CN107445843A - One kind is without the methylaniline preparation method of 3 chlorine of discoloration 2 - Google Patents
One kind is without the methylaniline preparation method of 3 chlorine of discoloration 2 Download PDFInfo
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- CN107445843A CN107445843A CN201710609005.8A CN201710609005A CN107445843A CN 107445843 A CN107445843 A CN 107445843A CN 201710609005 A CN201710609005 A CN 201710609005A CN 107445843 A CN107445843 A CN 107445843A
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- chloro
- methylaniline
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- chlorine
- discoloration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses one kind without the methylaniline preparation method of 3 chlorine of discoloration 2, comprise the following steps：（1）, hydrogenating reduction：The nitrotoleune of 6 chlorine of liquid 2 is added in reduction kettle, adds catalyst, carries out reduction reaction；（2）, press filtration：By material in reduction kettle and catalyst press-in filter, separation of material and catalyst；（3）, washing layering dehydration：The methylaniline crude product of 3 chlorine in surge tank 2 is added into water agitator treating, stratification, the obtained methylaniline of 3 chlorine of lower floor's material 2 is transferred to dehydrating kettle；（4）Rectifying：Chip solid sodium hydroxide is added into the methylaniline crude product of 3 chlorine 2, the methylaniline sterling of 3 chlorine of main distillate fraction 2 is evaporated under reduced pressure out and adds triethanolamine thereto, to protect product non-discolouring.Beneficial effects of the present invention：Product can keep colorless and transparent the long period, solve problem easy to change during the methylaniline of 3 chlorine 2 stores.
Description
Technical field
The invention belongs to one kind without discoloration 3- chloro-2-methyl aniline preparation methods.
Background technology
Existing preparation method is usually using 6- Chloro-2-Nitrobenzenes as raw material, adds the metallic catalysts such as iron, nickel, adds
Hydrogen reduction, layering dehydration remove the 3- chloro-2-methyl anilines for producing high content in crude product after moisture through rectifying column.Traditional rectifying
It is to distill out the higher 3- chloro-2-methyl anilines of purity by improving rectifying tower effect, the product prepared is in atmosphere quickly
Become brown.
The shortcomings that preparation method：1st, rectifying is high in tower effect input cost；2 product purities are higher but still easy to change, nothing
Method keeps colorless state for a long time.
The content of the invention
According to existing process technical deficiency, the present invention provides a kind of without discoloration 3- chloro-2-methyl aniline preparation methods, utilization
For nitrogen with production, using solid sodium hydroxide, triethanolamine, it is in colorless state for a long time to keep chloro- 2 methylanilines of 3-, is solved
The chloro- 2 methylaniline discoloration problems of 3-, good basis is established to prepare chloro- 2 methylanilines of top grade product 3-.
The present invention provides one kind without discoloration 3- chloro-2-methyl aniline preparation methods, comprises the following steps：
（1）, hydrogenating reduction：Liquid 6- Chloro-2-Nitrobenzenes are added in reduction kettle, add catalyst, carry out gas displacement, gas
Hydrogen is passed through after the completion of body displacement and carries out reduction reaction, reaction terminates to be passed through nitrogen into reduction kettle, and chemical equation is：
（2）, press filtration：By material in reduction kettle and catalyst press-in filter, separation of material and catalyst, catalyst return to reduction
Kettle continues to apply mechanically, and the chloro- 2 methylaniline crude products of 3- enter surge tank, and the protection of pressure-fired nitrogen is filled with surge tank.
（3）, washing layering dehydration：3- chloro-2-methyl anilines crude product in surge tank is pumped into washing kettle, adds water stirring to wash
Wash, stratification, and protected with pressure-fired nitrogen；Obtained chloro- 2 methylanilines of lower floor material 3- are transferred to dehydrating kettle, sloughed
Moisture in 3- chloro-2-methyl aniline crude products.
（4）Rectifying：3- chloro-2-methyl anilines after dehydration are transferred to small rectifying column, and decompression steams front-end volatiles, and sampling is qualified
Afterwards, material is transferred to big rectifying column, chip solid sodium hydroxide is added into big rectifying column, it is chloro- to be evaporated under reduced pressure out main distillate fraction 3-
2-aminotoluene sterling, triethanolamine is added into the pans of storage 3- chloro-2-methyl aniline sterlings, to protect product constant
Color.
