CN103044268A - Application of ammonia gas to preparation of o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene - Google Patents
Application of ammonia gas to preparation of o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene Download PDFInfo
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- CN103044268A CN103044268A CN2012105870295A CN201210587029A CN103044268A CN 103044268 A CN103044268 A CN 103044268A CN 2012105870295 A CN2012105870295 A CN 2012105870295A CN 201210587029 A CN201210587029 A CN 201210587029A CN 103044268 A CN103044268 A CN 103044268A
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Abstract
The invention discloses an application of ammonia gas to preparation of o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene. A preparation method for the o-chloroaniline comprises the steps as follows: taking the ortho-nitrochlorobenzene as a raw material, introducing the ammonia gas into an alcohol solution of the ortho-nitrochlorobenzene, carrying out the catalytic hydrogenation reaction under the pressure of 0.5-4.0 MPa at the temperature of 20-90 DEG in the presence of a catalyst-raney nickel, ending the reaction, and treating to obtain the o-chloroaniline, wherein the usage amount of the catalyst is 1-8% of the mass of the raw material. According to the application, the ammonia gas is taken as a dechlorination inhibitor for inhibiting side reaction of dechlorination, the reaction conditions are moderate, the reaction time is short, the selectivity of the prepared o-chloroaniline is more than 99%, the dechlorination amount is less than 0.4%, the yield of the o-chloroaniline is increased, the purity of the o-chloroaniline is improved, and the post-treatment process is simplified.
Description
Technical field
The present invention relates to ammonia and prepare application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene.
Technical background
Ortho-Chloro aniline is a kind of important organic intermediate, is widely used in the fields such as medicine, agricultural chemicals, dyestuff, spices.The method for preparing Ortho-Chloro aniline by o-Nitrochlorobenzene reduction has many, and common method has sodium sulfide reducing method, hydrazine hydrate reduction method, iron powder reducing method, electrolytic reduction, catalytic hydrogenating reduction method and hydrogen transference method etc.Sodium sulfide reducing method yield is lower, the wastewater treatment trouble; Hydrazine hydrate reduction method and iron powder reducing method three-waste pollution are heavier; Electrolytic reduction is cleaning procedure, but the electrolytic reduction facility investment is large, and industrialization is restricted; The hydrogen transference method needs higher alcohols to make hydrogen donor, and production cost is high; Catalytic hydrogenating reduction method yield is high, the three wastes are few, it is a kind of cleaning procedure, but prepare in catalytic hydrogenation of o-nitro-chlorobenzene C-Cl key hydrogenolysis dechlorination side reaction easily occurs in the process of Ortho-Chloro aniline, generate aniline and hydrogenchloride, reduced the activity of catalyzer, affected product purity and yield, the hydrogenchloride that generates simultaneously can cause corrosion to equipment.The dechlorination problem that solves in the hydrogenating reduction process has two kinds of methods usually: the one, in reaction system, add the dechlorination inhibitor; The 2nd, improve catalyst performance, reach the purpose that suppresses dechlorination.Dechlorination inhibitor commonly used is: quadrol, hexahydroaniline, ammoniacal liquor etc., though these dechlorination inhibitor can play certain dechlorination restraining effect, and poor effect, and need higher temperature of reaction and long reaction times.
Summary of the invention
Technical problem to be solved by this invention provides a kind of ammonia and prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, take ammonia as the dechlorination inhibitor, the generation of establishment dechlorination side reaction improves productive rate and product purity, reaction conditions is gentle, and can Reaction time shorten.
For solving the problems of the technologies described above, the invention provides a kind of ammonia and prepare application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, take o-Nitrochlorobenzene as raw material, ammonia is passed in the alcoholic solution of o-Nitrochlorobenzene, in the presence of catalyzer, carry out catalytic hydrogenation reaction under 20 ℃～90 ℃, 0.5～4.0 MPa pressure, reaction finishes aftertreatment and obtains Ortho-Chloro aniline, and described catalyzer is Raney's nickel.
Preferably, temperature of reaction is 50 ℃～60 ℃, and reaction pressure is 0.7～1.0 MPa.
This reacts described alcohol is methyl alcohol or ethanol, and pure consumption is 50%～300% of raw materials quality, and preferable amount is 100%.
The consumption of described catalyzer is 1%～8% of raw materials quality, and preferably, the consumption of catalyzer is 3%～6% of raw materials quality.
The source of ammonia of the present invention is: dilute ammonia solution is slowly joined in the sodium hydrate solid, and the solution heat when utilizing sodium hydrate solid water-soluble continues and stably obtains ammonia.
