CN100519521C

CN100519521C - Padan preparing method

Info

Publication number: CN100519521C
Application number: CNB2007100253217A
Authority: CN
Inventors: 周国平; 毛建平; 金克明; 王良; 陆振荣
Original assignee: JIANGSU TIANRONG GROUP CO Ltd
Current assignee: JIANGSU TIANRONG GROUP CO Ltd
Priority date: 2007-07-23
Filing date: 2007-07-23
Publication date: 2009-07-29
Anticipated expiration: 2027-07-23
Also published as: CN101103725A

Abstract

The invention discloses an environmental protection preparation method for cartap hydrochloride; rhodanide solution, water and catalyst are arranged inside a reactor, and chlorine hydride gas is input in the reactor for hydrolysis reaction for 15 to 24 hours under -18 to 25 DEG C, so that the cartap hydrochloride can be produced. The hydrolysis processing technique of the invention firstly adopts a hydrolyst method instead of a methyl alcohol alcoholysis for solving the problems of the exhaust gas and waste water from the prior processing technique, furthermore, the hydrolysis rate can reach 95 percent, the quality stability of the cartap hydrochloride product is good, and the processing to the recovery solvent and the mother liquor has unparalleled advantages than the prior art, which fully embodies the call of nation on energy saving and pollutants discharge reduction, thereby the invention has a great social and economic efficiency.

Description

The preparation method of cartap

Technical field

The invention belongs to the agricultural insecticide field, be specifically related to the bionical method for producing insecticide of a kind of clam worm poison derivative.

Background technology

Clam worm poison derivative is that a class is efficient, the bionical sterilant of low toxicity, wide spectrum, as desinsection amine, thiocyclam, desinsection leech, disosultap, desinsection list, cartap etc.Domestic in last century the seventies begin to develop the bionical sterilant of nereistoxin, suitability for industrialized production and apply mainly contain disosultap, desinsection list, three kinds of cartap.

The classical synthetic method of cartap is to be starting raw material with the disosultap, through generating thiocyanide and S-WAT with the sodium cyanide reaction, then thiocyanide is dissolved in the methanol solvate, feed hydrogen chloride gas, promptly generate cartap and byproduct chloromethane gas and (see " the synthetic and application of agricultural chemicals " Chen Wanyi chief editor, Chemical Industry Press, in June, 2000 first version).The defective of this method is that transformation efficiency is low, and product purity can only reach 95%, the production cost height.1998, it is starting raw material that our company has developed with the desinsection list, handle the innovative approach of the synthetic cartap of thiocyanide with solvent method, cyaniding, two step of hydrolysis total recovery are reached more than 90%, product purity reaches more than 98%, and calendar year 2001 obtains the Chinese invention patent mandate (patent No.: ZL98111505).Domestic enterprise generally all adopts this method to produce cartap at present.

Production practice show, waste gas, waste water because of using the methanol solvate alcoholysis to produce in hydrolysis reaction, and to the difficulty increasing of the post-reaction treatment and the disposal of three wastes, production cost increases, and makes a concrete analysis of as follows:

1, hydrolysis reaction uses the methyl alcohol alcoholysis, though improved reactive behavior, has improved reaction yield, can produce the methyl chloride gas of by-product.

If it is serious that 2, the methyl chloride gas of by-product is directly discharged environmental pollution, if recycle byproduct chloromethane, then facility investment is big, and the technological operation complexity does not have economy.

3, hydrolysis is because of using methyl alcohol reaction ratio overflow method, and the unnecessary methyl alcohol in reaction back is brought into and reclaimed in the solvent, must handle before solvent cycle is utilized, and processed waste water contains a large amount of methyl alcohol and be acid, has increased wastewater treatment difficulty and cost.

Summary of the invention

To the objective of the invention is in order addressing the above problem, to provide that a kind of technology is simple, yield is high, quality is good, the three wastes are few, but the cartap hydrolysis environment-friendly production process that heavy industrialization, commercialization are produced.

Purpose of the present invention can reach by following measure:

A kind of environment-friendly type preparation method of cartap, thiocyanide (I) solution and water, catalyzer are placed in the reactor, feed hydrogen chloride gas, reaction 15～24 hours is hydrolyzed under-18～25 ℃, preparation cartap (II), after the processing of cartap crude product water recrystallization, just obtain the cartap finished product, concrete reaction equation is:

Wherein the mol ratio of thiocyanide and water, hydrogenchloride is 1:10～20:1～3, is preferably 1:11～14:1.7～2.5; The mass ratio of water and catalyzer is 60～120:1, is preferably 79～101:1.

Wherein catalyzer is big alkyl saline catalyst, is preferably benzyl trioctylphosphine ammonium chloride, benzyl tributyl ammonium chloride, benzyl triethyl ammonium bromide or butyl trioctylphosphine brometo de amonio.