In hydrogenation reaction, temperature is that temperature is low, and reaction speed is slow an important factor for influenceing reaction speed, is not suitable for work
Industry metaplasia is produced, and temperature is too high, and side reaction can increase substantially；In hydrogenation reaction, pressure is also a factor that can not be ignored,
For the present invention by substantial amounts of experiment, preferable reaction temperature is 135 ~ 155 DEG C, and reaction pressure is between 0.5MPa ~ 1.0MPa.
3- chloro-2-methyl aniline crude products add water agitator treating, preferably 3- chloro-2-methyl anilines and water quality in washing kettle
Than for 7 ~ 10:1.
Chloro- 2 methylanilines of 3- slough moisture in dehydrating kettle, and then enter in distillation process, and preferably dehydration temperaturre is
100 DEG C, vacuum is -0.08 MPa.
The present invention, with production, solid sodium hydroxide, triethanolamine is separately added into before and after rectifying, keeps 3- using nitrogen
Chloro- 2 methylaniline is in colorless state for a long time, solves the chloro- 2 methylaniline discoloration problems of 3-, the solid sodium hydroxide of addition and three
The amount of monoethanolamine is a vital parameter, and preferably sodium hydroxide and the chloro- 2 methylaniline mass ratioes of 3- are 1 ~ 5：1000,
Triethanolamine is 4 ~ 10 with the chloro- 2 methylaniline mass ratioes of 3-：1000, during rectifying, preferably rectification temperature tower top is
125 ~ 145 DEG C, vacuum is -0.098 MPa.
The preparation method of o-fluorotobuene of the present invention is catalyzed in the presence of a catalyst using 6- Chloro-2-Nitrobenzenes as raw material
Hydrogenation adds solid sodium hydroxide and triethanolamine, Neng Gouyou for 3- chloro- 2 methylanilines in preparation process in stage of rectification
Effect prevents product from changing colour.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is general based on the embodiment in the present invention, this area
The every other embodiment that logical technical staff is obtained under the premise of creative work is not made, belongs to protection of the present invention
Scope.The experimental method of unreceipted actual conditions in the following example, generally according to normal condition, or according to manufacturer
Proposed condition, unless stated otherwise, ratio and percentage are based on weight.
The raw materials used embodiment of the present invention is commercially available.
Embodiment 1
1st, hydrogenating reduction：The 6- Chloro-2-Nitrobenzene 2000Kg that prior steam heating has been melted are added, add catalyst nickel
0.3kg, Ammonia suppress dechlorination auxiliary agent 1.3kg, detect oxygen content, inspection in gas in kettle by oxygen content detector after nitrogen displacement
Qualified rear progress hydrogen displacement is surveyed, hydrogen is finally passed through, opens stirring, adjusts recirculated water and chilled water pipeline valve, control kettle
140 DEG C of temperature, kettle pressure are 0.8MPa maintenance reactions, 150r/min stirrings, react 7 hours and sample, after gas chromatographic detection is qualified, stop
Only it is passed through hydrogen, and with hydrogen in nitrogen displacement kettle.
2nd, press filtration：Material in reduction kettle and catalyst are pressed into filter with 0.3-0.4MPa nitrogen, separation of material and urged
Agent, the blowback of catalyst nitrogen, which is returned in hydrogenation kettle, to be continued to apply mechanically, and chloro- 2 methylanilines of crude product material 3- enter surge tank, open
Surge tank nitrogen valve is filled with certain nitrogen, and it is in pressure-fired to make in surge tank.
3rd, washing layering dehydration：Chloro- 2 methylanilines of crude product 3- in surge tank are pumped into washing kettle and add water 160Kg, 50r/
Min agitator treating half an hour, stratification one hour, and protected with pressure-fired nitrogen, chloro- 2 first of lower floor material 3- that will be obtained
Base aniline is transferred to dehydrating kettle, opens jacket steam, controls 100 DEG C, vacuum -0.08MPa of temperature, sloughs 3- chloro-2-methyl benzene
Moisture in amine crude product.
4th, rectifying：3- chloro-2-methyl anilines after dehydration are transferred to small rectifying column, the heating of admittance deep fat, tower top temperature 100
DEG C, decompression steams front-end volatiles, opens reflux pump, after backflow is qualified, regulation reflux ratio extraction front-end volatiles, and small rectifying tower bottom sampling
After qualified, material is transferred to big rectifying column, in big rectifying column add chip solid sodium hydroxide 2Kg, 130 DEG C of tower top temperature,
Main distillate fraction 3- chloro-2-methyl anilines are evaporated under reduced pressure out, triethanolamine 9Kg are added in pans, to protect product non-discolouring.
Embodiment 2
1st, hydrogenating reduction：The 6- Chloro-2-Nitrobenzene 2000Kg that prior steam heating has been melted are added, add catalyst platinum
0.3kg, Ammonia suppress dechlorination auxiliary agent 1.3kg, detect oxygen content, inspection in gas in kettle by oxygen content detector after nitrogen displacement
Qualified rear progress hydrogen displacement is surveyed, hydrogen is finally passed through, opens stirring, adjusts recirculated water and chilled water pipeline valve, control kettle
145 DEG C of temperature, kettle pressure is 0.5MPa maintenance reactions, reacts 7 hours and samples, and after gas chromatographic detection is qualified, stopping is passed through hydrogen, and
It is unqualified to continue to react with hydrogen in nitrogen displacement kettle.
2nd, press filtration：Material in reduction kettle and catalyst are pressed into filter with 0.3-0.4MPa nitrogen, separation of material and urged
Agent, the blowback of catalyst nitrogen, which is returned in hydrogenation kettle, to be continued to apply mechanically, and chloro- 2 methylanilines of crude product material 3- enter surge tank, open
Surge tank nitrogen valve is filled with certain nitrogen, and it is in pressure-fired to make in surge tank.
3rd, washing layering dehydration：Chloro- 2 methylanilines of crude product 3- in surge tank are pumped into washing kettle and add water 180Kg washings half
Hour, stratification one hour, and protected with pressure-fired nitrogen, obtained chloro- 2 methylanilines of lower floor material 3- are transferred to dehydration
Kettle, jacket steam is opened, control 100 DEG C, vacuum -0.08MPa of temperature, slough the moisture in 3- chloro-2-methyl aniline crude products.
4th, rectifying：3- chloro-2-methyl anilines after dehydration are transferred to small rectifying column, the heating of admittance deep fat, tower top temperature 105
DEG C, decompression steams front-end volatiles, opens reflux pump, after backflow is qualified, regulation reflux ratio extraction front-end volatiles, and small rectifying tower bottom sampling
After qualified, material is transferred to big rectifying column, in big rectifying column add chip solid sodium hydroxide 4Kg, 135 DEG C of tower top temperature,
Main distillate fraction 3- chloro-2-methyl anilines are evaporated under reduced pressure out, triethanolamine 12Kg are added in pans, to protect product non-discolouring.
Embodiment 3
1st, hydrogenating reduction：The 6- Chloro-2-Nitrobenzene 2000Kg that prior steam heating has been melted are added, add palladium catalyst
0.300kg, Ammonia suppress dechlorination auxiliary agent 1.3kg, detect in kettle oxygen content in gas by oxygen content detector after nitrogen displacement,
Qualified rear progress hydrogen displacement is detected, hydrogen is finally passed through, opens stirring, adjust recirculated water and chilled water pipeline valve, control
150 DEG C of kettle temperature, kettle pressure is 1.0MPa maintenance reactions, reacts 7 hours and samples, and after gas chromatographic detection is qualified, stopping is passed through hydrogen,
And with hydrogen in nitrogen displacement kettle, it is unqualified to continue to react.
2nd, press filtration：Material in reduction kettle and catalyst are pressed into filter with 0.3-0.4MPa nitrogen, separation of material and urged
Agent, the blowback of catalyst nitrogen, which is returned in hydrogenation kettle, to be continued to apply mechanically, and chloro- 2 methylanilines of crude product material 3- enter surge tank, open
Surge tank nitrogen valve is filled with certain nitrogen, and it is in pressure-fired to make in surge tank.
3rd, washing layering dehydration：Chloro- 2 methylanilines of crude product 3- in surge tank are pumped into washing kettle and add water 200Kg washings half
Hour, stratification one hour, and protected with pressure-fired nitrogen, obtained chloro- 2 methylanilines of lower floor material 3- are transferred to dehydration
Kettle, jacket steam is opened, control 100 DEG C, vacuum -0.08MPa of temperature, slough the moisture in 3- chloro-2-methyl aniline crude products.