Described ammonia usage is 1%～6% of raw materials quality, and preferably, the consumption of ammonia is 2%～4% of raw materials quality.
The described reaction times is 4～11 hours.
Beneficial effect of the present invention is: the dechlorination inhibitor is simple and easy to, can effectively suppress the generation of dechlorination side reaction, reaction conditions is gentle, reaction times is short, and the crude product foreign matter content after having reacted reduces, and has simplified the subsequent disposal of Ortho-Chloro aniline, reduced cost, improved product purity, the selectivity of the Ortho-Chloro aniline that experiment makes is greater than 99%, and the dechlorination amount is less than 0.4%.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
In the high-pressure hydrogenation still of 1000 mL, drop into o-Nitrochlorobenzene 250 g, methyl alcohol 250 mL and Raney's nickel 15 g, add a certain amount of sodium hydrate solid at another in the reactor of Dropping feeder, drip 25% ammonia soln, the ammonia that produces passes in the above-mentioned reaction solution, and the add-on of controlling ammonia by under meter is 7.5 g.Close ammonia, use hydrogen exchange three times, regulating the still pressure is 1.0 MPa, open and stir, be warming up to 60 ℃ of reactions, reacted 4 hours, no longer change to pressure, stopped reaction takes out reaction solution, filter out catalyzer, filtrate is carried out liquid-phase chromatographic analysis, and the result shows that the transformation efficiency of nitro-chlorobenzene is 100%, the selectivity of Ortho-Chloro aniline is 99.3%, and the dechlorination amount is 0.30%.
Embodiment 2
In the high-pressure hydrogenation still of 1000 mL, drop into o-Nitrochlorobenzene 250 g, methyl alcohol 250 mL and Raney's nickel 7.5 g, add a certain amount of sodium hydrate solid at another in the reactor of Dropping feeder, drip 25% ammonia soln, the ammonia that produces passes in the above-mentioned reaction solution, and the add-on of controlling ammonia by under meter is 7.5 g.Close ammonia, use hydrogen exchange three times, regulating the still pressure is 0.8 MPa, open and stir, be warming up to 60 ℃ of reactions, reacted 6 hours, no longer change to pressure, stopped reaction takes out reaction solution, filter out catalyzer, filtrate is carried out liquid-phase chromatographic analysis, and the result shows that the transformation efficiency of nitro-chlorobenzene is 99.6%, the selectivity of Ortho-Chloro aniline is 99.0%, and the dechlorination amount is 0.33%.
Embodiment 3
In the high-pressure hydrogenation still of 1000 mL, drop into o-Nitrochlorobenzene 250 g, methyl alcohol 250 mL and Raney's nickel 15 g, add a certain amount of sodium hydrate solid at another in the reactor of Dropping feeder, drip 25% ammonia soln, the ammonia that produces passes in the above-mentioned reaction solution, and the add-on of controlling ammonia by under meter is 7.5 g.Close ammonia, use hydrogen exchange three times, regulating the still pressure is 0.8 MPa, open and stir, be warming up to 60 ℃ of reactions, reacted 9 hours, no longer change to pressure, stopped reaction takes out reaction solution, filter out catalyzer, filtrate is carried out liquid-phase chromatographic analysis, and the result shows that the transformation efficiency of nitro-chlorobenzene is 100%, the selectivity of Ortho-Chloro aniline is 99.3%, and the dechlorination amount is 0.29%.
Embodiment 4
In the high-pressure hydrogenation still of 1000 mL, drop into o-Nitrochlorobenzene 250 g, ethanol 250 mL and Raney's nickel 15 g, add a certain amount of sodium hydrate solid at another in the reactor of Dropping feeder, drip 25% ammonia soln, the ammonia that produces passes in the above-mentioned reaction solution, and the add-on of measuring ammonia by under meter is 2.5 g.Close ammonia, use hydrogen exchange three times, regulating the still pressure is 0.8 MPa, open and stir, be warming up to 56 ℃～60 ℃ reactions, reacted 11 hours, no longer change to pressure, stopped reaction takes out reaction solution, filter out catalyzer, filtrate is carried out liquid-phase chromatographic analysis, and the result shows that the transformation efficiency of nitro-chlorobenzene is 100%, the selectivity of Ortho-Chloro aniline is 99.0%, and the dechlorination amount is 0.40%.
Embodiment 5
In the high-pressure hydrogenation still of 1000 mL, drop into o-Nitrochlorobenzene 250 g, ethanol 130 mL and Raney's nickel 15 g, add a certain amount of sodium hydrate solid at another in the reactor of Dropping feeder, drip 25% ammonia soln, the ammonia that produces passes in the above-mentioned reaction solution, and the add-on of controlling ammonia by under meter is 7.5 g.Close ammonia, use hydrogen exchange three times, regulating the still pressure is 0.8 MPa, open and stir, be warming up to 60 ℃ of reactions, reacted 10 hours, no longer change to pressure, stopped reaction takes out reaction solution, filter out catalyzer, filtrate is carried out liquid-phase chromatographic analysis, and the result shows that the transformation efficiency of nitro-chlorobenzene is 100%, the selectivity of Ortho-Chloro aniline is 99.1%, and the dechlorination amount is 0.36%.
Claims (10)
1. ammonia prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, take o-Nitrochlorobenzene as raw material, it is characterized in that: take ammonia as the dechlorination inhibitor, ammonia is passed in the alcoholic solution of o-Nitrochlorobenzene, in the presence of catalyzer, carry out catalytic hydrogenation reaction under 20 ℃～90 ℃, 0.5～4.0 MPa pressure, reaction finishes aftertreatment and obtains Ortho-Chloro aniline, and described catalyzer is Raney's nickel.
2. prepare application in the Ortho-Chloro aniline such as the described ammonia of claim l in catalytic hydrogenation of o-nitro-chlorobenzene, it is characterized in that: described temperature of reaction is 50 ℃～60 ℃.
3. prepare application in the Ortho-Chloro aniline such as the described ammonia of claim l in catalytic hydrogenation of o-nitro-chlorobenzene, it is characterized in that: described pressure is 0.7～1.0 MPa.
4. prepare application in the Ortho-Chloro aniline such as the described ammonia of claim l in catalytic hydrogenation of o-nitro-chlorobenzene, it is characterized in that: described pure nail alcohol or ethanol.
5. ammonia as claimed in claim 4 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: the consumption of described alcohol is 50%～300% of raw materials quality.
6. ammonia as claimed in claim 1 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: the consumption of described catalyzer is 1%～8% of raw materials quality.
7. ammonia as claimed in claim 6 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: the consumption of described catalyzer is 3%～6% of raw materials quality.
8. ammonia as claimed in claim 1 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: described ammonia usage is 1%～6% of raw materials quality.
9. ammonia as claimed in claim 8 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: described ammonia usage is 2%～4% of raw materials quality.
10. ammonia as claimed in claim 1 prepares application in the Ortho-Chloro aniline in catalytic hydrogenation of o-nitro-chlorobenzene, and it is characterized in that: the described reaction times is 4～11 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796356A (en) * | 1954-08-06 | 1958-06-11 | Allied Chem & Dye Corp | Reduction of aromatic nitrogen compounds |
| US3546297A (en) * | 1969-07-01 | 1970-12-08 | Du Pont | Process for preparation of aromatic chloroamines |
| CN1660774A (en) * | 2004-12-28 | 2005-08-31 | 浙江工业大学 | Method for preparing o-chloroaniline |
| US20080033211A1 (en) * | 2006-08-04 | 2008-02-07 | National Central University | Hydrogenation process of chlorinated nitrobenzene |
| CN101195579A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system |
| CN101333169A (en) * | 2007-03-01 | 2008-12-31 | 淮安嘉诚高新化工股份有限公司 | Production method of o-chloroaniline |
-
2012
- 2012-12-29 CN CN2012105870295A patent/CN103044268A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796356A (en) * | 1954-08-06 | 1958-06-11 | Allied Chem & Dye Corp | Reduction of aromatic nitrogen compounds |
| US3546297A (en) * | 1969-07-01 | 1970-12-08 | Du Pont | Process for preparation of aromatic chloroamines |
| CN1660774A (en) * | 2004-12-28 | 2005-08-31 | 浙江工业大学 | Method for preparing o-chloroaniline |
| US20080033211A1 (en) * | 2006-08-04 | 2008-02-07 | National Central University | Hydrogenation process of chlorinated nitrobenzene |
| CN101195579A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system |
| CN101333169A (en) * | 2007-03-01 | 2008-12-31 | 淮安嘉诚高新化工股份有限公司 | Production method of o-chloroaniline |
Non-Patent Citations (1)
| Title |
|---|
| 闫茂文 等: "Raney-Ni催化剂加氢制备间氯苯胺", 《染料与染色》 * |
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Application publication date: 20130417 |