CN102649770A - Production method of high-content acetochlor by methylene method - Google Patents
Production method of high-content acetochlor by methylene method Download PDFInfo
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- CN102649770A CN102649770A CN2012100523819A CN201210052381A CN102649770A CN 102649770 A CN102649770 A CN 102649770A CN 2012100523819 A CN2012100523819 A CN 2012100523819A CN 201210052381 A CN201210052381 A CN 201210052381A CN 102649770 A CN102649770 A CN 102649770A
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- acetochlor
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- ammonium chloride
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- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002466 imines Chemical class 0.000 claims abstract description 17
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 12
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000019270 ammonium chloride Nutrition 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of high-content acetochlor by a methylene method. The production method comprises the following steps of: (a) adding 2-methyl-6 ethyl aniline and paraformaldehyde in a mol ratio of 1:1.5, adding catalyst triethylamine and MEA (Mono Etobaccool Amine) according to a mol ratio of 1:0.006, heating to 85 DEG C and preserving heat for two hours, decompressing to -0.095 Mpa to -0.1 Mpa, dehydrating and removing aldehyde to obtain imine, i.e., methylene; (2) adding the imine and chloroacetic chloride according to a mol ratio of 1:1.05, pumping weighed chloroacetic chloride into an addition kettle, then dropwise adding the imine at 60-80 DEG C and preserving heat at 85 DEG C for two hours; (3) adding amide and ethanol in a mol ratio of 1:4.5 into an alcoholysis kettle to react at normal temperature and adding ammonia gas serving as an acid-binding agent; and (4) post-treating and purifying. By using the new process such the methylene method, the cost is reduced, the content and the yield of a product are improved, and environmental protection is facilitated.
Description
Technical field
The present invention relates to the pesticide chemical technical field, in particular a kind of methene method high-content acetochlor working method.
Background technology
Acetochlor, english common name Acetochlor, chemical name is: 2 '-methyl-6 '-ethyl-N-(ethoxymethyl)-2-chloro acetanilide.In the selectivity preemergence herbicide of U.S. Monsanto company in 1971 development and production, can prevent and kill off annual gramineous weed and part broadleaf weeds.The acetochlor mechanism of action is: activeconstituents makes weeds dead through the protein synthesis that suppresses weeds in doing weeds after being absorbed by the young shoot of weeds and young root.This medical instrument have weeding activity high, to characteristics such as crop safety, applied range, lasting period are moderate, be good dry land herbicide.
At present, mainly adopt the high-load acetochlor of methene explained hereafter in the world, and domestic acetochlor production technique is in by among the chloromethyl ethyl ether normal direction methene Technology process of transition.
Chloromethyl ethyl ether method production technique has been produced the time of recent two decades at home, is generally adopted by domestic most of manufacturers, and its characteristics are: production technique is ripe relatively, stable, operates uncomplicatedly, and engineering equipment is characteristic of simple relatively also.But because starting material such as this process using POCl3s, " three wastes " quantity discharged is big, and environmental pollution is serious; Owing to used the main intermediate chloromethyl ethyl ether in the production process,, cause the security in the process of producing product to receive serious threat again owing to this material carcinogenic substance.From later stage nineteen nineties, the methene production technique is developed to merit gradually in the world, and is applied in the suitability for industrialized production.But also have the problem of utilizing aromatic solvents such as a large amount of YLENE in producing, cost is high, pollution is big, productive rate is low.
Summary of the invention
Technical problem to be solved by this invention is that the deficiency that is directed against prior art provides a kind of.