4th, rectifying：3- chloro-2-methyl anilines after dehydration are transferred to small rectifying column, the heating of admittance deep fat, tower top temperature 110
DEG C, decompression steams front-end volatiles, opens reflux pump, after backflow is qualified, regulation reflux ratio extraction front-end volatiles, and small rectifying tower bottom sampling
After qualified, material is transferred to big rectifying column, in big rectifying column add chip solid sodium hydroxide 6Kg, 140 DEG C of tower top temperature,
Main distillate fraction 3- chloro-2-methyl anilines are evaporated under reduced pressure out, triethanolamine 16.5Kg are added in pans, to protect product constant
Color.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (7)
1. the present invention provides one kind without discoloration 3- chloro-2-methyl aniline preparation methods, comprise the following steps：
（1）, hydrogenating reduction：Liquid 6- Chloro-2-Nitrobenzenes are added in reduction kettle, add catalyst, carry out gas displacement, gas
Hydrogen is passed through after the completion of body displacement and carries out reduction reaction, reaction terminates to be passed through nitrogen into reduction kettle；
（2）, press filtration：By material in reduction kettle and catalyst press-in filter, separation of material and catalyst, catalyst return to reduction
Kettle continues to apply mechanically, and the chloro- 2 methylaniline crude products of 3- enter surge tank, and the protection of pressure-fired nitrogen is filled with surge tank；
（3）, washing layering dehydration：3- chloro-2-methyl anilines crude product in surge tank is pumped into washing kettle, adds water agitator treating, it is quiet
Layering is put, and is protected with pressure-fired nitrogen；Obtained chloro- 2 methylanilines of lower floor material 3- are transferred to dehydrating kettle, it is chloro- to slough 3-
Moisture in 2-aminotoluene crude product；
（4）Rectifying：3- chloro-2-methyl anilines after dehydration are transferred to small rectifying column, and decompression steams front-end volatiles, will after sampling is qualified
Material is transferred to big rectifying column, and chip solid sodium hydroxide is added into big rectifying column, is evaporated under reduced pressure out main distillate fraction 3- chloro-2-methyls
Aniline sterling, triethanolamine is added into the pans of storage 3- chloro-2-methyl aniline sterlings, to protect product non-discolouring.
2. one kind according to claim 1 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Step（1）
Reaction temperature is 135 ~ 155 DEG C, reaction pressure： 0MPa≤P≤1.0MPa.
3. one kind according to claim 2 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Reaction pressure
Power：0.5MPa≤P≤1.0MPa.
4. one kind according to claim 1 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Step（3）
3- chloro-2-methyl anilines and water quality ratio are 7 ~ 10 in washing process:1.
5. one kind according to claim 1 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Step（3）
Dehydration temperaturre is 100 DEG C in dehydration, and vacuum is -0.08 MPa.
6. one kind according to claim 1 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Step（4）
Middle addition sodium hydroxide is 1 ~ 5 with the chloro- 2 methylaniline mass ratioes of 3-：1000, add triethanolamine and the chloro- 2 methylaniline matter of 3-
Amount is than being 4 ~ 10：1000.
7. one kind according to claim 1 is without discoloration 3- chloro-2-methyl aniline preparation methods, it is characterised in that：Step（4）
It is 125 ~ 145 DEG C to control rectification temperature tower top, and vacuum is -0.098 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710609005.8A CN107445843A (en) | 2017-07-25 | 2017-07-25 | One kind is without the methylaniline preparation method of 3 chlorine of discoloration 2 |
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| CN201710609005.8A CN107445843A (en) | 2017-07-25 | 2017-07-25 | One kind is without the methylaniline preparation method of 3 chlorine of discoloration 2 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890901A (en) * | 2022-06-17 | 2022-08-12 | 老河口华辰化学有限公司 | Synthesis method for synthesizing m-toluidine by 2-chloro-3-nitrotoluene one-step method |
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| CN1962609A (en) * | 2006-11-27 | 2007-05-16 | 浙江大学 | Herbicide intermediate 3-chloro-2-methyl aniline production process |
| CN102234236A (en) * | 2010-04-23 | 2011-11-09 | 龙口市福尔生化科技有限公司 | Synthetic method of 3-chloro-2-methylaniline |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
-
2017
- 2017-07-25 CN CN201710609005.8A patent/CN107445843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1962609A (en) * | 2006-11-27 | 2007-05-16 | 浙江大学 | Herbicide intermediate 3-chloro-2-methyl aniline production process |
| CN102234236A (en) * | 2010-04-23 | 2011-11-09 | 龙口市福尔生化科技有限公司 | Synthetic method of 3-chloro-2-methylaniline |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
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| Title |
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| 何福春 等: "100 t/a 99.5% 3-氯-2-甲基苯胺的生茶技术和经济分析", 《湖北化工》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890901A (en) * | 2022-06-17 | 2022-08-12 | 老河口华辰化学有限公司 | Synthesis method for synthesizing m-toluidine by 2-chloro-3-nitrotoluene one-step method |
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Application publication date: 20171208 |