
| 4 | 600 | 90 | 680 | 85.1 | 96.4 |
| 5 | 600 | 90 | 680 | 85.1 | 96.5 |
| 6 | 600 | 90 | 680 | 84.9 | 96.2 |
Table 1 experimental result shows, adopt 90% ethanol carry out react obtain phosphorous acid ester content and yield can reach adopt dehydrated alcohol carry out react obtain phosphorous acid ester content and yield concentration.Specifically, when adopting 90% ethanol, phosphorous acid ester content average out to 85.0%, yield average out to 96.4%; When adopting dehydrated alcohol, phosphorous acid ester content average out to 85.0%, yield average out to 96.3%.Obviously, adopt 90% ethanol can reach equally adopt dehydrated alcohol time level, decrease ethanol consumption, reduce production cost.
Embodiment 2
The feed liquid generate embodiment 1 and mineral alkali carry out saponification reaction continuously, and this mineral alkali can be ammonia soln.Concrete steps are: by 800L mass percent be 10% ammoniacal liquor be added to 3000L lass lining aerofoil profile stirred autoclave, stir, open cooling water temperature, question response temperature in the kettle is down to 5 DEG C, start the phosphorous acid ester feed liquid that dropping embodiment 1 continuously obtains, carry out saponification reaction, in dropping process, keep temperature to be no more than 45 DEG C, time for adding 3-4 hour, be warming up to 45-50 DEG C after dropping terminates, reaction 3-5 hour, obtains ammonium phosphite feed liquid.In the present embodiment, adopt phosphorous acid ester to carry out three groups of parallel laboratory tests to the just dropping in ammonia soln and anti-dropping mode respectively, the results are shown in Table 2, wherein, just dripping and referring to that ammoniacal liquor drips in phosphorous acid ester solution, anti-dropping refers to that phosphorous acid ester drips in ammoniacal liquor.
table 2 different dropping mode experimental result
| Lot number | Dropping mode | Phosphorous acid ester feed liquid (Kg) | Single ethyl phosphorous acid ammonium content (%) | Single ethyl phosphorous acid ammonium yield (%, in phosphorus trichloride) |
| 1 | Just drip | 1,420 | 30.7 | 89.6 |
| 2 | Just drip | 1,420 | 30.6 | 89.5 |
| 3 | Just drip | 1,420 | 30.8 | 89.7 |
| 4 | Anti-dropping | 1,420 | 33.8 | 98.8 |
| 5 | Anti-dropping | 1,420 | 33.7 | 98.6 |
| 6 | Anti-dropping | 1,420 | 33.8 | 98.9 |
Table 2 experimental result shows, adopts the single ethyl phosphorous acid ammonium content and yield that instead drip and carry out reacting acquisition apparently higher than just dripping the single ethyl phosphorous acid ammonium content and yield concentration that carry out reacting acquisition.Specifically, adopting anti-dropping to carry out reacting the single ethyl phosphorous acid ammonium average content obtained is 33.8%, and average yield is 98.8%; Adopting and just dripping the single ethyl phosphorous acid ammonium average content carrying out reacting acquisition is 30.7%, and average yield is 89.6%.Obviously, adopt anti-drip single ethyl phosphorous acid ammonium content of carrying out reacting and obtaining and yield better, and with just drip compared with mode, its average yield improves 10.3%, reduces production cost.
Embodiment 3
First in preparation still, add 750Kg water, stir, add 50Kg Solid aluminum sulfate simultaneously, stirring and dissolving 0.5 hour, be mixed with 40% alum liquor, squeeze into scale tank, saponification list motor mix ammonium phosphite embodiment 2 obtained squeezes into another scale tank, open the blanking valve of alum liquor and ammonium phosphite solution scale tank simultaneously, enter continuously in replacement(metathesis)reaction still, react, controlling 40% Tai-Ace S 150 flow is 1,250Kg/ hour, ammonium phosphite solution flow is Isosorbide-5-Nitrae 20Kg/ hour.Temperature of reaction is 80-85 DEG C, namely reaction generates fosetylaluminium slurry instantaneously, slurry is separated through vacuum level band filter (filter cloth 300 order) continuous filtration, then the water that flow velocity is 100Kg/ hour is used to carry out continuous washing, be fed through XSG Rotatingandflashstreamingdrier continuously finally by wet mass transfer roller and carry out drying, packaging, obtains product.The different feed way adding ammonium phosphite solution with Tai-Ace S 150 carry out three groups of parallel contrast experiments, obtain fosetylaluminium respectively, the results are shown in Table 3.
table 3 different Tai-Ace S 150 feed way experimental result
| Lot number | Feed way | Fosetylaluminium (Kg) | Fosetylaluminium content (%) | Fosetylaluminium yield (%, in phosphorus trichloride) |
| 1 | Solid aluminum sulfate adds ammonium phosphite solution reaction | 483 | 95.6 | 90.2 |
| 2 | Solid aluminum sulfate adds ammonium phosphite solution reaction | 488 | 96.0 | 91.3 |
| 3 | Solid aluminum sulfate adds ammonium phosphite solution reaction | 486 | 95.7 | 90.8 |
| 4 | Tai-Ace S 150 is made into 40% solution and ammonium phosphite feed liquid dropwise reaction simultaneously | 499 | 98.0 | 95.6 |
| 5 | Tai-Ace S 150 is made into 40% solution and ammonium phosphite feed liquid dropwise reaction simultaneously | 502 | 97.9 | 96.0 |
| 6 | Tai-Ace S 150 is made into 40% solution and ammonium phosphite feed liquid dropwise reaction simultaneously | 498 | 98.1 | 95.5 |
Table 3 experimental result shows, the fosetylaluminium content that adopt Tai-Ace S 150 to be made into mode that 40% solution and ammonium phosphite feed liquid drip simultaneously obtains and yield add ammonium phosphite solution higher than Solid aluminum sulfate and react the fosetylaluminium content and yield concentration that obtain.Specifically, the fosetylaluminium content average content that adopt Tai-Ace S 150 to be made into mode that 40% solution and ammonium phosphite feed liquid drip simultaneously obtains is 98%, and average yield is 95.7%; Fosetylaluminium average content that ammonium phosphite solution reaction obtains is 95.8% to adopt Solid aluminum sulfate to add, and average yield is 90.8%, and obviously, it is better that Tai-Ace S 150 is made into the mode that 40% solution and ammonium phosphite feed liquid drip simultaneously.
