CN101245010A - Method for producing civil dinitrotoluene - Google Patents
Method for producing civil dinitrotoluene Download PDFInfo
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- CN101245010A CN101245010A CNA2008100177415A CN200810017741A CN101245010A CN 101245010 A CN101245010 A CN 101245010A CN A2008100177415 A CNA2008100177415 A CN A2008100177415A CN 200810017741 A CN200810017741 A CN 200810017741A CN 101245010 A CN101245010 A CN 101245010A
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- dinitrotoluene
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Abstract
The invention provides a new technique for synthesized civil (DNT) with good quality, which regards toluene and nitric acid as raw materials, concentrated sulfuric acid as catalyst, and carbon tetrachloride with low boiling point as solvents; in certain conditions, the DNT is produced directly, the yield of the products can reach 96.4 percent, the purity is above 98 percent, and the quality of the products satisfies the first-rate standards, 2,4-DNT/2,6-DNT is equal to 80 plus or minus 1/20 plus or minus 1, as organic solvent is introduced, little influence of temperature is caused towards the isomer ratio of products in reaction, and the conditions of nitration reaction are mild, the ratio of isomer produced is easy to be controlled, the density of waste liquid is high, and nitrate containing amount is low, which is beneficial for the concentration of waste liquid and the reduce of emission of waste water, primary nitrification and secondary nitrification are both carried on in the same reaction kettle, the technique is simple, the production cost is low, the requirement of environmental protection is satisfied, so the new technique for synthesized civil DNT with good quality has rather great implementary value and social economic benefits.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of preparation technology of dinitrotoluene (DNT), relate in particular to a kind of preparation technology of dinitrotoluene (DNT) (DNT) of civil standards.
Background technology
Toluene is the gross ton position product of petrochemical complex industry, and enrich in cheap, source, to the exploitation of its derived product, is subjected to the attention of chemical industry always.Toluene is by deep processing, can make many valuable chemical products, for example oxidation prepares phenylcarbinol, phenylformic acid, chloro synthesize benzyl chlorine, sulfonation prepares toluene sulfonic acide, nitrated preparation 2-nitrotoluene, 3-nitrotoluene, a series of important drugs intermediates such as para-nitrotoluene, can make its added value increase manyfold, have appreciable economic benefit.
In the derived product of toluene, dinitrotoluene (DNT) (DNT) is very important Chemicals, at medicine industry, dyestuff, agricultural chemicals, there is purposes widely aspect such as macromolecular material and national defence, especially (standard of civilian dinitrotoluene (DNT) is: 2 with civilian dinitrotoluene (DNT), 4-DNT/2,6-DNT=80 ± 1/20 ± 1, purity is all more than 98%) be reduced into diaminotoluene, further reaction can get tolylene diisocyanate (TDI), as the important intermediate of producing macromolecular materials such as urethane, have a wide range of applications, market outlook are very good.
For many years, it is raw material that domestic industry production dinitrotoluene (DNT) all adopts toluene, nitric acid, and sulfuric acid is catalyzer, is finished by one-stage nitration, two stage nitration and aftertreatment technology, wherein one-stage nitration and two stage nitration separately carry out in two reactors, the technology more complicated; Sulfuric acid adds at twice, and the dense low sulphuric acid soln (concentration is at sulfuric acid about 65%) that adds dilution in the one-stage nitration reactor is with control isomery ratio; Add the vitriol oil in the two stage nitration reactor.Like this, caused the sulfuric acid usage quantity big, and produced a large amount of lower spent acid of sulfur acid concentration, strengthened the difficulty that spent acid is handled, produced a large amount of waste water, environment has been caused severe contamination; Simultaneously, because the requirement to temperature is relatively harsher in the one-stage nitration reaction, the dinitrotoluene (DNT) product isomery ratio of production is difficult to control, and quality product is not high, and productive rate is also not high (productive rate is 85～90%) generally.
Summary of the invention
The objective of the invention is provides a kind of yield height in order to overcome the defective that prior art exists, and quality product is excellent, and spent acid is handled easily, and cost is low, the preparation technology of the simple civilian dinitrotoluene (DNT) product of technology.
The technology of the synthetic civilian dinitrotoluene (DNT) (DNT) of the present invention may further comprise the steps:
One-stage nitration: toluene and the tetracol phenixin volume ratio with 1: 0.5～1: 2.5 is added in the reaction vessel, be warming up to 30～50 ℃, slowly add the nitrosonitric acid with the toluene equimolar amount, under agitation react 10～60min;
Two stage nitration: slowly add the nitrosonitric acid of 1～1.2 times of toluene molar weight, be warming up to 50～70 ℃; Slowly add toluene molar weight 2.5～3.5 times of amounts, concentration then and be 88%～98.2% the vitriol oil, continue reaction 30～90min;
Aftertreatment technology: standing demix, isolate organic phase while hot, steam and reclaim organic solvent, obtain dinitrotoluene (DNT); Isolating inorganicly extract with extraction solvent steams and reclaims extraction solvent, separates out the solid dinitrotoluene (DNT); Merge the dinitrotoluene (DNT) product, and wash to pH=7～8 with the aqueous sodium carbonate of dinitrotoluene (DNT) quality 2.5%～3.5%, wash with water to neutrality again, drying obtains the dinitrotoluene (DNT) product.
Its synthetic route is as follows:
Extraction solvent in the described postprocessing working procedures is a methylene dichloride, trichloromethane, tetracol phenixin etc.
Feeding intake of the vitriol oil can add before the one-stage nitration reaction, and the vitriol oil both played katalysis to one-stage nitration like this, also can react katalysis to the two stage nitration of proceeding; The vitriol oil also can add in one-stage nitration reaction back, and the one-stage nitration reaction is also can carry out under the sulphuric acid catalysis not having like this, and the vitriol oil plays katalysis to two stage nitration, also can obtain good result.
The present invention compared with prior art has the following advantages:
1, the present invention is a raw material with toluene, nitric acid, is catalyzer with the vitriol oil, is aided with lower boiling tetracol phenixin and makes solvent, direct under certain conditions synthesizing dinitrotoluene product.The productive rate of products obtained therefrom can reach 96.4%, and purity is all more than 98%, and quality product meets civilian excellent standard: 2, and 4-DNT/2,6-DNT=80 ± 1/20 ± 1.
2, because the introducing of organic solvent, make in the reaction temperature little to the influence of product isomery ratio, and the nitration reaction mild condition, produce isomer proportion and be easy to control.
3, Fan Ying organic solvent solvent boiling point is low, is easy to recycle.
4, reaction gained acid-spending strength height, and it is low to contain the nitre amount, is easy to the minimizing of the concentrated and wastewater discharge of spent acid;
5, one-stage nitration and two stage nitration carry out in same reactor, and technology is simple, and production cost is lower, and compliance with environmental protection requirements has bigger implementary value and economic results in society.
Embodiment:
Embodiment 1
One-stage nitration: the tetracol phenixin of 4mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 50 ℃, reaction 20min.
Two stage nitration: slowly drip the 7mL vitriol oil (concentration 98%), be warming up to the nitrosonitric acid that drips 2.4mL after 65 ℃, continue stirring reaction 60min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the methylene dichloride of 20mL mutually and extract at twice, steam methylene chloride and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 2.5% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 89.9%, 2,4-DNT/2,6-DNT=80.8: 19.2.
Embodiment 2
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 30 ℃, slowly drip the 7mL vitriol oil (concentration 98.2%), reaction 30min.
Two stage nitration: after being warming up to 65 ℃, drip the nitrosonitric acid of 2.4mL, continue stirring reaction 60min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, and organic phase steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the trichloromethane of 20mL mutually and extract at twice, steam the solvent trichloromethane and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 3% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 92.8%, 2,4-DNT/2,6-DNT=80.5: 19.5.
Embodiment 3
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 50 ℃, reaction 10min.
Two stage nitration: slowly drip the 7mL vitriol oil (98.2%), be warming up to the nitrosonitric acid that drips 2.4mL after 65 ℃, continue stirring reaction 90min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the trichloromethane of 20mL mutually and extract at twice, steam the solvent trichloromethane and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality 3.5% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 92.2%, 2,4-DNT/2,6-DNT=80.7: 19.3.
Embodiment 4
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 3mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 30 ℃, reaction 20min.
Two stage nitration: slowly drip the 7mL vitriol oil (98.2%), be warming up to the nitrosonitric acid that drips 2.4mL after 50 ℃, continue stirring reaction 70min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the methylene dichloride of 20mL mutually and extract at twice, steam methylene chloride and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 3% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 93.1%, 2,4-DNT/2,6-DNT=79.8: 20.2.
Embodiment 5
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 50 ℃, continue reaction 20min.
Two stage nitration: slowly drip the 6mL vitriol oil, be warming up to the nitrosonitric acid that drips 2.4mL after 65 ℃, continue stirring reaction 60min.
Post-reaction treatment: reaction finishes the back standing demix, tell out while hot organic phase then, inorganicly make solvent with the methylene dichloride of 20mL mutually and extract at twice, merge organic phase, earlier with 3% sodium carbonate solution be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, steam organic solvent again and separate out product (DNT), product is dried to constant weight in predrying one day final vacuum of room temperature, weighs and get an amount of DNT and do gas-chromatography.Productive rate: 94.2%, 2,4-DNT/2,6-DNT=79.8: 20.2.
Embodiment 6
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 3mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 40 ℃, continue reaction 10min.
Two stage nitration: after being warming up to 60 ℃, slowly drip the nitrosonitric acid of 2.4mL, slowly drip the 7mL vitriol oil more immediately, continue stirring reaction 60min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the tetracol phenixin of 20mL mutually and extract at twice, steam the solvent tetracol phenixin and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 3.2% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 94.5%, 2,4-DNT/2,6-DNT=79.9: 20.1.
Embodiment 7
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 50 ℃, reaction 20min.
Two stage nitration: after being warming up to 65 ℃, slowly drip the nitrosonitric acid of 2.4mL, slowly drip the 7mL vitriol oil (98.2%) more immediately, continue stirring reaction 70min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the methylene dichloride of 20mL mutually and extract at twice, steam methylene chloride and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 3% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 96.4%, 2,4-DNT/2,6-DNT=79.9: 20.1.
Embodiment 8
One-stage nitration: the tetracol phenixin of 8mL and the toluene of 4mL are added in the pyriform bottle of 100mL successively, be warming up to the nitrosonitric acid that slowly drips 1.8mL after 40 ℃, reaction 20min.
Two stage nitration: slowly drip the nitrosonitric acid of 2.4mL, be warming up to 55 ℃ after, slowly drip the 7mL vitriol oil (98.2%) immediately, continue stirring reaction 60min.
Post-reaction treatment: reaction finishes the back standing demix, tells organic phase then while hot, steams the solvent tetracol phenixin and separates out product DNT; Inorganicly make solvent with the methylene dichloride of 20mL mutually and extract at twice, steam methylene chloride and separate out product DNT.Merge product DNT, earlier with the sodium carbonate solution of DNT quality about 2.5% be washed till pH extremely value use an amount of washing then 2 to 3 times 7～8, be dried to constant weight in predrying one day final vacuum of room temperature, weigh and get an amount of DNT and do gas-chromatography.Productive rate: 93.7%, 2,4-DNT/2,6-DNT=80.4: 19.6.
Claims (5)
1, a kind of preparation technology of civilian dinitrotoluene (DNT) may further comprise the steps:
One-stage nitration: toluene and the organic solvent volume ratio with 1: 0.5～1: 2.5 is added in the reaction vessel, be warming up to 30～50 ℃, add the nitric acid with the toluene equimolar amount, under agitation react 10～60min;
Two stage nitration: add the nitric acid of 1～1.2 times of amount of toluene mole, be warming up to 50～70 ℃; Add toluene molar weight 2.5～3.5 times of amounts, concentration then and be 88%～98.2% the vitriol oil, continue reaction 30～90min;
Aftertreatment technology: standing demix, isolate organic phase while hot, steam and reclaim organic solvent, obtain dinitrotoluene (DNT); Inorganicly steam and reclaim extraction solvent, separate out dinitrotoluene (DNT) with extraction solvent extraction; Merge the dinitrotoluene (DNT) product, and wash to pH=7～8 with the aqueous sodium carbonate of dinitrotoluene (DNT) quality 2.5%～3.5%, wash with water to neutrality again, drying obtains the dinitrotoluene (DNT) product.
2, the preparation technology of civilian dinitrotoluene (DNT) according to claim 1, it is characterized in that: described nitric acid is nitrosonitric acid.
3, the preparation technology of civilian dinitrotoluene (DNT) according to claim 1, it is characterized in that: described organic solvent is a tetracol phenixin.
4, the preparation technology of civilian dinitrotoluene (DNT) according to claim 1, it is characterized in that: the extraction solvent in the described postprocessing working procedures is methylene dichloride or trichloromethane or tetracol phenixin.
5, the preparation technology of civilian dinitrotoluene (DNT) according to claim 1 is characterized in that: the described vitriol oil adds before the one-stage nitration reaction or in one-stage nitration reaction back adding.
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| CN2008100177415A CN101245010B (en) | 2008-03-08 | 2008-03-08 | Method for producing civil dinitrotoluene |
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| CN2008100177415A CN101245010B (en) | 2008-03-08 | 2008-03-08 | Method for producing civil dinitrotoluene |
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| CN101245010B CN101245010B (en) | 2011-06-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557179A (en) * | 2011-11-17 | 2012-07-11 | 南京理工大学 | Method for removing nitrotoluene in high-concentration waste acid |
| CN103508850A (en) * | 2013-10-24 | 2014-01-15 | 浙江鼎龙科技有限公司 | Preparation method for 2,6-dihydroxytoluene |
| CN111269191A (en) * | 2018-12-04 | 2020-06-12 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of pesticide intermediate aryl triazolinone compound |
| CN111499517A (en) * | 2020-04-15 | 2020-08-07 | 北京格林凯默科技有限公司 | Preparation method of m-nitrobenzotrifluoride |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099080A (en) * | 1991-03-08 | 1992-03-24 | Olin Corporation | Process for preparing dinitrotoluene |
| US5245092A (en) * | 1991-03-15 | 1993-09-14 | Olin Corporation | Process for preparing dinitrotoluene with low by-product content |
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2008
- 2008-03-08 CN CN2008100177415A patent/CN101245010B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557179A (en) * | 2011-11-17 | 2012-07-11 | 南京理工大学 | Method for removing nitrotoluene in high-concentration waste acid |
| CN103508850A (en) * | 2013-10-24 | 2014-01-15 | 浙江鼎龙科技有限公司 | Preparation method for 2,6-dihydroxytoluene |
| CN103508850B (en) * | 2013-10-24 | 2015-05-13 | 浙江鼎龙科技有限公司 | Preparation method for 2,6-dihydroxytoluene |
| CN111269191A (en) * | 2018-12-04 | 2020-06-12 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of pesticide intermediate aryl triazolinone compound |
| CN111499517A (en) * | 2020-04-15 | 2020-08-07 | 北京格林凯默科技有限公司 | Preparation method of m-nitrobenzotrifluoride |
| CN111499517B (en) * | 2020-04-15 | 2022-11-08 | 北京格林凯默科技有限公司 | Preparation method of m-nitrobenzotrifluoride |
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