CN106316857A - Method for adjusting p/o ratio of chlorobenzene nitration product in micro-channel reactor - Google Patents
Method for adjusting p/o ratio of chlorobenzene nitration product in micro-channel reactor Download PDFInfo
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- CN106316857A CN106316857A CN201510335856.9A CN201510335856A CN106316857A CN 106316857 A CN106316857 A CN 106316857A CN 201510335856 A CN201510335856 A CN 201510335856A CN 106316857 A CN106316857 A CN 106316857A
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Abstract
The invention relates to a method for adjusting the p/o ratio of a chlorobenzene nitration product in a micro-channel reactor. The method is characterized in that a certain amount of phosphoric acid is added to a mixed acid chlorobenzene nitration system in order to adjust the proportions of p-nitrchlorobenzene and o-nitrchlorobenzene. The method adopting a continuous feeding reaction mode has the advantages of simplicity, good effect, short nitration time not exceeding 120 s, and high chlorobenzene conversion rate reaching 97% or above, and allows the p/o ratio of the product to be lower than that of routine methods and to be controlled in a range of 1.0-1.6.
Description
Technical field
The present invention relates to a kind of micro passage reaction regulates the Benzene Chloride nitration product method to neighbour's ratio, i.e. in nitration mixture Chlorobenzene Nitration system, added a certain amount of phosphoric acid, regulate the ratio of paranitrochlorobenzene in product, o-nitrochlorobenzene.
Background technology
The nitrification mode of nitric-sulfuric acid that at present Chlorobenzene Nitration of commercial plant all uses, is substantially secured to about 1.8 to neighbour's ratio.Owing to the ortho isomer market demand is bigger, recently for neighbour is explored heavier regarding than regulation.Lv Chunxu etc. are in " selective nitration of chlorobenzene in nitric acid-sulfuric acid-Phosphoric Acid " literary composition, it is noted that add the nitration method of phosphoric acid.Reaction condition 70 DEG C, reacts more than 3 hours, uses nitration mixture dropwise reaction mode, in literary composition and not mentioned concrete conversion ratio, can to neighbour than regulation to about 1.2.Being referred to a kind of interval adiabatic nitration mode adding phosphoric acid in CN 1438214A, conversion ratio is less than 95%, and neighbour's ratio is adjustable to about 1.4.Wei Wenlong etc. refer to add the nitrification mode of phosphoric acid in " improvement of Chlorobenzene Nitration technique " literary composition, uses dropping nitration mixture technique, reacts 2 ~ 3 hours, neighbour's ratio is adjustable to about 1.3, and yield is relatively low, can be only achieved 85 ~ 91% after adding promoter.Also refer to add the nitrification mode of phosphoric acid in Master's thesis " location nitration process for chlorobenzene ", reaction is carried out in four-hole bottle, and employing dropping nitration mixture mode, but not mentioned conversion ratio are adjustable to about 1.3 to neighbour's ratio.
There is presently no to mention in document uses the mode adding phosphoric acid to regulate neighbour's ratio in micro passage reaction.
Summary of the invention
The present invention relates to a kind of micro passage reaction regulates the Benzene Chloride nitration product method to neighbour's ratio, i.e. in nitration mixture Chlorobenzene Nitration system, added a certain amount of phosphoric acid, regulate the ratio of paranitrochlorobenzene in product, o-nitrochlorobenzene.Method is simple, respond well, and chlorobenzene transformation ratio is high, and it is lower that neighbour is compared existing conventional method by product.
Regulating the Benzene Chloride nitration product method to neighbour's ratio in micro passage reaction, its feature is adding a certain amount of phosphoric acid in nitration mixture Chlorobenzene Nitration system, is regulating the ratio of paranitrochlorobenzene in product, o-nitrochlorobenzene.
For reaching object above, the technical scheme that the present invention is usually taken is as follows: regulate the Benzene Chloride nitration product method to neighbour's ratio in micro passage reaction, it is characterised in that the method includes:
1) adding phosphoric acid in the nitration mixture that nitrification uses, phosphoric acid consumption is 0.1 ~ 10 times of nitric acid mole；Described nitration mixture is concentrated sulphuric acid, concentrated nitric acid mixture, sulfonitric mol ratio 1 ~ 8；
2) nitric acid, the mol ratio of Benzene Chloride are 1.0 ~ 1.2；
3) using two strands of feeding manners, enter reaction in micro passage reaction, reaction temperature controls at 40 ~ 80 DEG C；
4) time of staying 30 ~ 120s in reactor；
5) cryogenic conditions collects reactant mixture, adds solvent extraction product, and separatory removes spent acid, and washing is to neutral；
6) chlorobenzene transformation ratio be more than 97%, nitration product to neighbour than scope control 1.0 ~ 1.6.
