CN1064688C - Dichlorvos producing technology - Google Patents
Dichlorvos producing technology Download PDFInfo
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- CN1064688C CN1064688C CN96106328A CN96106328A CN1064688C CN 1064688 C CN1064688 C CN 1064688C CN 96106328 A CN96106328 A CN 96106328A CN 96106328 A CN96106328 A CN 96106328A CN 1064688 C CN1064688 C CN 1064688C
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- trichlorphon
- alkaline hydrolysis
- weak base
- highly basic
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Abstract
The present invention relates to a new technology for producing dichlorvos of organic phosphorus pesticide. Under the condition that the technological line generally used in China of trichlorfon alkaline hydrolysis is not changed, the compounding ratios, formulas and technologies of reaction materials are optimized, which enables the synthesis yield of dichlorvos to trichlorfon to be improved to about 90%, and the crude oil of the produced dichlorvos is stabilized to 95% to 99% (by a chemical analysis method). The present invention has the advantages of strong practicability, little investment, rapid action, high profit, stable product quality, simple technology, less 'three waste', etc.
Description
The present invention relates to the novel process that Trichlorphon alkaline hydrolysis legal system is equipped with SD-1750.SD-1750 is a kind of high-efficiency low-toxicity organic phosphorous insecticide, and its chemical structural formula is
Once had many technical information to report the preparation method of SD-1750 both at home and abroad, wherein main method is Trichlorphon alkaline hydrolysis method and trimethyl phosphite and the direct acting position rotaring rearrangement method of trichoro-aldehyde (ester-interchange method).
Patents such as EP 69442, DD 112273, US 2956073 have reported that all the position rotaring rearrangement method synthesizes SD-1750, adopt this method to have the advantages that yield is higher, consumption is lower, but this method exists crude content not high enough, yield is subjected to the bigger shortcoming of raw material trimethyl quality influence, and the stench of trimethyl all has baneful influence to environment and workman's physical and mental health.
Patent reports such as U.S.S.R.814280/545647 with the synthetic SD-1750 of highly basic alkaline hydrolysis Trichlorphon, this method is compared with ester-interchange method, raw material is easy to get, easy and simple to handle, produce stablize, crude content is higher, facility investment is less, is convenient to industrial production.
At present industrial, the domestic Trichlorphon alkaline hydrolysis method production SD-1750 that adopt more, this method is in the mixed solvent of water and organic solvent, Trichlorphon is carried out alkaline hydrolysis with highly basic sodium hydroxide come the production SD-1750.Its reaction formula is as follows:
Production process is as follows:
Drop into water, benzene (or trieline etc.), Trichlorphon in the reactor successively, under 20～30 ℃ of temperature, with the disposable adding of liquid caustic soda (3O%NaOH solution), need 1～5 minute approximately, liquid caustic soda adds serge, continue to stir 10～15 minutes, top temperature is about 68 ℃, after reaction finishes, and standing demix, the thick product precipitation that reduces pressure promptly gets DDVP oil.
In RO 58663, reported with weak base such as yellow soda ash alkaline hydrolysis Trichlorphon to prepare SD-1750, but yield can only reach 8O%, and the reaction times is longer, is unsuitable for industrial production.
The present inventor has been carried out understanding in depth by existing Trichlorphon alkaline hydrolysis method production technique and a large amount of experiment is found: use excessive alkali in the old technology, in alkaline hydrolysis Trichlorphon, also can be with the further alkaline hydrolysis of SD-1750 that generates, but the alkali deficiency can cause the Trichlorphon alkaline hydrolysis incomplete again.In addition, alkaline hydrolysis Trichlorphon is to carry out in immiscible two-phase, and two-phase proportion differs bigger, therefore, this reaction pair stirs and requires the efficient height, and the equipment state of old technology generally all is difficult to reach mass transfer, heat-transfer effect preferably at present, and this just causes the local anti-generation of alkaline hydrolysis of paying easily.Above-mentioned all multifactor old technology of present domestic Trichlorphon alkaline hydrolysis method production SD-1750 that makes exists the shortcoming that yield is on the low side, consumption is higher.SD-1750 (folding hundred) is generally 70～79% to the yield of Trichlorphon (folding hundred), and crude content is also not too high, and great majority are lower than 95% (chemical analysis).
