CN101070286A - Process for producing mirbane oil by gas-phase nitration - Google Patents
Process for producing mirbane oil by gas-phase nitration Download PDFInfo
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- CN101070286A CN101070286A CN 200710049206 CN200710049206A CN101070286A CN 101070286 A CN101070286 A CN 101070286A CN 200710049206 CN200710049206 CN 200710049206 CN 200710049206 A CN200710049206 A CN 200710049206A CN 101070286 A CN101070286 A CN 101070286A
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- catalyzer
- mirbane
- acid
- nitric acid
- benzene
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Abstract
This invention takes benzene and nitric acid as raw material, under catalyzer presence, by vapor-phase nitration to prepare nitrobenzene.The preparation method of catalyzer is isometricimmersion method, use chlorosulfonic acid and silica gel as raw material to prepare HSO3Cl/SiO2 catalyzer. HSO3Cl content is 10 to 50%. Nitration temperature is controlled at 140 to 220 deg. The mol ratio of benzene and nitric acid is 1 to 4:1. Liquid airspeed is 0.1 to 10h hso3cl/ 1. HSso3cl / sio2 catalyzer possess high catalytic activity and long service life. The invention avoid slather sulfuric acid, has high nitric acid percent conversion, few free acid of the reaction product, easy separation, discharge few, technical process simple, reach environmental requirements, realize green produce of nitrobenzene.
Description
Technical field
Involved in the present invention is the technology that the benzene vaporphase nitration prepares oil of mirbane, and concrete is to prepare solid acid catalyst, carries out the method for the nitrated production oil of mirbane of benzene gas phase catalysis in fixed bed.
Background technology
Oil of mirbane one class important chemical material can be used as the intermediate of explosive, medicine, agricultural chemicals, dyestuff etc.Oil of mirbane is main, and purposes is arranged is to produce aniline, nearly hundred kinds of the derived product of aniline, and oil of mirbane itself also can be used as the chemical reaction solvent simultaneously, and therefore, oil of mirbane has the great market requirement.The main technique of industrial production oil of mirbane is the nitric-sulfuric acid method at present, the mixture of benzene and sulfuric acid and nitric acid reacts under violent stirring and generates oil of mirbane, this process has higher benefit, but, this process need uses a large amount of sulfuric acid, reacted spent acid is handled complicated, produces a large amount of waste water, damage to the environment.
Replace the use of a large amount of fluid sulphuric acids, realize that clean nitration is the developing direction that oil of mirbane is produced.The clean nitration technology of report is more at present, and the employing solid acid mainly contains zeolite, clay, strong-acid ion exchange resin, perfluorinated sulfonic resin, solid super-strong acid and supports sulfuric acid and support acidic oxide.The technology that adopts has liquid-phase nitration and vaporphase nitration.
Vaporphase nitration is avoided using a large amount of sulfuric acid, and the transformation efficiency height of nitric acid, and the free acid in the reaction product is few, separates easily, and discharging is few, is considered to environmentally friendly technology.
H
2SO
4With sulfonic acid class ion exchange resin be the good catalyzer of catalytic nitration reaction, U.S. Pat 5030776 has been reported to support H
2SO
4Be catalyzer, carry out the work of mirbane oil by gas-phase nitration, the carrier that is adopted has SiO
2, SiC, TiO
2, ZrO
2, Al
2O
3At 140 ℃ of temperature of reaction, air speed 1500h
-1Under the condition, with H
2SO
4/ SiO
2, H
2SO
4/ SiC is a catalyzer, HNO
3Transformation efficiency reach 97.5%, the oil of mirbane selectivity reaches 98.5%.Because the method that Preparation of Catalyst adopted is a pickling process, after being about to carrier and sulphuric acid soln mixing, evaporate, be drying to obtain, so activity of such catalysts component sulfuric acid easily runs off in reaction process, catalytic activity descends very fast, has only by constantly replenish H in reaction process
2SO
4, could keep catalyst activity.Sulfonic acid class ion exchange resin is mainly used in the liquid-phase nitration reaction, because sulfonic acid class ion exchange resin softening temperature is low, is unsuitable for the vaporphase nitration reaction.
Summary of the invention
The present invention improves activity of such catalysts and work-ing life by improving the Preparation of catalysts method.
The technical solution used in the present invention is:
Adopt equi-volume impregnating to prepare HSO
3Cl/SiO
2, HSO
3Cl can with SiO
2Surface-OH reacts, and makes sulfonic acid at SiO
2The surface is immobilized, improves catalyzer duration of service.