Wherein thiocyanide solution is benzene, toluene, ethylene dichloride, tetracol phenixin or the chloroformic solution of thiocyanide, and wherein the mass content of thiocyanide is 20～30%.

An important breakthrough point of Technology of the present invention depends on selection of catalysts, requires catalyzer to have following feature:

1, hydrolysis has obvious catalysis to water law.

2, it is obvious that technological operation makes logical hydrogenchloride terminal point simply as far as possible, and hydrolytic process is convenient to control, and engineering equipment is convenient to operation.

3, have higher yield and quality.

4, take into account cost, toxicity, danger etc. simultaneously.

We have tested multiple catalyzer, and emphasis has compared tens kinds of quaternary ammonium salts and the three kinds of aminated compoundss catalytic effect to system in detail, these catalyzer all have certain katalysis, but effect is variant, the commonly used catalyzer of organic synthesis is unsatisfactory to the catalytic effect of this reaction system, and big alkyl salt for example benzyl trioctylphosphine ammonium chloride, butyl trioctylphosphine brometo de amonio, the catalyzed reaction yield is higher, be respectively 95% and 93%, this may be because they have more suitably fat-soluble.

Cartap hydrolysis production technique of the present invention, adopted first without the methyl alcohol alcoholysis and adopted the hydrolyst method, solved the reluctant problem of waste gas, waste water that produces in the original production process, and the hydrolysis yield can reach 95%, it is pure white to isolate the cartap color and luster, outward appearance is loose easily dry, constant product quality is good, simultaneously the processing of reclaiming solvent is applied mechanically and all more former technology of processing of mother liquor has incomparable superiority, demonstrate fully the call of national energy-saving and emission-reduction, had very important social benefit and economic benefit.

New water catalyst method hydrolysis process, simple and reliable, raw material is easy to get, good product quality, the yield height can reach more than 95%, and product purity can reach 98%.This technology can make full use of the infrastructure device and the general facilities of existing desinsection list manufacturer, only need a small amount of investment can produce the upgraded product cartap, instant effect, can satisfy domestic and international at present a large amount of requirements to cartap, and the three wastes are few, handle simple and conveniently, also meet the policy of national energy-saving and emission-reduction, have very important social benefit and economic benefit.

Embodiment

Embodiment 1

With the dichloroethane solution (mass content is 25%) of the thiocyanide of 0.2mol and the water of 2.8mol, 0.5g benzyl trioctylphosphine ammonium chloride catalyzer together places in the reactor, feed hydrogen chloride gas then, the feeding amount is 0.35mol, its temperature of reaction is controlled at 20 ℃, make its reaction 20 hours that is hydrolyzed, its reaction formula is

With behind the cartap crude product water recrystallization that obtains, obtain the cartap product of 0.19mol at last.

Embodiment 2

With the toluene solution (mass content is 30%) of the thiocyanide of 0.2mol and the water of 2.2mol, 0.5g butyl trioctylphosphine brometo de amonio catalyzer together places in the reactor, feed hydrogen chloride gas then, the feeding amount is that its temperature of reaction of 0.5mol is controlled at-10 ℃, make its reaction 15 hours that is hydrolyzed, with behind the cartap crude product water recrystallization that obtains, obtain the cartap product of 0.186mol at last.

Embodiment 3

With the carbon tetrachloride solution (mass content is 20%) of the thiocyanide of 0.2mol and the water of 2.5mol, 0.4g benzyl tributyl ammonium chloride catalyzer together places in the reactor, feed hydrogen chloride gas then, the feeding amount is 0.4mol, its temperature of reaction is controlled at 10 ℃, make its reaction 24 hours that is hydrolyzed, with behind the cartap crude product water recrystallization that obtains, obtain the cartap product of about 0.188mol at last.

Claims

1, a kind of preparation method of cartap is characterized in that thiocyanide (I) solution and water, catalyzer are placed in the reactor, feeds hydrogen chloride gas, the reaction 15～24 hours that under-18～25 ℃, is hydrolyzed, and preparation cartap (II),

Wherein the mol ratio of thiocyanide and water, hydrogenchloride is 1:10～20:1～3, the mass ratio of water and catalyzer is 60～120:1, and described catalyzer is benzyl trioctylphosphine ammonium chloride, benzyl tributyl ammonium chloride, benzyl triethyl ammonium bromide or butyl trioctylphosphine brometo de amonio.

2, preparation method according to claim 1, the mol ratio that it is characterized in that thiocyanide and water, hydrogenchloride is 1:11～14:1.7～2.5, the mass ratio of water and catalyzer is 79～101:1.

3, according to right 1 described preparation method, it is characterized in that thiocyanide solution is benzene, toluene, ethylene dichloride, tetracol phenixin or the chloroformic solution of thiocyanide, wherein the mass content of thiocyanide is 20～30%.