Adopt highly basic and weak base successively to add to come two alkali alkaline hydrolysis methods of the synthetic SD-1750 of alkaline hydrolysis Trichlorphon, yet there are no report.
The present inventor found through experiments, weak base is alkaline hydrolysis Trichlorphon optionally, and be not easy to react with SD-1750, can remedy the alkaline shortcoming, therefore add a part of highly basic earlier, most of Trichlorphon alkaline hydrolysis, add weak base again and come alkaline hydrolysis residue Trichlorphon, effect should be better with highly basic than single, and the result proves so really can obtain high yield and high-content, so finished improvement synthetic method of the present invention.
Method according to improved synthetic SD-1750 of the present invention, on the basis of existing Trichlorphon alkaline hydrolysis method, the present inventor has carried out the industrial experiment of a large amount of reaction mass proportionings and manufacturing condition optimization, can increase substantially the new process of production that SD-1750 is produced yield and improved DDVP oil content thereby formed.
The change that the present invention is done old explained hereafter condition has:
1, in the selection of reaction mass
Use weak base such as Na
2CO
3, K
2CO
3, ammoniacal liquor, ammonia, NaHCO
3, KHCO
3, one or more and highly basic (as NaOH, KOH) in the triethylamine, pyridine etc. is used as the used alkali of alkaline hydrolysis Trichlorphon, substitutes single highly basic NaOH.
2, on reaction conditions
Under certain temperature and time conditions, add highly basic and above-mentioned weak base with elder generation's weak order in strong back.
3, on industrial equipments
In industrial alkaline hydrolysis still, inner coil pipe, guide shell or flow-stopping plate are installed, to strengthen the mass-and heat-transfer effect.
The present invention to the condition of SD-1750 production technology optimization is:
1, with weak base (as Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, ammoniacal liquor, ammonia, triethylamine, pyridine etc.) be used as the used alkali of alkaline hydrolysis Trichlorphon with highly basic (as NaOH, KOH), preferred highly basic is NaOH and KOH, weak base is Na
2CO
3, K
2CO
3, ammoniacal liquor and ammonia.Highly basic and weakly alkaline ratio can be allocated according to different situations, generally are greater than 3.Add the alkali mode and add weak base after adding highly basic earlier, alkali all can with solution, solid or gas form.Above-mentioned weak base can be wherein one or more, when two or more weak base uses jointly, whole weak base can be mixed adding or adding successively, and control total alkali equivalent is about normal 1.0～5.0 times of Trichlorphon, is preferably 1.5～3.0 times.
2, the alkaline hydrolysis reaction control temperature is: the alkaline hydrolysis starting temperature is 15～45 ℃, and top temperature is lower than 70 ℃, and the alkaline hydrolysis time is 1～60 minute, is preferably 10～60 minutes.
3, in the industrial alkaline hydrolysis still inner coil pipe, guide shell or flow-stopping plate are housed.
Novel process of the present invention has been carried out omnibearing optimization to the various conditions of the old technology of Trichlorphon alkaline hydrolysis method production SD-1750, substantially do not changing production process route, the equipment of industrial product changes under the little situation, make SD-1750 produce yield and bring up to about 90%, crude content is stabilized in more than 95% (chemical analysis).It has advantages such as little, the instant effect of investment, yield height, the three wastes are few.
For helping better to understand the present invention, below enumerate the lab scale experiment under some processing condition and embodiment, the reference examples (DDVP represents SD-1750 in the example) of industrial experiment.
Table 1: for novel process part industrial experiment result (weight unit is Kg, temperature ℃, content and yield are %,
Synopsis 1 together)
Synopsis 1: be old process portion industrial production results
Test-results shows: the reaction conditions of adopting new technology, can not only make SD-1750 produce yield and improve more than 8% (average out to 88.91%), and can make the DDVP oil stable content of producing at higher level (chemical analysis average content 97.91%).
Novel process can be continued to use the mixed solvent of forming in water and various organic solvent such as benzene, trieline, toluene, chloroform, tetracol phenixin etc., confirms as the result of embodiment 1 to embodiment 8.
