CN106565609B - A kind of preparation method of carbendazim - Google Patents
A kind of preparation method of carbendazim Download PDFInfo
- Publication number
- CN106565609B CN106565609B CN201610859624.8A CN201610859624A CN106565609B CN 106565609 B CN106565609 B CN 106565609B CN 201610859624 A CN201610859624 A CN 201610859624A CN 106565609 B CN106565609 B CN 106565609B
- Authority
- CN
- China
- Prior art keywords
- liquid
- carbendazim
- esterifying liquid
- preparation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a kind of preparation methods of carbendazim, and in particular to using electrodialysis separation calcium salt and cyanamide base methyl formate, the method for raising condensation reaction carbendazim synthesis mass yield.The characteristics of present invention is for lime nitrogen hydrolysis esterifying liquid, proposes removal of the electroosmose process for calcium salt in esterifying liquid, this method can efficiently separate cyanamide base methyl formate and CaCl in esterifying liquid2, the loss of cyanamide base methyl formate is reduced, carbendazim quality and yield are improved, there is simple process, easy to operate, the advantages that finished product is with high purity.To achieve the goals above, the present invention, which adopts the following technical scheme that, is: lime nitrogen hydrolysis esterification obtains calcium salt esterifying liquid, acid adding adjusts suitable pH, and esterifying liquid realizes the separation of calcium chloride and cyanamide base methyl formate by electrodialysis after above-mentioned acidification, is subsequently used for carbendazim synthesis.
Description
Technical field
The present invention relates to a kind of preparation methods of carbendazim, and in particular to using electrodialysis separation calcium salt and cyanamide Ji Jia
Sour methyl esters, the method for improving condensation reaction carbendazim synthesis mass yield.
Background technique
Carbendazim, chemical name N- (2- benzimidazolyl)-methyl carbamate belong to benzimidazoles compound, are one
Kind high-efficiency low-toxicity absorbability wide-spectrum bactericide, chemical property are stablized, and have interior suction therapeutic and protective effects, to Ascomycotina, load
Daughter bacteria subphylum and many diseases of Deuteromycotina have preventive and therapeutic effect.
The domestic main preparation process of carbendazim is lime nitrogen method.Cyanamide hydrogen calcium is produced in lime nitrogen hydrolysis, is crossed and is filtered out residue, so
Esterification is occurred into for cyanamide hydrogen calcium solution and methylchloroformate afterwards and generates cyanamide base methyl formate calcium salt soln, the latter again with neighbour
Phenylenediamine occurs condensation reaction and obtains carbendazim.There are main problems for the technique, first is that condensation reaction is due to CaCl2It deposits
Influencing carbendazim quality and yield；Second is that generating waste water contains a large amount of calcium chloride and ammonium chloride, processing difficulty is big, it is difficult to resource
Change the disadvantages of utilizing.
A kind of method that lime nitrogen efficiently synthesizes cyanamide is mentioned about calcium ion removal Chinese patent CN103922365A,
Hydrolysis terminates to lead to CO into system2It generates calcium carbonate mode and removes calcium ion, there are problem CO2Concentration requires high, cyanamide waste residue filtering
Incomplete problem.
A kind of method that Chinese patent CN104445276A mentions efficiently preparation cyanamide solution, by improving kiln gas air inlet
The processes such as mode, micro porous filtration, ion exchange resin deliming, evaporation and concentration prepare cyanamide solution, and there are problem process flows
It is long, cumbersome, the disadvantages of ion exchange resin needs frequent regeneration.
Electrodialytic technique is a technology more mature in membrane separating process, can efficiently separate electrolyte and non-electrolytic
Matter is widely used in the fields such as sea water desalination, wastewater treatment, and electrodialysis not will cause environmental pollution, low in cost.The present invention will
Removal of the electrodialytic technique for by-product calcium salt in lime nitrogen hydrolysis esterifying liquid, is used for Methyl cyanocarbamate separating-purifying state
It is inside and outside not yet to study at present.
Summary 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
Acidification, separation Methyl cyanocarbamate and calcium salt byproduct, then carry out condensation reaction with o-phenylenediamine, improve the matter of carbendazim
Amount and yield reduce wastewater treatment difficulty.
It is a further object to provide a kind of electrodialysis methods for separating Methyl cyanocarbamate and calcium salt pair
Product.This method can substantially reduce the loss of cyanamide base methyl formate, have many advantages, such as simple process, easy to operate.
