CN106565609A - Preparation method of carbendazim - Google Patents
Preparation method of carbendazim Download PDFInfo
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- CN106565609A CN106565609A CN201610859624.8A CN201610859624A CN106565609A CN 106565609 A CN106565609 A CN 106565609A CN 201610859624 A CN201610859624 A CN 201610859624A CN 106565609 A CN106565609 A CN 106565609A
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- carbendazim
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- esterifying liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/30—Nitrogen atoms not forming part of a nitro radical
- C07D235/32—Benzimidazole-2-carbamic acids, unsubstituted or substituted; Esters thereof; Thio-analogues thereof
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of carbendazim, specifically to a method for increasing carbendazim synthesis quality and yield of a condensation reaction by electrodialysis and separation of calcium salt and methyl cyanocarbamate. By characteristic of a lime nitrogen hydrolysis esterifying liquid, an electrodialysis method is used for removal of calcium salt in the esterifying liquid. By the method, methyl cyanocarbamate and CaCl2 in the esterifying liquid can be effectively separated, loss of methyl cyanocarbamate is reduced, and quality and yield of carbendazim are enhanced. The method has advantages of simple process, convenient operation, high purity of the finished product, etc. In order to achieve the above purpose, the invention adopts the following technical scheme: lime nitrogen undergoes hydrolysis esterification to obtain a calcium salt esterifying liquid; acid is added to regulate pH to a proper level; and the above acidified esterifying liquid undergoes electrodialysis to realize separation of calcium chloride and methyl cyanocarbamate, and then is used for synthesis of carbendazim.
Description
Technical field
The present invention relates to a kind of preparation method of carbendazim, and in particular to separate calcium salt and cyanamide Ji Jia to using electrodialysis
Sour methyl ester, improves the method that condensation reaction carbendazim synthesizes mass yield.
Background technology
Carbendazim, chemical name N- (2- benzimidazolyls)-methyl carbamate belongs to benzimidazoles compound, is one
High-efficiency low-toxicity absorbability wide-spectrum bactericide is planted, stable chemical nature has interior suction to treat and protective effect, to Ascomycotina, load
Many diseases of daughter bacteria subphylum and Deuteromycotina have preventive and therapeutic effect.
The main preparation technology of domestic carbendazim is lime nitrogen method.Cyanamide hydrogen calcium is produced in lime nitrogen hydrolysis, is crossed and is filtered residue, so
Be there is into esterification in cyanamide hydrogen calcium solution and methylchloroformate afterwards and generates cyanamide base methyl formate calcium salt soln, the latter again with neighbour
Carbendazim obtained and condensation reaction in phenylenediamine there is.There is subject matter in the technique, one is condensation reaction due to CaCl2Deposit
Affecting carbendazim quality and yield；Two is to produce waste water containing a large amount of calcium chloride and ammonium chloride, and intractability is big, it is difficult to resource
Change the shortcomings of utilizing.
Chinese patent CN103922365A is removed with regard to calcium ion mention a kind of method that lime nitrogen efficiently synthesizes cyanamide,
Hydrolysis terminates to lead to CO into system2Generate Calcium Carbonate mode and remove calcium ion, have problems CO2Concentration requirement is high, and cyanamide waste residue is filtered
Incomplete problem.
Chinese patent CN104445276A mentions a kind of efficient method for preparing cyanamide solution, by improving kiln gas air inlet
The operations such as mode, microporous filter, ion exchange resin deliming, evaporation and concentration prepare cyanamide solution, and have problems technological process
It is long, it is cumbersome, the shortcomings of ion exchange resin needs frequent regeneration.
Electrodialytic technique is a technology more ripe in membrane separating process, can efficiently separate electrolyte and non-electrolytic
Matter, is widely used in the fields such as desalinization, wastewater treatment, and electrodialysis do not result in environmental pollution, with low cost.The present invention will
Electrodialytic technique is used for the removal that lime nitrogen hydrolyzes by-product calcium salt in esterifying liquid, for Methyl cyanocarbamate separating-purifying state
It is inside and outside not yet to study at present.
The content of the invention
A primary object of the present invention is to provide a kind of preparation method of carbendazim, hydrolyzes esterifying liquid to lime nitrogen first
Acidifying, separates Methyl cyanocarbamate and calcium salt side-product, and condensation reaction is then carried out with o-phenylenediamine, improves the matter of carbendazim
Amount and yield, reduce wastewater treatment difficulty.
It is a further object to provide a kind of electrodialysis methods are used to separate Methyl cyanocarbamate and calcium salt pair
Product.The method can substantially reduce the loss of cyanamide base methyl formate, with process is simple, the advantages of easy to operate.
To achieve these goals, the present invention is comprised the following steps using technical scheme：
(1) with water there are hydrolysis in lime nitrogen, then with methylchloroformate esterification, obtain finite concentration lime nitrogen
Hydrolysis esterifying liquid；
(2) lime nitrogen hydrolysis esterifying liquid concentration 5-30%, pH value 7-8 adds first acid for adjusting pH value 2-5 to be acidified, acid
Cyanamide base methyl formate calcium salt generates cyanamide base methyl formate and by-product calcium salt in esterifying liquid after change；
Above-mentioned esterifying liquid acidization, it can be that sulphuric acid, hydrochloric acid, acetic acid, nitric acid etc. are preferably hydrochloric acid to adjust pH acid.
(3) esterifying liquid after acidifying is cooled to the light room of 0-30 DEG C of introducing electrodialyzer, liquid will be drawn and introduced electrodialyzer
Dense room, respectively in electrodialyzer circulate.Open and adjust DC source so that electrodialyzer works, by-product in esterifying liquid
Thing calcium salt, by anion and cation exchange membrane, is drawn in liquid under electric field action into dense room, when calcium ion contains in light room esterifying liquid
Amount is down to 1000-2000ppm, completes esterifying liquid deliming operation.
Above-mentioned electrodialysis remove calcium salt process, and drawing liquid can be for water, acid solution and dilute saline solution, preferred water.
Above-mentioned electrodialysis remove calcium salt process, and homogeneous ion-exchange membrane, membrane resistance 1.8- are provided for ASTOM using electrodialytic membraness
5.0Ω/cm2。
(4) with o-phenylenediamine there are in acid condition many bacterium of condensation reaction generation in the esterifying liquid through electrodialysis decalcification
Spirit, through filtering, washing, be dried to obtain finished product.
Above-mentioned condensation reaction, Methyl cyanocarbamate and o-phenylenediamine molar ratio range 1: 0.90-1: 1.00, preferably
1∶0.92-1∶0.98。
Above-mentioned condensation reaction, acid condition is by Deca hydrochloric acid control ph 3-6, preferred 4.0-4.5.
The present invention has compared with prior art following advantage：
1. technological process is simple, and labor intensity is little.Using electroosmose process avoid the heavy filter process of the sedimentation method and from
The frequent resin regeneration process of sub-exchange resin method；
2. consuming little energy, low cost.Calcium salt and cyanamide base methyl formate process are separated, is not undergone phase transition, electric energy is only
Be for migrating esterifying liquid in the ion that dissociated；
3. good separating effect, the cyanamide base methyl formate response rate is high.Using scheme of the present invention, stone can be efficiently separated
Cyanamide base methyl formate and calcium salt in grey nitrogen hydrolysis esterifying liquid, reduce the loss of cyanamide base methyl formate, and the response rate is high；
4. good product quality, high income.Esterifying liquid, for carbendazim synthesis, can significantly improve carbendazim through deliming
Quality and yield；
5. waste water component is single, is easy to resource.It is ammonium chloride through be condensed washing to obtain carbendazim wastewater key component,
It is advantageously implemented waste water reclaiming.
Reaction mechanism is as follows：
2CaCN2+2H2O→Ca(HCN2)2+Ca(OH)2
Ca(HCN2)2+Ca(OH)2+2ClCOOCH3→Ca(NCNCOOCH3)2+CaCl2+2H2O
Ca(NCNCOOCH3)2+2HCl→2NCNHCOOCH3+CaCl2
Description of the drawings
Fig. 1 is the operating diagram of electrodialysis used in the present invention (SED).
Specific embodiment
The specific embodiment of the invention is illustrated below in conjunction with Fig. 1.
Process unit used herein mainly includes electrodialyzer, dosing pump, D.C. regulated power supply.Wherein electrodialyzer
Critical piece is anions and canons exchange membrane, electrode and dividing plate, by 30 couples of 200*400mm2Membrane stack is constituted, and wherein CM is cation
Exchange membrane, AM is anion exchange membrane, the homogeneous ion-exchange membrane for using ASTOM offers of the invention, the Ω of membrane resistance 3.0/
cm2。
Embodiment 1
The esterifying liquid pH7.5 that lime nitrogen hydrolysis, esterification are obtained, cyanamide base methyl formate calcium concentration wherein contains for 10.0%
Calcium ion 4.0%, with hydrochloric acid esterifying liquid pH to 3 is adjusted so that cyanamide base methyl formate calcium salt acidifying in esterifying liquid obtains cyanamide
Base methyl formate and calcium chloride mixing esterifying liquid, by above-mentioned esterifying liquid be cooled to 10 DEG C with water do draw liquid respectively with
100L/h flows pump into the dense room of electrodialysis and light room, circulate about 1h.
Open DC source and adjust voltage 4V, electrodialyzer is started working.Calcium ion is remained in light room exports esterifying liquid
1500ppm is down to, calcium salt clearance 95.5% closes DC source and circulating pump, electrodialysis working time common 10h.Operation knot
Beam calculates power consumption 5.0wh/l, esterifying liquid concentration 8.3%, the cyanamide base methyl formate response rate 99.1%.
Decalcification is processed in esterifying liquid input reactor, the neighbour of mol ratio 0.95 is put into according to the amount of cyanamide base methyl formate
Phenylenediamine carries out condensation reaction, during Deca hydrochloric acid adjust pH4.0-4.5, condensation reaction terminates, and filters, and washing is dried, and obtains
To carbendazim finished product, with o-phenylenediamine rate of collecting 92.3%, product content 99.0%, whiteness 92.6.
Example 2,3,4 changes initial esterifying liquid concentration in example 1, is respectively increased to 12.0%, 14.0% and 16.0%, electric
Dialyser import esterifying liquid containing calcium salt and draw that flow velocity is constant, electrodialysis direct current power source voltage is constant, is esterified with the outlet of light room
Calcium ion is down to 1500ppm meters in liquid, during electrodialysis power consumption, calcium salt clearance, cyanamide base methyl formate yield and many
Bacterium spirit content yield is as shown in table 1 respectively.
Esterifying liquid containing calcium salt in example 3 is respectively 2,4 with salt acid for adjusting pH by example 5,6, and other processes are constant, then electric osmose
Analysis power consumption, calcium salt clearance, cyanamide base methyl formate yield and carbendazim content yield are as shown in table 1 respectively.
The temperature of esterifying liquid containing calcium salt in example 3 is adjusted to 5 DEG C, 20 DEG C by example 7,8, and other processes are constant, then electrodialysis
Power consumption, calcium salt clearance, cyanamide base methyl formate yield and carbendazim content yield are as shown in table 1 respectively.
Table 1
Claims (10)
1. a kind of preparation method of carbendazim, it is characterised in that comprise the following steps,
(1) with water there are hydrolysis in lime nitrogen, then with methylchloroformate esterification, obtain lime nitrogen hydrolysis esterifying liquid；
(2) lime nitrogen hydrolysis esterifying liquid is acidified with acid regulation pH value to 2-5, cyanamide base methyl formate calcium salt in esterifying liquid after acidifying
Generate cyanamide base methyl formate and by-product calcium salt；
(3) esterifying liquid cooling after acidifying is introduced the light room of electrodialyzer, the dense room of liquid introducing electrodialyzer will be drawn, existed respectively
Circulate in electrodialyzer, open and adjust DC source so that electrodialyzer works, by-product calcium salt is made in electric field in esterifying liquid
With under, by anion and cation exchange membrane, draw in liquid into dense room, when calcium ion content is down to 1000- in light room esterifying liquid
2000ppm, completes esterifying liquid deliming operation；
(4) with o-phenylenediamine there is in acid condition condensation reaction generation carbendazim, Jing in the esterifying liquid through electrodialysis decalcification
Filter, wash, be dried to obtain finished product.
2. the preparation method of carbendazim according to claim 1, it is characterised in that lime nitrogen hydrolyzes concentration 5- of esterifying liquid
30%, pH value 7-8.
3. the preparation method of carbendazim according to claim 1, it is characterised in that it is sulphuric acid, hydrochloric acid, vinegar to adjust pH acid
Acid, nitric acid.
4. the preparation method of carbendazim according to claim 3, it is characterised in that it is hydrochloric acid to adjust pH acid.
5. the preparation method of carbendazim according to claim 1, it is characterised in that step is cooled to 0-30 DEG C in (3).
6. the preparation method of carbendazim according to claim 1, it is characterised in that liquid is drawn in step (3) for water, acid it is molten
Liquid and dilute saline solution.
7. the preparation method of carbendazim according to claim 6, it is characterised in that liquid is drawn in step (3) for water.
8. the preparation method of carbendazim according to claim 1, it is characterised in that electrodialytic membraness are used in step (3)
ASTOM provides homogeneous ion-exchange membrane, membrane resistance 1.8-5.0 Ω/cm2。
9. the preparation method of carbendazim according to claim 1, it is characterised in that cyanogen amino first in esterifying liquid in step (4)
Sour methyl ester is 1 with o-phenylenediamine molar ratio range：0.90-1：1.00.
10. the preparation method of carbendazim according to claim 9, it is characterised in that cyanogen amino in esterifying liquid in step (4)
Methyl formate is 1 with o-phenylenediamine molar ratio range：0.92-1：0.98.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188831A (en) * | 2017-07-12 | 2017-09-22 | 安徽广信农化股份有限公司 | A kind of carbendazim intermediate cyanamide base methyl formate synthesis technique |
| CN111718283A (en) * | 2020-07-28 | 2020-09-29 | 安徽东至广信农化有限公司 | Production method of medicine intermediate methyl cyanamide formate |
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| US4550174A (en) * | 1983-06-25 | 1985-10-29 | Hoechst Aktiengesellschaft | Process for reducing the proportions of by products in the preparation of carbendazim |
| CN101735153A (en) * | 2009-11-13 | 2010-06-16 | 安徽广信集团铜陵化工有限公司 | Production technology of carbendazim |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188831A (en) * | 2017-07-12 | 2017-09-22 | 安徽广信农化股份有限公司 | A kind of carbendazim intermediate cyanamide base methyl formate synthesis technique |
| CN111718283A (en) * | 2020-07-28 | 2020-09-29 | 安徽东至广信农化有限公司 | Production method of medicine intermediate methyl cyanamide formate |
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