Table 1. novel process part industrial experiment result
Reactant section and consumption thereof: Trichlorphon 300kg, 137 liters of 30%NaOH, solid Na
2CO
322kg
Solvent: 260 liters of trielines, water 800kg
| The test lot number | Throw the Trichlorphon amount | The reaction top temperature | DDVP crude oil | Yield | |||||
| Lot number | Roll over hundred gross weights | Must measure | Contain DDVP | Contain Trichlorphon | Acidity | Moisture content | |||
| 1 | 3 | 800 | 50～56 | 640 | 95.48 | 0.89 | 0.12 | 0.03 | 88.95 |
| 2 | 4 | 1064 | 54～56 | 874 | 96.85 | 1.71 | 1.10 | 0.02 | 92.66 |
| 3 | 4 | 101.9 | 53～55 | 787 | 98.09 | 1.90 | 0.12 | 0.05 | 88.20 |
| 4 | 4 | 1082 | 52～59 | 819 | 98.14 | 1.95 | 0.17 | ″ | 86.65 |
| 5 | 4 | 1234 | 50～55 | 932 | 99.00 | 0.63 | 0.15 | ″ | 87.14 |
| 6 | 5 | 1039 | 50～55 | 793 | 98.79 | 0.59 | 0.16 | ″ | 87.87 |
| 7 | 4 | 1072 | 53～55 | 875 | 97.37 | 1.61 | 0.10 | 0.03 | 92.61 |
| 8 | 4 | 1097 | 54～59 | 830 | 99.00 | 0.88 | 0.10 | 0.02 | 87.18 |
| On average | 97.91 | 88.91 | |||||||
Synopsis 1 old process portion production result.
Reaction mass and consumption thereof: Trichlorphon 300kg, 165 liters of 30%NaOH
Solvent: 260 liters of trielines, water 800kg
| The test lot number | Throw the Trichlorphon amount | The reaction top temperature | DDVP crude oil | Yield | |||||
| Lot number | Roll over hundred gross weights | Must measure | Contain DDVP | Contain Trichlorphon | Acidity | Moisture content | |||
| 1 | 10 | 2722 | 54～58 | 1881 | 97.5 | 1.01 | 0.10 | 0.03 | 78.5 |
| 2 | 12 | 3168 | 55～59 | 2220 | 97.0 | 0.81 | 1.12 | 0.03 | 79.2 |
| 3 | 8 | 1920 | 53～59 | 1329 | 97.2 | 1.10 | 0.10 | 0.04 | 78.40 |
| 4 | 10 | 2850 | 54～60 | 1986 | 95.8 | 1.12 | 0.15 | 0.05 | 77.85 |
| 5 | 9 | 2484 | 54～57 | 1722 | 96.8 | 0.73 | 0.13 | 0.03 | 78.24 |
| 6 | 10 | 2670 | 52～60 | 1862 | 97.0 | 0.93 | 0.10 | 0.02 | 78.87 |
| 7 | 12 | 3192 | 51～59 | 2229 | 96.57 | 1.98 | 0.12 | 0.05 | 79.51 |
| 8 | 10 | 2745 | 50～58 | 1909 | 97.50 | 0.80 | 0.12 | 0.02 | 79.0 |
| On average | 96.91 | 78.55 | |||||||
[industrial implementation example 1]
Under the new process conditions.Under 30 ℃, with 260 liters of trielines, 800kg water, 300Kg 88.47% Trichlorphon drops into the alkaline hydrolysis still successively, stirs down to add 136 liters of 30%NaOH, stirs after 3 minutes, adds 22kg solid Na
2CO
3, continue to stir 10 minutes 53 ℃ of reaction top temperatures, standing demix, thick oil obtains DDVP crude oil 216kg behind falling liquid film, still decompression precipitation, chemical analysis records and contains DDVP98.0%, Trichlorphon content 1.5%, acidity 0.10%, moisture content 0.03%, yield 93.0%.[industrial reference examples 1]
Old processing condition.Under 25 ℃, with 260 liters of trielines, 800Kg water, 304Kg 90% Trichlorphon drops in the alkaline hydrolysis still successively, stirs down 170 liters of 30%NaOH are added the alkaline hydrolysis still, and the reaction top temperature is 52 ℃, stirring reaction 3 minutes, standing demix, thick oil is behind falling liquid film, still decompression precipitation, obtain DDVP crude oil 191Kg, chemical analysis records and contains DDVP96%, Trichlorphon content 0.8%, acidity 0.15%, moisture content 0.03%, yield 78%.[industrial implementation example 2]
Under the new process conditions.Under 30 ℃, with 260 liters of trielines, 800kg water, 300kg 89.5% Trichlorphon drops into the alkaline hydrolysis still successively, stirs down to add 133 liters of 30%NaOH, reacts 3 minutes, adds 220 liters of 10%Na
2CO
3Solution continues reaction 5 minutes, 56 ℃ of reaction top temperatures, standing demix, thick oil obtains DDVP crude oil 213kg behind falling liquid film, still decompression precipitation, chemical analysis records crude oil and contains DDVP99.0%, Trichlorphon content 0.6%, acidity 0.1%, moisture content 0.03%, yield 91.2%.[embodiment 1] toluene solvant