Technical scheme of the present invention is following:
A kind of methene method high-content acetochlor working method; May further comprise the steps: (1) feeds intake in the ratio of mol than 1: 1.5 with 2-methyl-6 MEA and Paraformaldehyde 96; Catalyst of triethylamine and MEA press the amount of mol than 1: 0.006 and add, and are heated to 85 ℃ of insulations two hours, decompression-0.095Mpa extremely-0.1Mpa; It is methene that dehydration, full gear obtain imines, and the aldehyde of deviating from absorbs recycle in the next batch imine reaction with MEA;
(2) imines fed intake than 1: 1.05 by mol with chloroacetyl chloride, in the chloroacetyl chloride suction addition still that measures, between 60 °-80 °, dripped imines then, and 85 ° are incubated 2 hours, obtain acid amides;
(3) with acid amides and ethanol in the reaction under the normal temperature in the alcoholysis still that feeds intake of the ratio of mol than 1: 4.5, add the acid binding agent ammonia.
(4) aftertreatment, purification: at first carry out solid-liquid separation: use the barrier film press filtration that the acetochlor mixed solution is carried out solid-liquid separation, attached resultant solid ammonium chloride is separated from acetochlor solution, filter cake is solid ammonium chloride; Still contain 10% acetochlor in the filter cake; Utilize the method for ammonium chloride recrystallization, in extraction kettle, extract content, increase yield at 96% acetochlor; The ammonium chloride of recrystallization is sold, and used water jacket is used; Filtrating is proceeded liquid liquid and separated: filtrating adds water and washes in the washing still: washing back organic phase is advanced scrapper thin film evaporator, and it is 98% acetochlor that precipitation gets content; Water after the washing distills out that ethanol is laggard goes into water treatment.
Adopt methene method novel process promptly to reduce cost, improved the content and the yield of product, help environmental protection again.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Embodiment 1
Technical process:
(1) feeds intake in the ratio of mol with Paraformaldehyde 96 with 2-methyl-6 MEA (being called for short MEA) than 1: 1.5; Catalyst of triethylamine is pressed the amount of mol than 1: 0.006 with MEA and is added; Be heated to 85 ℃ of insulations two hours; Decompression-0.095Mpa is to-0.1Mpa, and it is methene that dehydration, full gear obtain imines, and the aldehyde of deviating from absorbs recycle in the next batch imine reaction with MEA.
(2) imines fed intake than 1: 1.05 by mol with chloroacetyl chloride, in the chloroacetyl chloride suction addition still that measures, between 60 °-80 °, dripped imines then, and 85 ° are incubated 2 hours, obtain acid amides.
This step reaction scheme of prior art is that imines is added drop-wise in the chloroacetyl chloride and reacts, and YLENE is made solvent.The reaction back decrease temperature crystalline that finishes filters out acid amides and carries out next step reaction from solvent, also will handle the solvent that leaches simultaneously at this, and distillation, neutralization, distillation obtain high-load YLENE at last and apply mechanically with depleted raffinate and waste water and drain.And reaction scheme of the present invention is imines to be added drop-wise in the chloroacetyl chloride (seeing pilot plant test report among the embodiment 3), under the situation of solubilizing agent not, reacts, and reaction finishes and changes the acid amides reaction solution over to next step direct reaction.Such benefit is: a, reduced working strength of workers; B, do not have the discharging of waste residue and waste water, avoided waste gas, waste liquid pollution on the environment: c, do not had solvent consumption, reduced production cost, acid amides does not have the possibility that runs off yet.
(3) with acid amides and ethanol in the reaction under the normal temperature in the alcoholysis still that feeds intake of the ratio of mol than 1: 4.5, in reaction process, make reaction be difficult to carry through to the end owing to produce the hydrogenchloride of an one's share of expenses for a joint undertaking; And hydrogenchloride and ethanol synthesis generation monochloroethane and water (intensification impels this reaction to quicken), water can make acid amides decompose; Therefore this process adds the acid binding agent ammonia, with absorption hydrogenchloride, reduces the generation of water and impels the reaction generation acetochlor of carrying through to the end.Selecting for use of acid binding agent meets following principle: do not produce water in the N-process; Simultaneously alkalescence should not be too strong (alkalescence too strong easily with the acetochlor molecule in chloromethyl reaction generation by product); And compliance with environmental protection requirements, the ammonium chloride that generates thus can be used as the by-product utilization.