To achieve the goals above, the present invention is using the technical scheme comprises the following steps:
(1) lime nitrogen obtains a certain concentration lime nitrogen then with methylchloroformate esterification with water generation hydrolysis
Hydrolyze esterifying liquid；
(2) lime nitrogen hydrolyzes esterifying liquid concentration 5-30%, pH value 7-8, and first plus acid for adjusting pH value 2-5 is 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, adjusting pH and can be sulfuric acid, hydrochloric acid, acetic acid, nitric acid etc. with acid is preferably hydrochloric acid.
(3) esterifying liquid after acidification is cooled to the light room of 0-30 DEG C of introducing electric dialyzator, liquid will be drawn and introduce electric dialyzator
Dense room, recycled in electric dialyzator respectively.DC power supply is opened and adjusts, so that electric dialyzator works, by-product in esterifying liquid
Object 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 removes calcium salt process, and drawing liquid can be water, acid solution and dilute salting liquid, preferably water.
Above-mentioned electrodialysis removes calcium salt process, provides homogeneous ion-exchange membrane, film resistance 1.8- using electrodialytic membranes for ASTOM
5.0Ω/cm2。
(4) the more bacterium of condensation reaction generation occur in acid condition for the esterifying liquid Jing Guo electrodialysis decalcification and o-phenylenediamine
Spirit by filtering, washes, is 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 control pH value 3-6, preferably 4.0-4.5 by the way that hydrochloric acid is added dropwise.
The present invention has the advantage that compared with prior art
1. process flow is simple, labor intensity is small.The filter process that avoids the precipitation method heavy using electroosmose process and from
The frequent resin regeneration process of sub-exchange resin method；
2. consuming little energy, at low cost.Calcium salt and cyanamide base methyl formate process are separated, there is no phase transformations, and electric energy is only
It is for migrating the ion dissociated in esterifying liquid；
3. good separating effect, the cyanamide base methyl formate rate of recovery 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 rate of recovery is high；
4. good product quality, high income.Esterifying liquid passes through deliming, synthesizes for carbendazim, can significantly improve carbendazim
Quality and yield；
5. waste water component is single, it is convenient for recycling.Obtaining carbendazim wastewater main component by condensation washing is ammonium chloride,
It is advantageously implemented waste water reclaiming.
The 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
Detailed description of the invention
Fig. 1 is the operation schematic diagram of electrodialysis used in the present invention (SED).
Specific embodiment
Illustrate the specific embodiment of the invention below in conjunction with Fig. 1.
Process unit used herein mainly includes electric dialyzator, metering pump, D.C. regulated power supply.Wherein electric dialyzator
Main component is anions and canons exchange membrane, electrode and partition, by 30 couples of 200*400mm2Membrane stack composition, wherein CM is cation
Exchange membrane, AM are anion-exchange membrane, the homogeneous ion-exchange membrane that the present invention is provided using ASTOM, 3.0 Ω of film resistance/
cm2。
Embodiment 1
The esterifying liquid pH7.5 that lime nitrogen hydrolysis, esterification obtain, cyanamide base methyl formate calcium concentration wherein contain for 10.0%
Calcium ion 4.0% adjusts esterifying liquid pH to 3 with hydrochloric acid, so that cyanamide base methyl formate calcium salt is acidified to obtain cyanamide in esterifying liquid
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 flow is pumped into the dense room of electrodialysis and light room, recycles about 1h.
It opens DC power supply and adjusts voltage 4V, electric dialyzator is started to work.Calcium ion is remained when light room exports in esterifying liquid
It is down to 1500ppm, calcium salt removal rate 95.5% closes DC power supply and circulating pump, electrodialysis working time total 10h.Operation knot
Beam calculates power consumption 5.0wh/l, esterifying liquid concentration 8.3%, the cyanamide base methyl formate rate of recovery 99.1%.
By in decalcification processing esterifying liquid investment reaction kettle, the neighbour of molar ratio 0.95 is put into according to the amount of cyanamide base methyl formate
Phenylenediamine carries out condensation reaction, and hydrochloric acid is added dropwise in the process and adjusts pH4.0-4.5, and condensation reaction terminates, and filters, and washes, dry, obtains
To carbendazim finished product, with o-phenylenediamine collecting rate 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
It dialyzer import esterifying liquid containing calcium salt and draws that flow velocity is constant, and electrodialysis direct current power source voltage is constant, is exported and be esterified with light room
Calcium ion is down to 1500ppm meter in liquid, in the process electrodialysis power consumption, calcium salt removal rate, cyanamide base methyl formate yield and more
Bacterium spirit content yield difference is as shown in table 1.