The objective of the invention is to realize in the following way:
A certain amount of catalyzer that has prepared is packed in the reaction tubes, rise to temperature of reaction, temperature is controlled at 130～220 ℃; Nitric acid with 68% and benzene are squeezed into respectively in the preheater by certain flow rate simultaneously with liquor pump, and the total liquid air speed of material is controlled at 0.1～10h
-1, the mol ratio of benzene and nitric acid is controlled at 1～4: 1; Two kinds of raw materials enter reactor after gasification mixes, and carries out nitration reaction in catalyzer, flows out reaction tubes then, after cooling, obtains product liquid.
The Preparation of catalysts method is an equi-volume impregnating, HSO
3Cl/SiO
2In HSO
3Cl content is 10～50%, and its preparation method is as follows:
Take by weighing a certain amount of chlorsulfonic acid, add organic solvent diluting, add a certain amount of 60-80 purpose silica gel incipient impregnation then, left standstill one day, kept five hours at 50 ℃, 120 ℃ of oven dry.
Hydroxyl is contained on the silica gel surface, and (OH) ,-OH has the certain reaction activity, compound formation Si-O-R key that can be high with reactive behavior.The reactive behavior height of S-Cl in the chlorsulfonic acid forms the Si-O-S key with can reacting with the Si-O-H on surface after silica gel mixes, and sulfonic acid solid is stated from the silica gel surface, reduces the loss of active constituent in reaction process, prolongs catalyzer duration of service.
Of the present invention have a following beneficial effect:
Avoid using a large amount of sulfuric acid, the duration of service of catalyzer is long, nitric acid transformation efficiency height, and the free acid in the reaction product is few, separates easily, and discharging is few, and technical process is simple, reaches environmental requirement, can realize the green production of oil of mirbane.
Description of drawings
The bed temperature that Fig. 1 represents different catalysts over time
Specific embodiment
Embodiment one
Take by weighing the 2g chlorsulfonic acid,, add 15g silica gel for chromatography (60-80 order), left standstill one day, kept five hours,, get catalyst-loaded then 120 ℃ of oven dry at 50 ℃ with the dilution of 58ml tetracol phenixin.
Getting 5ml gained catalyzer packs in the reaction tubes, the ceramic plate that about 20cm is equipped with on reaction tubes top is used for the gasification of raw material, and the temperature of entire reaction pipe is risen to 140 ℃, pumps into 65% nitric acid and benzene respectively, nitric acid charging flow velocity is 2.0ml/h, and benzene charging flow velocity is 5.0ml/h.
Reaction conditions: 155 ℃ of temperature of reaction;
Liquid air speed 1.4h
-1
Benzene and nitric acid mol ratio=2: 1;
Reaction result: nitric acid transformation efficiency 96.1%;
The selectivity 98.9% of oil of mirbane.
Embodiment two
With embodiment one, change benzene charging flow velocity, the charging flow velocity of benzene is 2.5ml/h.
Reaction conditions: 155 ℃ of temperature of reaction;
Liquid air speed 0.9h
-1
Benzene and nitric acid mol ratio=1: 1;
Reaction result: nitric acid transformation efficiency 88.2%;
The selectivity 98.5% of oil of mirbane
Embodiment three
Take by weighing the 4g chlorsulfonic acid,, add 15g silica gel for chromatography (60-80 order), left standstill one day, kept five hours,, get catalyst-loaded then 120 ℃ of oven dry at 50 ℃ with the dilution of 56ml tetracol phenixin.
Getting 5ml gained catalyzer packs in the reaction tubes, the ceramic plate that about 20cm is equipped with on reaction tubes top is used for the gasification of raw material, and the temperature of entire reaction pipe is risen to 140 ℃, pumps into 65% nitric acid and benzene respectively, nitric acid charging flow velocity is 2.0ml/h, and benzene charging flow velocity is 2.5ml/h.
Reaction conditions: 155 ℃ of temperature of reaction;
Liquid air speed 0.9h
-1
Benzene and nitric acid mol ratio=1: 1;
Reaction result: nitric acid transformation efficiency 89.1%;
The selectivity 99.2% of oil of mirbane.
Embodiment four
The active contrast of different catalysts.
Catalyzer 1: immersion process for preparing, take by weighing the 4g vitriol oil, add in the 56ml water, add 15g silica gel for chromatography (60-80 order), left standstill one day, kept five hours at 50 ℃, then 120 ℃ of oven dry, get catalyst-loaded.
Catalyzer 2: immersion process for preparing, take by weighing the 4g chlorsulfonic acid, add in the 56ml tetracol phenixin, add 15g silica gel for chromatography (60-80 order), left standstill one day, kept five hours at 50 ℃, then 120 ℃ of oven dry, get catalyst-loaded.