Under the room temperature, with 52ml toluene, 160kg water, 60kg90% Trichlorphon places reaction flask, stirs down to add 38g30%NaOH, reacts 3 minutes, adds 5.5g solid Na
2O
3, continue to stir 10 minutes 55 ℃ of reaction top temperatures.Standing demix, thick oil obtains DDVP crude oil 44g behind the decompression precipitation, and chemization is analysed method and is recorded crude oil and contain DDVP97.8%, yield 92.9%.[reference examples 1] toluene solvant
Under the room temperature, with 52ml toluene, 160g water, 60g 90% Trichlorphon places reaction flask, stir and add 44g30%NaOH down, reacted 56 ℃ of reaction top temperatures, standing demix 3 minutes, thick oil is behind the decompression precipitation, obtain DDVP crude oil 37.5g, chemical analysis records crude oil and contains DDVP95.8%, yield 77.6%.[reference examples 2] toluene solvant
Under the room temperature, with 52ml toluene, 120g water, 60g90% Trichlorphon places reaction flask, stirs to add 22g solid Na down
2CO
3, reacted 30 minutes, 56 ℃ of reaction top temperatures, standing demix, thick oil obtains DDVP crude oil 40.5g behind the decompression precipitation, and chemical analysis records crude oil and contains DDVP91.8%, yield 80.3%.[embodiment 2] benzene solvent
Under the room temperature, with 85ml benzene, 140g water, 60g91% Trichlorphon drop in the reaction flask, stir down to add 39g30%NaOH, react 3 minutes, add 5.5g solid Na
2CO
3, continuing to stir 10 minutes, 65 ℃ of reaction top temperatures leave standstill branch, and thick oil obtains DDVP crude oil 43.59 behind the decompression precipitation, and chemical analysis records and contains DDVP97.0% in the crude oil, yield 90%.[reference examples 1] benzene solvent
Under the room temperature, with 85ml benzene, 140g water, 60g91% Trichlorphon places reaction flask, add 43g30%NaOH under stirring, reacted 59 ℃ of reaction top temperatures, standing demix 15 minutes, thick oil is after underpressure distillation, obtain DDVP crude oil 38g, chemical analysis records and contains DDVP95.2%, yield 78.1%.[embodiment 3] chloroform solvent
Under the room temperature, with the 52ml chloroform, 160g water, 58g90.2% Trichlorphon places reaction flask, stirs down to add 38g 30%NaOH, reacts after 3 minutes, adds 55g10%Na
2CO
3Solution continues reaction 8 minutes, 50 ℃ of reaction top temperatures, and standing demix, thick oil obtains DDVP crude oil 41.79 behind the decompression precipitation, and chemical analysis records and contains DDVP98.5% in the crude oil, yield 88.7%.[embodiment 4] carbon tetrachloride solvent
Reaction conditions is identical with embodiment 3, and the result is: DDVP crude oil 41.09, chemical analysis record and contain DDVP98.0% in the crude oil, yield 86.4%.[embodiment 5] chloroform solvent
Under the room temperature, with the 52ml chloroform, 160g water, 58g90.2% Trichlorphon places reaction flask, stirs down to add 38g30%KOH, reacts after 3 minutes, adds 55g10%K
2CO
3Solution continues reaction 8 minutes, 55 ℃ of reaction top temperatures, and standing demix, thick oil obtains DDVP crude oil 42.7g behind the decompression precipitation, and chemical analysis records and contains DDVP97.5% in the crude oil, yield 89.7%.[embodiment 6] NaOH+ ammoniacal liquor
Under the room temperature, with 85ml benzene, 140g water, 60g90% Trichlorphon places reaction flask, stirs down to add 39g30%NaOH, reacts 3 minutes, add 8g28% ammoniacal liquor then, continue to stir 10 minutes 52 ℃ of reaction top temperatures, standing demix, thick oil is after underpressure distillation, obtain DDVP crude oil 41g, chemical analysis records and contains DDVP98.2% in the crude oil, yield 87%.[embodiment 7] NaOH+NaHCO
3+ KHCO
3+ K
2CO
3+ Na
2CO
3
Under the room temperature, with the 52ml chloroform, 160g water, 60g90% Trichlorphon drop in the reaction flask, stir down 10g30%NaOH is added, and react after 3 minutes, add 6.4gNaHCO
3/ 7.6gKHCO
3/ 5.2gK
2CO
3/ 4gNa
2CO
3Mixture reacted 5 minutes, 55 ℃ of reaction top temperatures, and standing demix, thick oil obtains DDVP crude oil 41g after underpressure distillation, and chemical analysis records and contains DDVP96.5% in the crude oil, yield 85%.[embodiment 8] NaOH+NH
3
Under the room temperature, with 85ml benzene, 140g water, 60g90% Trichlorphon drop in the reaction flask, stir down to add 35g30%NaOH, react after 3 minutes, feed 2gNH in reaction solution
3, continue to stir 10 minutes, 55 ℃ of reaction top temperatures, standing demix, thick oil obtains DDVP crude oil 42.1g after underpressure distillation, and chemical analysis records and contains DDVP97.5% in the crude oil, yield 88.4%.
Claims (12)
1, a kind of method for preparing SD-1750, it is raw material with Trichlorphon, and the Trichlorphon alkaline hydrolysis is generated SD-1750, it is characterized in that: be used with highly basic and weak base Trichlorphon is carried out two alkaline hydrolysis.
2, according to the method for claim 1, used highly basic is sodium hydroxide and potassium hydroxide.
3, according to the method for claim 2, used weak base is: yellow soda ash, salt of wormwood, ammonia, ammoniacal liquor, sodium bicarbonate, saleratus, triethylamine, pyridine.
4, according to the method for claim 3, used weak base is yellow soda ash, salt of wormwood, ammoniacal liquor and ammonia.
5, according to the method for claim 1～4, highly basic and weakly alkaline total yield are normal 1.0～5.0 times of Trichlorphon.
6, according to the method for claim 1～4, the alkaline hydrolysis starting temperature is 15～45 ℃, and top temperature is no more than 70 ℃, and the alkaline hydrolysis time is 10～60 minutes.
7, according to the method for claim 1～4, weak base can be solid-state, solution or gas.
8, according to the method for claim 1～4, add highly basic earlier, after add weak base.
9, according to the method for claim 1～4, two kinds (containing two kinds) can mix whole weak base adding or adding successively earlier when above weak base uses jointly.
10, according to the method for claim 1～4, the reaction system solvent is water and organic solvent.
11, according to the method for claim 10, organic solvent is trieline, benzene, toluene, chloroform, tetracol phenixin.
12,, inner coil pipe, guide shell or flow-stopping plate are installed in the industrial alkaline hydrolysis still according to the method for claim 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106328A CN1064688C (en) | 1996-06-17 | 1996-06-17 | Dichlorvos producing technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106328A CN1064688C (en) | 1996-06-17 | 1996-06-17 | Dichlorvos producing technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1168380A CN1168380A (en) | 1997-12-24 |
| CN1064688C true CN1064688C (en) | 2001-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106328A Expired - Fee Related CN1064688C (en) | 1996-06-17 | 1996-06-17 | Dichlorvos producing technology |
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|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234292B (en) * | 2010-04-30 | 2013-12-18 | 山东大成农化有限公司 | New process for dipterex purification |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD144264A5 (en) * | 1978-06-15 | 1980-10-08 | Inst Przemyslu Organiczego | PROCESS FOR PREPARING #, # - DIMETHYL - # - 2,2-DICHLORVINYL PHOSPHATE |
-
1996
- 1996-06-17 CN CN96106328A patent/CN1064688C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD144264A5 (en) * | 1978-06-15 | 1980-10-08 | Inst Przemyslu Organiczego | PROCESS FOR PREPARING #, # - DIMETHYL - # - 2,2-DICHLORVINYL PHOSPHATE |
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| Publication number | Publication date |
|---|---|
| CN1168380A (en) | 1997-12-24 |
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