It is 2,4 that esterifying liquid containing calcium salt in example 3 is used salt acid for adjusting pH by example 5,6 respectively, and other processes are constant, then electric osmose
It is as shown in table 1 to analyse power consumption, calcium salt removal rate, cyanamide base methyl formate yield and carbendazim content yield difference.
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 removal rate, cyanamide base methyl formate yield and carbendazim content yield difference are as shown in table 1.
Table 1
Claims (9)
1. a kind of preparation method of carbendazim, which is characterized in that include the following steps,
(1) hydrolysis occurs for lime nitrogen and water, then with methylchloroformate esterification, obtains lime nitrogen hydrolysis esterifying liquid；
(2) lime nitrogen hydrolysis esterifying liquid be acidified with acid adjust pH value to 2-5, cyanamide base methyl formate calcium salt in esterifying liquid after acidification
Generate cyanamide base methyl formate and by-product calcium salt；
(3) the light room that esterifying liquid cooling after acidification is introduced to electric dialyzator, will draw the dense room of liquid introducing electric dialyzator, exists respectively
It is recycled in electric dialyzator, opens and adjust DC power supply, so that electric dialyzator works, by-product calcium salt is made in electric field in esterifying liquid
It under, by anion and cation exchange membrane, is drawn in liquid into dense room, when calcium ion content is down to 1000- in light room esterifying liquid
2000ppm completes esterifying liquid deliming operation；Electrodialytic membranes provides homogeneous ion-exchange membrane for ASTOM, and film resistance 1.8-5.0 Ω/
cm2；
(4) condensation reaction generation carbendazim, warp occur in acid condition for the esterifying liquid Jing Guo electrodialysis decalcification and o-phenylenediamine
It filters, wash, be dried to obtain finished product.
2. the preparation method of carbendazim according to claim 1, which is characterized in that the concentration 5- of lime nitrogen hydrolysis esterifying liquid
30%, pH value 7-8.
3. the preparation method of carbendazim according to claim 1, which is characterized in that adjusting pH with acid is sulfuric acid, hydrochloric acid, vinegar
Acid, nitric acid.
4. the preparation method of carbendazim according to claim 3, which is characterized in that adjusting pH with acid is hydrochloric acid.
5. the preparation method of carbendazim according to claim 1, which is characterized in that step is cooled to 0-30 DEG C in (3).
6. the preparation method of carbendazim according to claim 1, which is characterized in that it is molten for water, acid to draw liquid in step (3)
Liquid and dilute salting liquid.
7. the preparation method of carbendazim according to claim 6, which is characterized in that drawing liquid in step (3) is water.
8. 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 esters and o-phenylenediamine molar ratio range are 1:0.90-1:1.00.
9. the preparation method of carbendazim according to claim 8, it is characterised in that cyanogen amino first in esterifying liquid in step (4)
Sour methyl esters and o-phenylenediamine molar ratio range are 1:0.92-1:0.98.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859624.8A CN106565609B (en) | 2016-09-28 | 2016-09-28 | A kind of preparation method of carbendazim |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610859624.8A CN106565609B (en) | 2016-09-28 | 2016-09-28 | A kind of preparation method of carbendazim |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565609A CN106565609A (en) | 2017-04-19 |
| CN106565609B true CN106565609B (en) | 2019-04-23 |
Family
ID=58532526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610859624.8A Active CN106565609B (en) | 2016-09-28 | 2016-09-28 | A kind of preparation method of carbendazim |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106565609B (en) |
Families Citing this family (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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997553A (en) * | 1969-06-25 | 1976-12-14 | E. I. Du Pont De Nemours And Company | 2-Benzimidazolecarbamic acid esters by the cyanamide process |
| 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 |
| CN103058932A (en) * | 2013-02-01 | 2013-04-24 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of N-(2-benzimidazolyl)-methyl carbamate |
| CN103922365A (en) * | 2014-04-10 | 2014-07-16 | 宁夏宝马化工集团有限公司 | Method for efficient synthesis of hydrogen cyanamide employing lime nitrogen |
| CN104445276A (en) * | 2014-12-08 | 2015-03-25 | 古浪鑫辉化工有限公司 | Method for efficiently preparing monocyanamide solution |