Although illustrate and describe exemplary embodiments more of the present invention, but those skilled in the art should know, without departing from the principles and spirit of the present invention, can make change to these exemplary embodiments, scope of the present invention is limited by claim and equivalent thereof.
Claims (5)
1. produce a method for technical-grade fosetyl-aluminum, said method comprising the steps of:
Adopt static mixing reactor to mix continuously phosphorus trichloride and ethanol and carry out esterification generation phosphorous acid ester feed liquid;
Described phosphorous acid ester feed liquid and mineral alkali are carried out saponification reaction continuously and generates ammonium phosphite feed liquid;
Described ammonium phosphite feed liquid and water-soluble aluminum salt are carried out replacement(metathesis)reaction continuously and generates fosetylaluminium soup compound;
Described fosetylaluminium soup compound carried out precipitate, be continuously separated, successive drying, obtain technical-grade fosetyl-aluminum;
Described phosphorous acid ester feed liquid and mineral alkali being carried out continuously saponification reaction is joined by inorganic alkali solution in reactor to carry out stirring, cooling, and drips phosphorous acid ester continuously;
Described ammonium phosphite feed liquid and water-soluble aluminum salt are carried out replacement(metathesis)reaction is continuously: be 80-85 DEG C in temperature, in replacement(metathesis)reaction still, add ammonium phosphite feed liquid and water-soluble aluminum salt continuously simultaneously;
Described water-soluble aluminum salt adopts mass percent to be the alum liquor of 40%;
Described mineral alkali adopts mass percent to be the ammonia soln of 10%.
2. the method for production technical-grade fosetyl-aluminum according to claim 1, it is characterized in that, described phosphorus trichloride and ethanol are mixed continuously carry out esterification be use canned-motor pump make phosphorus trichloride and ethanol after static mixing reactor mixes continuously by under meter, enter esterifying kettle and carry out esterification, the reaction formula of esterification is as follows:
。
3. the method for production technical-grade fosetyl-aluminum according to claim 1 and 2, is characterized in that, described ethanol is 90% ethanolic soln by mass percentage.
4. the method for production technical-grade fosetyl-aluminum according to claim 1, is characterized in that, the reaction formula of described saponification reaction is as follows:
。
5. the method for production technical-grade fosetyl-aluminum according to claim 1, is characterized in that, the reaction formula of replacement(metathesis)reaction is as follows:
。
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| CN103238623A (en) * | 2013-05-24 | 2013-08-14 | 齐齐哈尔大学 | Novel copper bactericide and synthetic method thereof |
| CN105622332A (en) * | 2015-12-30 | 2016-06-01 | 利民化工股份有限公司 | Recovery method for chloroethane tail gas in fosetyl-aluminum production |
| CN106967114B (en) * | 2017-04-05 | 2020-01-17 | 利民化学有限责任公司 | Recycling comprehensive treatment method and system for fosetyl-aluminum wastewater |
| CN112661786A (en) * | 2020-12-24 | 2021-04-16 | 利民化学有限责任公司 | Method and system for preparing fosetyl-aluminum |
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| GB2017706A (en) * | 1978-03-24 | 1979-10-10 | Philagro Sa | Process for the manufacture of aluminium monoethylphosphite |
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| CN101891763A (en) * | 2009-05-19 | 2010-11-24 | 李其奎 | Production method of N-(phosphonomethyl)glycine |
| CN101955497A (en) * | 2009-11-09 | 2011-01-26 | 浙江嘉华化工有限公司 | Process technology for producing high content phosethyl-Al original drug |
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Patent Citations (7)
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|---|---|---|---|---|
| US4139616A (en) * | 1973-12-14 | 1979-02-13 | Pepro | Fungicidal compositions based on phosphorous acid esters and salts thereof |
| GB2017706A (en) * | 1978-03-24 | 1979-10-10 | Philagro Sa | Process for the manufacture of aluminium monoethylphosphite |
| US4272448A (en) * | 1978-03-24 | 1981-06-09 | Philagro | Process for the manufacture of aluminum monoethyl phosphite |
| CN1939926A (en) * | 2005-09-30 | 2007-04-04 | 北京清华紫光英力化工技术有限责任公司 | Production of glyphosate by glycine method |
| CN101525302A (en) * | 2009-04-30 | 2009-09-09 | 济南科赛基农化工有限公司 | Method for coproducing fungicide phosethyl-Al in acetochlor production |
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Effective date of registration: 20200119 Address after: 221400 Xinyi Economic Development Zone, Jiangsu, Xuzhou Patentee after: Limin Chemical Co., Ltd. Address before: 221400 Xinyi Economic Development Zone, Jiangsu, Xuzhou Patentee before: Limin Chemical Co., Ltd. |