(4) aftertreatment, purification: the aftertreatment technology of acetochlor mixed solution reduces blowdown flow rate for water saving, increases product yield; Acetochlor is purified and at first carried out solid-liquid separation: use the barrier film press filtration that the acetochlor mixed solution is carried out solid-liquid separation, attached resultant solid ammonium chloride is separated from acetochlor solution, filter cake is solid ammonium chloride; Still contain 10% acetochlor in the filter cake; Utilize the method for ammonium chloride recrystallization, in extraction kettle, extract content, increase yield at 96% acetochlor; The ammonium chloride of recrystallization is sold, and used water jacket is used.Filtrating (containing ethanol, acetochlor solution) is proceeded liquid liquid and separated: filtrating adds water and washes in the washing still: washing back organic phase (being the acetochlor bullion) is advanced scrapper thin film evaporator, and it is 98% acetochlor that precipitation gets content; Water after the washing (containing ethanol, water) distills out that ethanol is laggard goes into water treatment.
The influence that different post-treating methods causes (see embodiment 2 medium and small having a try test report) also inequality; Originally the acetochlor after the neutralization directly adds water treatment; So could be with ethanol and ammonium chloride flush away owing to have ammonium chloride and ethanol will add a large amount of washing four times in the acetochlor solution; And could water and organic phase better be separated, so just reduce the yield of finished product in order layering also to want solubilizing agent YLENE to change density difference; Increased wastewater flow rate; Ethanol is also by xylene pollution, increased the difficulty that ethanol reclaims, and the ammonium chloride of handling out relatively pure do not reach requirement yet and can't sell utilization.
Embodiment 2
The lab scale laboratory report
Experiment purpose: optimization experiment (change post processing mode)
Table 1 feeds intake and output, measure unit: g
Explain: neutralizer refers to the acetochlor mixed solution after ammonia is led in alcoholysis in the table 1.
Table 2 lab scale analysis of experiments result
Explain: yield=actual finished product must be measured/main raw material * content/molecular weight * finished product molecular weight * 100
Little test result shows: from reduce cost, environmental protection, raising product content, yield equal angles prove that all novel process is feasible, improved product yield simultaneously.
Embodiment 3
The pilot experiment report:
Experiment purpose: optimize the acid amides reaction process
Table 3 feeds intake and output measure unit: kg
Pilot-scale experiment shows: novel process is compared with former technology, identical charging capacity, and the weight of amide solution increases under the situation of solubilizing agent not, has saved the operation that reclaims solvent, also without the effluent waste liquid, has played environmental-protection function accordingly.
To sum up, adopt methene method novel process promptly to reduce cost, improved the content and the yield of product, help environmental protection again.
Should be understood that, concerning those of ordinary skills, can improve or conversion, and all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (1)
1. methene method high-content acetochlor working method; It is characterized in that, may further comprise the steps: (1) feeds intake in the ratio of mol than 1: 1.5 with 2-methyl-6 MEA and Paraformaldehyde 96, and catalyst of triethylamine is pressed the amount of mol than 1: 0.006 with MEA and added; Be heated to 85 ℃ of insulations two hours; Decompression-0.095Mpa is to-0.1Mpa, and it is methene that dehydration, full gear obtain imines, and the aldehyde of deviating from absorbs recycle in the next batch imine reaction with MEA;
(2) imines fed intake than 1: 1.05 by mol with chloroacetyl chloride, in the chloroacetyl chloride suction addition still that measures, between 60 °-80 °, dripped imines then, and 85 ° are incubated 2 hours, obtain acid amides;
(3) with acid amides and ethanol in the reaction under the normal temperature in the alcoholysis still that feeds intake of the ratio of mol than 1: 4.5, add the acid binding agent ammonia;
(4) aftertreatment, purification: at first carry out solid-liquid separation: use the barrier film press filtration that the acetochlor mixed solution is carried out solid-liquid separation, attached resultant solid ammonium chloride is separated from acetochlor solution, filter cake is solid ammonium chloride; Still contain 10% acetochlor in the filter cake; Utilize the method for ammonium chloride recrystallization, in extraction kettle, extract content, increase yield at 96% acetochlor; The ammonium chloride of recrystallization is sold, and used water jacket is used; Filtrating is proceeded liquid liquid and separated: filtrating adds water and washes in the washing still: washing back organic phase is advanced scrapper thin film evaporator, and it is 98% acetochlor that precipitation gets content; Water after the washing distills out that ethanol is laggard goes into water treatment.
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| CN2012100523819A CN102649770A (en) | 2012-03-02 | 2012-03-02 | Production method of high-content acetochlor by methylene method |
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| CN2012100523819A CN102649770A (en) | 2012-03-02 | 2012-03-02 | Production method of high-content acetochlor by methylene method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387287A (en) * | 2014-12-18 | 2015-03-04 | 山东胜邦绿野化学有限公司 | Method for purifying acetochlor crude oil |
| CN106366013A (en) * | 2016-08-31 | 2017-02-01 | 中农发河南农化有限公司 | Recycling and reusing method for 2-methyl-6-ethyl methylenimine residual liquid |
| CN107868020A (en) * | 2017-10-30 | 2018-04-03 | 安徽富田农化有限公司 | A kind of preparation method of alachlor |
| CN109970599A (en) * | 2017-12-28 | 2019-07-05 | 山东侨昌化学有限公司 | A kind of method of continuous synthesis Acetochlor intermediate N 2- methyl -6- ethylphenyl azomethine |
| CN113860995A (en) * | 2021-10-12 | 2021-12-31 | 迈奇化学股份有限公司 | Recovery treatment process and treatment device for waste liquid generated in acetochlor production |
| CN114031519A (en) * | 2021-12-08 | 2022-02-11 | 浙江工业大学 | A kind of method of synthesizing N-arylimine |
| CN116178199A (en) * | 2022-12-04 | 2023-05-30 | 辽阳恒业化工有限公司 | Preparation method of N-chloroacetanilide herbicide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101565387A (en) * | 2009-05-15 | 2009-10-28 | 北京颖泰嘉和科技股份有限公司 | Preparation method of N-methylene-2-methyl-6-ethylaniline |
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2012
- 2012-03-02 CN CN2012100523819A patent/CN102649770A/en active Pending
Patent Citations (1)
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387287A (en) * | 2014-12-18 | 2015-03-04 | 山东胜邦绿野化学有限公司 | Method for purifying acetochlor crude oil |
| CN104387287B (en) * | 2014-12-18 | 2015-11-25 | 山东胜邦绿野化学有限公司 | A kind of method of acetochlor oil purifying |
| CN106366013A (en) * | 2016-08-31 | 2017-02-01 | 中农发河南农化有限公司 | Recycling and reusing method for 2-methyl-6-ethyl methylenimine residual liquid |
| CN107868020A (en) * | 2017-10-30 | 2018-04-03 | 安徽富田农化有限公司 | A kind of preparation method of alachlor |
| CN109970599A (en) * | 2017-12-28 | 2019-07-05 | 山东侨昌化学有限公司 | A kind of method of continuous synthesis Acetochlor intermediate N 2- methyl -6- ethylphenyl azomethine |
| CN113860995A (en) * | 2021-10-12 | 2021-12-31 | 迈奇化学股份有限公司 | Recovery treatment process and treatment device for waste liquid generated in acetochlor production |
| CN113860995B (en) * | 2021-10-12 | 2024-05-24 | 迈奇化学股份有限公司 | Recovery treatment process and treatment device for waste liquid produced in production of acetochlor |
| CN114031519A (en) * | 2021-12-08 | 2022-02-11 | 浙江工业大学 | A kind of method of synthesizing N-arylimine |
| CN114031519B (en) * | 2021-12-08 | 2024-04-26 | 浙江工业大学 | Method for synthesizing N-aryl imine |
| CN116178199A (en) * | 2022-12-04 | 2023-05-30 | 辽阳恒业化工有限公司 | Preparation method of N-chloroacetanilide herbicide |
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Application publication date: 20120829 |