Preferred embodiments of the present invention:
1, the 0.1 ~ 10 of phosphoric acid nitric acid mol ratio, preferably 1 ~ 3.
2, chlorine nitrate benzene mole ratio is 1.0 ~ 1.2, preferably 1.05 ~ 1.10.
3, reaction temperature controls 40 ~ 80 DEG C, preferably 50 ~ 60 DEG C.
4, the time of staying 30 ~ 120s, preferably 50 ~ 100s in reactor.
5, for being the rapid cancellation of pyroreaction mixture, reactant mixture is collected cryogenic conditions and is under the conditions of ice-water bath.
Beneficial effects of the present invention:
1, in the present invention, the Chlorobenzene Nitration time is short, less than 120s., it is significantly shorter than prior art.
2, in the present invention, chlorobenzene transformation ratio reaches more than 97%, is better than prior art.
3, the present invention introduces phosphoric acid in Benzene Chloride nitrating agent, makes isomer in product that neighbour's ratio is down to about 1.0.
4, comparing existing document, reduce sulphuric acid, phosphoric acid consumption in a large number, reduce spent acid amount, technique is more environmentally friendly.
5, the present invention uses method for continuously synthesizing, react with existing batch tank compared with, more convenient operation, safety.
Accompanying drawing explanation
Fig. 1 is the middle micro passage reaction feeding manner schematic diagram of embodiment of the present invention method.
Detailed description of the invention
Being described in further detail technical scheme below in conjunction with embodiment, protection scope of the present invention is not limited to following detailed description of the invention.
In following example, phosphoric acid is added in the nitration mixture that nitrification uses, as shown in accompanying drawing 1, use two strands of feeding manners of A, B (A, B material selects acid or Benzene Chloride by pump performance), entering reaction in micro passage reaction shown in accompanying drawing 1, raw material A preheats in plate 1, and raw material B preheats in plate 2, then mixing and pass sequentially through Sptting plate 3 ~ 8 continuously, reaction temperature controls 40 ~ 80 DEG C.The time of staying 30 ~ 120s in reactor.Cryogenic conditions collects reactant mixture, adds solvent extraction product, and separatory removes spent acid, and washing is to neutral.Product is by gas chromatographic analysis content.
Embodiment
1
65% nitric acid-98% sulphuric acid of mol ratio 1:1.2, chlorobenzene nitric acid mol ratio is 1.05, and two strands enter microchannel reaction, time of staying 60s, reaction temperature 60 DEG C.In product, paranitrochlorobenzene content 60.57%, o-nitrochlorobenzene content 37.86%, to neighbour's ratio 1.60, chlorobenzene transformation ratio 99.21%.
Embodiment
2
85% phosphoric acid-65% nitric acid-98% sulphuric acid of mol ratio 1:1:1.2, chlorobenzene nitric acid mol ratio is 1.1, and two strands enter microchannel reaction, time of staying 70s, reaction temperature 60 DEG C.In product, paranitrochlorobenzene content 59.56%, o-nitrochlorobenzene content 37.94%, to neighbour's ratio 1.57, chlorobenzene transformation ratio 98.28%.
Embodiment
3
85% phosphoric acid-65% nitric acid-98% sulphuric acid of mol ratio 2:1:1.2, chlorobenzene nitric acid mol ratio is 1.1, and two strands enter microchannel reaction, time of staying 100s, reaction temperature 60 DEG C.In product, paranitrochlorobenzene content 55.78%, o-nitrochlorobenzene content 41.26%, to neighbour's ratio 1.35, chlorobenzene transformation ratio 97.81%.
Embodiment
4
85% phosphoric acid-65% nitric acid-98% sulphuric acid of mol ratio 2:1:4, chlorobenzene nitric acid mol ratio is 1.05, and two strands enter microchannel reaction, time of staying 100s, reaction temperature 60 DEG C.In product, paranitrochlorobenzene content 51.21%, o-nitrochlorobenzene content 45.72%, to neighbour's ratio 1.12, chlorobenzene transformation ratio 97.54%.
Embodiment
5
85% phosphoric acid-65% nitric acid-98% sulphuric acid of mol ratio 3:1:5, chlorobenzene nitric acid mol ratio is 1.08, and two strands enter microchannel reaction, time of staying 100s, reaction temperature 60 DEG C.In product, paranitrochlorobenzene content 49.21%, o-nitrochlorobenzene content 47.77%, to neighbour's ratio 1.03, chlorobenzene transformation ratio 97.66%.
Comprehensive above embodiment, compared with prior art, present invention have the advantage that
1, in the present invention, the Chlorobenzene Nitration time is short, less than 120s., it is significantly shorter than prior art.
2, in the present invention, chlorobenzene transformation ratio reaches more than 97%, is better than prior art.
3, the present invention introduces phosphoric acid in Benzene Chloride nitrating agent, makes isomer in product that neighbour's ratio is down to about 1.0.
4, comparing existing document, reduce sulphuric acid, phosphoric acid consumption in a large number, reduce spent acid amount, technique is more environmentally friendly.
5, the present invention uses method for continuously synthesizing, react with existing batch tank compared with, more convenient operation, safety.
Claims (6)
1. a micro passage reaction regulates the Benzene Chloride nitration product method to neighbour's ratio, it is characterised in that the method includes:
1) adding phosphoric acid in the nitration mixture that nitrification uses, phosphoric acid consumption is 0.1 ~ 10 times of nitric acid mole；Described nitration mixture is concentrated sulphuric acid, concentrated nitric acid mixture, sulfonitric mol ratio 1 ~ 8；
2) nitric acid, the mol ratio of Benzene Chloride are 1.0 ~ 1.2；
3) using two strands of feeding manners, enter reaction in micro passage reaction, reaction temperature controls at 40 ~ 80 DEG C；
4) time of staying 30 ~ 120s in reactor；
5) cryogenic conditions collects reactant mixture, adds solvent extraction product, and separatory removes spent acid, and washing is to neutral；
6) chlorobenzene transformation ratio be more than 97%, nitration product to neighbour than scope control 1.0 ~ 1.6.
Method the most according to claim 1, it is characterised in that phosphoric acid consumption is 1 ~ 3 times of nitric acid mole.
Method the most according to claim 1, it is characterised in that nitric acid, Benzene Chloride mol ratio are 1.05 ~ 1.10.
Method the most according to claim 1, it is characterised in that reaction temperature controls at 50 ~ 60 DEG C.
Method the most according to claim 1, it is characterised in that the time of staying 50 ~ 100s in reactor.
Method the most according to claim 1, it is characterised in that reactant mixture is collected cryogenic conditions and is under the conditions of ice-water bath.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510335856.9A CN106316857A (en) | 2015-06-17 | 2015-06-17 | Method for adjusting p/o ratio of chlorobenzene nitration product in micro-channel reactor |
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| CN201510335856.9A CN106316857A (en) | 2015-06-17 | 2015-06-17 | Method for adjusting p/o ratio of chlorobenzene nitration product in micro-channel reactor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560084A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Preparation method and application of nitration catalyst |
| CN111362803A (en) * | 2018-12-25 | 2020-07-03 | 南京大学淮安高新技术研究院 | Microchannel reaction process for continuously synthesizing 1-nitro mesitylene |
| CN111763156A (en) * | 2020-07-14 | 2020-10-13 | 苏州富士莱医药股份有限公司 | Preparation method of apatinib intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957890A (en) * | 1973-05-09 | 1976-05-18 | Monsanto Company | Process for the nitration of haloaromatics |
| CN102432471A (en) * | 2011-11-07 | 2012-05-02 | 常州大学 | Method for undergoing chlorobenzene nitration reaction by using micro-channel reactor |
-
2015
- 2015-06-17 CN CN201510335856.9A patent/CN106316857A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957890A (en) * | 1973-05-09 | 1976-05-18 | Monsanto Company | Process for the nitration of haloaromatics |
| CN102432471A (en) * | 2011-11-07 | 2012-05-02 | 常州大学 | Method for undergoing chlorobenzene nitration reaction by using micro-channel reactor |
Non-Patent Citations (2)
| Title |
|---|
| 余武斌等: "微通道反应器内氯苯硝化反应研究", 《精细化工》 * |
| 吕春绪等: "硝酸一硫酸一磷酸体系中氯苯的选择性硝化", 《科技进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560084A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Preparation method and application of nitration catalyst |
| CN111362803A (en) * | 2018-12-25 | 2020-07-03 | 南京大学淮安高新技术研究院 | Microchannel reaction process for continuously synthesizing 1-nitro mesitylene |
| CN111763156A (en) * | 2020-07-14 | 2020-10-13 | 苏州富士莱医药股份有限公司 | Preparation method of apatinib intermediate |
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