| CN104557728A (en) * | 2014-12-22 | 2015-04-29 | 江苏扬农化工集团有限公司 | Method for preparing carbendazol from o-phenylenediamine rectification residues |
| CN105601572A (en) * | 2016-01-22 | 2016-05-25 | 江苏宝众宝达药业有限公司 | Carbendazim preparation technology |
-
2016
- 2016-09-28 CN CN201610859624.8A patent/CN106565609B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997553A (en) * | 1969-06-25 | 1976-12-14 | E. I. Du Pont De Nemours And Company | 2-Benzimidazolecarbamic acid esters by the cyanamide process |
| 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 |
| CN103058932A (en) * | 2013-02-01 | 2013-04-24 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of N-(2-benzimidazolyl)-methyl carbamate |
| CN103922365A (en) * | 2014-04-10 | 2014-07-16 | 宁夏宝马化工集团有限公司 | Method for efficient synthesis of hydrogen cyanamide employing lime nitrogen |
| CN104445276A (en) * | 2014-12-08 | 2015-03-25 | 古浪鑫辉化工有限公司 | Method for efficiently preparing monocyanamide solution |
| CN104557728A (en) * | 2014-12-22 | 2015-04-29 | 江苏扬农化工集团有限公司 | Method for preparing carbendazol from o-phenylenediamine rectification residues |
| CN105601572A (en) * | 2016-01-22 | 2016-05-25 | 江苏宝众宝达药业有限公司 | Carbendazim preparation technology |
Non-Patent Citations (4)
| Title |
|---|
| 化学镀镍老化液再生中Ca2+脱除技术的研究;邢明秀;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20110915(第09期);第B015-64页尤其是第2.3.2、4.1和4.3节 |
| 多菌灵的合成研究;庄海燕;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20050315(第01期);第B016-422页 |
| 氰胺基甲酸甲酯半先过滤法生产多菌灵;江阴农药厂;《江苏化工》;19781231(第04期);第7-8页 |
| 氰胺基甲酸甲酯连续化生产;鄂南化工厂多菌灵小组;《农药工业》;19790302(第02期);第18-20页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106565609A (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103449653B (en) | Combined treatment method for sodium chloride-containing wastewater generated in dressing and smelting of rare earth | |
| CN107915360A (en) | Zero-emission crystallization divides salt device and technique | |
| CN102627300B (en) | Double-membrane-method technology for refining brine and equipment for the same | |
| CN105060545A (en) | System and method for softening treatment of desulfurization wastewater of coal-fired power plant | |
| CN109250856A (en) | It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource | |
| CN101538021B (en) | Method and device for producing concentrated sulfuric acid by recycling waste acid from sulfate process titanium dioxide production | |
| CN109680295B (en) | A kind of method that industry level lithium carbonate solid prepares lithium hydroxide | |
| CN108689522A (en) | A kind of Treatment and recovery recovery method of photovoltaic industry nitration mixture waste water | |
| CN105671587A (en) | Method and device for preparing methionine and recovering by-product-carbon dioxide | |
| CN106565609B (en) | A kind of preparation method of carbendazim | |
| CN110451707A (en) | A kind of waste water of mine Zero discharge treatment method | |
| CN104495925B (en) | The preparation method of sodium metavanadate | |
| CN106242145A (en) | A kind of desulfurization wastewater reverse osmosis reconcentration device | |
| CN110937728A (en) | Desulfurization wastewater treatment method and system | |
| CN106186437A (en) | A kind of process technique producing the waste water manufacturing demineralized water generation in viscose rayon | |
| CN104710319A (en) | Green environmentally-friendly method for combined production of amino acid and analog thereof by using membrane integration technology | |
| CN109678183A (en) | A kind of method that technical grade soluble lithium salt prepares lithium hydroxide | |
| CN110342559A (en) | A kind of system and method being recycled evaporated waste ammonia liquid joint-producing anhydrous sodium carbonate | |
| CN204939142U (en) | A kind for the treatment of facility of desulfurization wastewater of flue gas desulphurization system discharge | |
| CN103664569A (en) | Method for cleanly producing citric acid by coupling calcium salt method with precipitation displacement | |
| CN115305574B (en) | Method for rapidly preparing whisker by using phosphogypsum and saline | |
| CN109368850A (en) | A kind of desulfurization wastewater recycling treatment system and application method | |
| CN105152405A (en) | Method and device for treating desulfurization wastewater discharged by flue gas desulfurization system | |
| CN109231252B (en) | Separation of SO from high-concentration brine in plasma flue gas treatment42-Preparation of CaSO4Method and system of | |
| CN111892222B (en) | Ammonium sulfate wastewater recycling method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |