CN102276470A - Method for nitrifying aromatic hydrocarbon compound by continuous countercurrent - Google Patents
Method for nitrifying aromatic hydrocarbon compound by continuous countercurrent Download PDFInfo
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- CN102276470A CN102276470A CN2010101944337A CN201010194433A CN102276470A CN 102276470 A CN102276470 A CN 102276470A CN 2010101944337 A CN2010101944337 A CN 2010101944337A CN 201010194433 A CN201010194433 A CN 201010194433A CN 102276470 A CN102276470 A CN 102276470A
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Abstract
The present invention belongs to the technical field of organic chemistry, and relates to a method for nitrifying an aromatic hydrocarbon compound by continuous countercurrent. The invention is characterized in that the aromatic hydrocarbons compound is reacted with mixed acid by using a counter current contact mode, the aromatic hydrocarbons compound is entered from a feed inlet at the upper part of a separator on the lower part of a reactor, mixed acid is entered from a feed inlet at the lower part of the separator on the upper part of the reactor. The method provided in the invention is not limited to nitrify aromatic hydrocarbons, but also for mixing, reacting and separating of two liquids with different concentration and insolubility which are two liquids with different concentration and insolubility after reacting, the processes of mixing, performing a countercurrent contact reaction and separating products can integrally completed, so that the invention has the advantages of high mass transfer efficiency, low energy consumption, high reaction conversion rate and the like, and has low content by-product impurity.
Description
Technical field: the invention belongs to technical field of organic chemistry, relate to a kind of continuous countercurrent nitrifying method of aromatic hydroxy compound.
Background technology: the reaction of two kinds of liquid that do not dissolve each other mutually or dissolve each other a little is recurrent.Typical this class reaction comprises that a kind of water and a kind of immiscible organic phase react.Because this class reaction mainly occurs in the two-phase interface place usually, therefore in order to obtain the higher reaction conversion ratio and the speed of reaction of hope, require the two-phase thorough mixing, wherein a kind of liquid must fully be distributed in the another kind of liquid, makes two alternate enough big contact area to be arranged.In order to realize this purpose, several different methods is arranged at present.A kind of method is the two-phase liquid while or successively enters a retort that adopt the high-speed stirring oar, machinery promotes to make two-phase be able to hybrid reaction.Because the characteristic of reactor, the transformation efficiency of this method reaction is lower, and the energy consumption of high-speed stirring is also higher, simultaneously, be subjected to the restriction of reactor and stirring rake manufacture craft, industrial scale is amplified limited, particularly when the mixing requirement was quite high, rotating speed of agitator just can't reach requirement.Another kind method is that two-phase liquid enters tubular reactor, is filled with static mixing element in the tubular reactor, and under certain pressure, two-phase liquid and stream enter next unit by static mixing element after the hybrid reaction.This method, because two-phase liquid will enter pipeline reactor with certain pressure, energy consumption is higher, and be reflected in the pipeline reactor skewness on the liquid working direction, particularly enter the second half section, speed of reaction is slack-off, therefore is that the reactor efficiency of benchmark is lower with the reactor length.
The nitration reaction of aromatic hydroxy compound is exactly that such reacts good example.The nitrated system oil of mirbane of industrial important nitrifying process such as benzene, the nitrated system nitro-chlorobenzene of chlorobenzene, methylbenzene nitration system dinitrotoluene (DNT) etc. all realizes by the two-phase hybrid reaction.
Usually, the nitration reaction of aromatic hydroxy compound aromatic hydroxy compound in the presence of sulfuric acid mixes with nitric acid and carries out.A kind of adiabatic process that is used for preparing oil of mirbane has been described in the US2256999 of Castner.In order to obtain industrial acceptable response speed, Castner adopts a succession of stirred pot to implement described reaction.But there are a plurality of problems in this method, mainly is that stirring is inhomogeneous, and reaction mass can produce local superheating, thereby causes low yield and form high-load nitropheneol impurity, also has excessive nitration product dinitrobenzene and trinitrobenzene.
The USP of cyanamide company 4091042 has set forth the adiabatic nitration process.Nitration mixture and excessive about 10% benzene add four pots of placed in-line adiabatic reactors, transformation efficiency 99.5% continuously under the room temperature.But there is same problem in the method that this method and Castner describe.
The patent CN 1406924A of Bayer AG has described aromatic hydroxy compound and the adiabatic nitrations of haloarene compounds in tubular reactor such as toluene.The patent CN 1208123C of Dow global technical company has described the method for nitrofying aromatic hydrocarbon compound in tubular reactor, when described aromatic hydroxy compound and nitration mixture during by static mixing element, a kind of small droplets of phase be distributed to other mutually in, when mixture flow through subsequently Colaesce district, these drops carried out combination and are separated to small part.
The nitrifying method of Bayer AG and the Dow Chemical Company is similar, difference is the structure and the distribution of static mixing element, all obtained higher reaction efficiency, but all there is identical shortcoming in it, the reaction mass flow pattern is a plug flow, in order to obtain preferably mixed effect and to be separated, two-phase liquid must overcome elevated pressures in pipeline reactor, energy consumption is higher, and in the pipeline reactor second half section, speed of reaction is slack-off, and efficient is still lower.
Summary of the invention: the objective of the invention is to propose a kind of new aromatic nitration method, adopt it can make two-phase liquid carry out reactive liquid solution effectively, the two-phase that participates in reaction is mixed, can control reaction preferably again, Fan Ying transformation efficiency height simultaneously, by product is few.
The present invention realizes by the following method: aromatic hydroxy compound and be used for nitrated nitration mixture and take the mode of counter current contact to react; Be that aromatic hydroxy compound enters from separator top, reactor below opening for feed, the mixing acid that contains sulfuric acid or phosphoric acid, nitric acid, water is entered from the opening for feed of separator bottom, reactor top, wherein, (1) at first closes down the separator discharge port, when reactant is filled reactor, just progressively open separator discharge port down; (2) the separator discharge port flows out material flow about the control, so that aromatic hydroxy compound upwards flows through tubular reactor, nitration mixture flows downward and passes through tubular reactor; (3) organic phase and the inorganic effect by filler in reactor are constantly disperseed, contact, are reacted, and nitration product upwards flows, and flow out through the top separator outlet, and the spent acid of formation flows downward, and flows out through the below separator outlet.
Specifically, be exactly under reaction conditions, aromatic hydroxy compound nitrated is that to be connected with the continuous countercurrent that carries out in the reactor of upper and lower separator at two ends nitrated.Utilize gravitational difference that two-phase has and immiscible characteristic, aromatic hydroxy compound is entered from the top opening for feed that is arranged on reactor below separator, and from bottom to top through following separator, material sparger inflow reactor, make and contain sulfuric acid or phosphoric acid, nitric acid, the mixture of water enters from the underfeed mouth that is arranged on reactor top separator, simultaneously, material flow is flowed out in control separator discharge port up and down, so that aromatic hydroxy compound upwards flows through reactor, nitration mixture flows downward and passes through reactor, aromatic hydroxy compound and nitration mixture be the effect by filler in reactor, counter current contact constantly, reaction, disperse, the nitration product of generation upwards flows, and enters separator, and through separate upward separator of outflow with mixing acid, the spent acid that forms flows downward, and enters down separator, and flows out separator down through separating with aromatic hydroxy compound.
The inventive method is not limited to aromatic nitration, can be at two kinds of different densities, do not dissolve each other mutually, and after the reaction also for mixing, the reaction of different densities, two kinds of liquid not dissolving each other mutually with separate, mixing, counter current contact reaction, product separate one and finish, have the mass-transfer efficiency height, energy consumption is little, characteristics such as reaction conversion ratio height, and, have the by-product impurity of low levels.
Adopt this method to carry out nitration reaction, owing to the nitration mixture inlet end at reactor, nitration mixture is excessive in a large number with respect to aromatic hydroxy compound, aromatic hydrocarbons inlet end at reactor, aromatic hydroxy compound is excessive in a large number with respect to nitration mixture, therefore helps the thoroughly nitrated of aromatic hydroxy compound, has improved transformation efficiency.Simultaneously, because general such adiabatic nitration adopts nitration mixture big with comparing of aromatic hydrocarbons, the upper semisection temperature of charge more at nitration mixture is lower, and therefore hot(test)-spot temperature helps reducing the generation of nitrated by product near the aromatic hydroxy compound inlet end.And material flowing in tubular reactor relies on fluid gravity and buoyancy fully, and the pressure-losses of fluid flow is reduced to minimum level, effectively reduces energy expenditure and production cost.
Nitration reaction for aromatic hydroxy compound, in last separator in order to make nitration product do not taken back reactor by nitration mixture, nitration mixture does not flow out with nitration product and goes up separator simultaneously, in following separator, in order to make not Returning reactor of spent acid, aromatic hydroxy compound is not taken down out of separator by spent acid simultaneously, and reaction mass must have enough residence time in the separator up and down, as 1～60min, be preferably 5～15min.
In order to make two phase materials contact reacts fully, reaction mass also must have enough residence time in tubular reactor, and this residence time should be preferably 3～60min greater than 3min, is preferably 10～30min.
The nitrated multiple different aromatic hydroxy compound of this reactor adapted as benzene, toluene, chlorobenzene etc., is particularly suitable for the adiabatic mono-nitration of benzene.
In these reactions, the nitric acid (HNO in aromatic hydroxy compound and the mixing acid
3) to enter reactor near stoichiometric ratio.For the mono-nitration reaction, the mol ratio of benzene and nitric acid is 0.8～1.5: 1, is preferably 0.95～1.2: 1, be preferably 0.95～1.05: 1; In two nitration reactions, the mol ratio of aromatic hydroxy compound and nitric acid is 0.4～0.75: 1, is preferably 0.42～0.6: 1, be preferably 0.45～0.55: 1.
The concentration of described mixing acid by weight percentage, contains HNO
32%～8%, H
2SO
455%～70%, H
2O28%～37%.
Described nitration reaction is thermopositive reaction, and reaction process can be to reactor cooling removing reaction heat, but preferably adopt adiabatic method, and control reaction temperature is less than 160 ℃, is preferably 120～150 ℃.
Described mixing acid and aromatic hydroxy compound before the separator, can be heated to 45～120 ℃ about entering, be preferably 60～100 ℃, are preferably 80～90 ℃.
Described aromatic nitration reacts, and obtains the thick itrated compound of low impurity content.For the adiabatic mono-nitration of benzene, under the yield more than 98.5%, the total content of dinitrobenzene and trinitrobenzene is no more than 300ppm in the described thick itrated compound, and described nitrophenol impurity is lower than 1000ppm, better is to be lower than 800ppm, and best is to be lower than 500ppm.
Embodiment: followingly come the present invention is added on explanation, but be not limitation of the invention with example.
Embodiment 1
At first, prepare nitration mixture in the nitration mixture preparing tank, its weight percent of the nitration mixture of preparation is HNO
32.98%, H
2SO
460.06%, H
2O 36.96%.Then, control is separator material outlet valve down, go into to go up the separator material inlet by the pumping nitration mixture, described nitration mixture is preheated to 81 ℃ before the separator on entering, treat that nitration mixture fills tubular reactor, go into separator material inlet down by pumping benzene, control this moment is the separator outlet valve up and down, so that nitration mixture enters tubular reactor downwards, benzene upwards enters tubular reactor, nitration mixture flow 20.54L/h, benzene flow 1.55L/h is after the counter current contact reaction, thick oil of mirbane upwards leaves reactor, go out to go up separator again, spent acid leaves reactor downwards, goes out separator down again.Described reactor size is φ 20 * 20000, and separator size φ 80 * 600 adorns corrugated plate packing in the tubular reactor up and down.
Reaction is carried out with adiabatic method, because heat release, 115 ℃ of reaction back spent acid temperature, 80.7 ℃ of nitration product temperature.
Nitric acid transformation efficiency 93.56%, yield 98.6% contains dinitrobenzene 198ppm in the thick oil of mirbane, dinitrophenol 769ppm, total nitrophenol content 886ppm.
Embodiment 2
At first, prepare nitration mixture in the nitration mixture preparing tank, its weight percent of the nitration mixture of preparation is HNO
33.03%, H
2SO
466.73%, H
2O 30.24%.Then, control is separator material outlet valve down, go into to go up the separator material inlet by the pumping nitration mixture, described nitration mixture is preheated to 85 ℃ before the separator on entering, treat that nitration mixture fills tubular reactor, go into separator material inlet down by pumping toluene, control this moment is the separator outlet valve up and down, so that nitration mixture enters tubular reactor downwards, toluene upwards enters tubular reactor, nitration mixture flow 19.16L/h, toluene flux 1.67L/h is after the counter current contact reaction, thick nitrotoluene upwards leaves reactor, go out to go up separator again, spent acid leaves reactor downwards, goes out separator down again.Described reactor size is φ 20 * 20000, and separator size φ 80 * 600 adorns corrugated plate packing in the tubular reactor up and down.
Reaction is carried out with adiabatic method, because heat release, 118 ℃ of reaction back spent acid temperature, 86.5 ℃ of nitration product temperature.
Nitric acid transformation efficiency 91.82% mixes nitrotoluene yield 99.1%, contains 2,4 dinitrotoluene (DNT) 715ppm in the thick nitrotoluene of blended, 2,6 dinitrotoluene (DNT) 123ppm, dinitrocreasol 931ppm.
Embodiment 3
At first, prepare nitration mixture in the nitration mixture preparing tank, its weight percent of the nitration mixture of preparation is HNO
33.01%, H
2SO
463.58%, H
2O 33.41%.Then, control is separator material outlet valve down, go into to go up the separator material inlet by the pumping nitration mixture, described nitration mixture is preheated to 78 ℃ before the separator on entering, treat that nitration mixture fills tubular reactor, go into separator material inlet down by the pumping chlorobenzene, control this moment is the separator outlet valve up and down, so that nitration mixture enters tubular reactor downwards, chlorobenzene upwards enters tubular reactor, nitration mixture flow 20.21L/h, chlorobenzene flow 1.70L/h is after the counter current contact reaction, the thick nitro-chlorobenzene that mixes upwards leaves reactor, go out to go up separator again, spent acid leaves reactor downwards, goes out separator down again.Described reactor size is φ 20 * 20000, and separator size φ 80 * 600 adorns corrugated plate packing in the tubular reactor up and down.
Reaction is carried out with adiabatic method, because heat release, 116 ℃ of reaction back spent acid temperature, 81.7 ℃ of nitration product temperature.
Nitric acid transformation efficiency 92.38% mixes nitro-chlorobenzene yield 99.3%, contains dinitrobenzene 372ppm in the thick nitro-chlorobenzene of blended.
Claims (10)
1. the method for a continuous countercurrent nitrofying aromatic hydrocarbon compound is characterized in that aromatic hydroxy compound and is used for nitrated nitration mixture taking the mode of counter current contact to react; Being aromatic hydroxy compound enters from separator top, reactor below opening for feed, and the mixing acid that contains sulfuric acid or phosphoric acid, nitric acid, water is entered from the opening for feed of separator bottom, reactor top, wherein,
(1) at first closes down the separator discharge port, when reactant is filled reactor, just progressively open separator discharge port down;
(2) the separator discharge port flows out material flow about the control, so that aromatic hydroxy compound upwards flows through tubular reactor, nitration mixture flows downward and passes through tubular reactor;
(3) organic phase and the inorganic effect by filler in reactor are constantly disperseed, contact, are reacted, and nitration product upwards flows, and flow out through the top separator outlet, and the spent acid of formation flows downward, and flows out through the below separator outlet.
2. method according to claim 1 is characterized in that the residence time of reaction mass in upper and lower separator is 1～60min.
3. method according to claim 1 and 2 is characterized in that the residence time of reaction mass in upper and lower separator is 5～15min.
4. method according to claim 1 is characterized in that the residence time of reaction mass in reactor is 3～60min.
5. according to claim 1 or 4 described methods, it is characterized in that the residence time of reaction mass in reactor is 10～30min.
6. method according to claim 1 is characterized in that described aromatic hydroxy compound is benzene, toluene or chlorobenzene.
7. according to claim 1 or 6 described methods, the mol ratio that it is characterized in that described aromatic hydroxy compound and nitric acid is 0.4～0.75: 1.
8. according to claim 1 or 6 described methods, it is characterized in that described aromatic hydroxy compound is a benzene, the mol ratio of benzene and nitric acid is 0.8～1.5: 1.
9. method according to claim 1 is characterized in that described mixing acid contains weight percent 2%～8%HNO
3, 55%～70%H
2SO
4, 28%～37%H
2O.
10. method according to claim 1 is characterized in that mixing acid and aromatic hydroxy compound before the separator, are heated to 45～120 ℃ about entering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102628847A (en) * | 2012-03-28 | 2012-08-08 | 上海北裕分析仪器有限公司 | Method and device for quickly oxidizing ammonia nitrogen |
| CN107033005A (en) * | 2015-07-14 | 2017-08-11 | 北京化工大学苏州（相城）研究院 | A kind of nitration method of aromatic compound |
| CN108586256A (en) * | 2018-03-20 | 2018-09-28 | 淮海工学院 | A kind of method of continuous flow upstream nitrification production dinitrobenzene |
| CN112742337A (en) * | 2020-12-29 | 2021-05-04 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing methanesulfonyl fluoride through continuous reaction |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102628847A (en) * | 2012-03-28 | 2012-08-08 | 上海北裕分析仪器有限公司 | Method and device for quickly oxidizing ammonia nitrogen |
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| CN108586256A (en) * | 2018-03-20 | 2018-09-28 | 淮海工学院 | A kind of method of continuous flow upstream nitrification production dinitrobenzene |
| CN112742337A (en) * | 2020-12-29 | 2021-05-04 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing methanesulfonyl fluoride through continuous reaction |
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