Catalyzer 3: sol-gel method, take by weighing the 59.67g tetraethyl silicate, add in the 40ml water, add the dilute hydrochloric acid of 12g 0.05N, stir into colloidal sol, add 130g dilute sulphuric acid (30%) then, stir, leave standstill after 8 hours and wore out the vacuum-drying of gained gel in two days, obtain solids, solid is crushed and screened, get 40-60 order particle, put into 120 ℃ of baking ovens earlier, kept three hours, be warming up to 200 ℃ then and kept 0.5 hour, take out cooling, get solid catalyst.
Reaction conditions: 155 ℃ of temperature of reaction;
Liquid air speed 1.4h
-1
Benzene and nitric acid mol ratio=2: 1;
Reaction result: see Table
The table different catalysts is to the nitration reaction result
| Catalyzer | Nitric acid transformation efficiency (%) | Oil of mirbane selectivity (%) |
| Catalyzer 1 | 96.5 | 98.8 |
| Catalyzer 2 | 96.2 | 99.1 |
| Catalyzer 3 | 95.1 | 99.2 |
Support chlorsulfonic acid and support sulfuric acid catalyst and all have advantages of high catalytic activity.
Embodiment five
The inactivation situation contrast of different catalysts, catalyzer is with embodiment four, getting 5ml gained catalyzer packs in the reaction tubes, the ceramic plate that about 20cm is equipped with on reaction tubes top is used for the gasification of raw material, the temperature of entire reaction pipe is risen to 140 ℃, pump into 65% nitric acid and benzene respectively, nitric acid charging flow velocity is 4.0ml/h, and benzene charging flow velocity is 10ml/h.。
Reaction conditions: liquid air speed 2.8h
-1
Benzene and nitric acid mol ratio=2: 1;
Reaction result: temperature of reaction over time as shown in the figure.
Nitric acid and benzene are strong exothermal reactions, are not changing radiating condition, increase the liquid air speed, the consumption that has then increased the unit time reactant, and the generation that has strengthened heat raises reaction bed temperature.Reaction bed temperature raises and can cause vitriolic loss quickening in the catalyzer, easily makes catalyst deactivation.Catalyzer 1 bed temperature descends very fast, show that the deactivation rate of catalyzer is fast, and the bed temperature of catalyzer 2 and catalyzer 3 is basicly stable, shows that catalyzer 2 and catalyzer 3 are active more stable.Because the reactive behavior of catalyzer 3 is constant substantially at 1000 hours, so catalyzer 2 also should have long catalyzer duration of service.
Claims (5)
1, a kind of method of producing oil of mirbane is characterized in that with benzene and nitric acid being that raw material gas phase catalytic nitration is produced oil of mirbane.
2,, it is characterized in that catalyst system therefor is is that raw material prepares by equi-volume impregnating with chlorsulfonic acid and silica gel, HSO in the catalyzer according to the described production oil of mirbane of claim 1 method
3Cl content 10～50%, method for preparing catalyst is as follows:
(1), HSO
3Cl dilutes with certain amount of organic solvent;
(2), above-mentioned solution adds in the silica gel, leave standstill;
(3), said mixture is 40-200 ℃ of oven dry.
3, the method for the described production oil of mirbane of claim 1 is characterized in that 140～220 ℃ of temperature of reaction.
4, the method for production oil of mirbane according to claim 1 is characterized in that entering the total liquid air speed of reactor at 0.1～10h
-1
5, the method for production oil of mirbane according to claim 1, the mole proportioning that it is characterized in that benzene and nitric acid is 1～4: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710049206 CN101070286A (en) | 2007-05-31 | 2007-05-31 | Process for producing mirbane oil by gas-phase nitration |
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|---|---|---|---|
| CN 200710049206 CN101070286A (en) | 2007-05-31 | 2007-05-31 | Process for producing mirbane oil by gas-phase nitration |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529881A (en) * | 2018-11-12 | 2019-03-29 | 刘晓菊 | A kind of preparation method for treating Parkinson medicinal intermediate 5- nitro vanillic acid |
| CN111635318A (en) * | 2020-06-14 | 2020-09-08 | 盐城师范学院 | Application of silicon dioxide-based sulfonic acid in improving p/o value of toluene mononitration |
| CN111729673A (en) * | 2020-06-14 | 2020-10-02 | 盐城师范学院 | Application of silicon dioxide-based sulfonic acid in toluene nitration reaction |
-
2007
- 2007-05-31 CN CN 200710049206 patent/CN101070286A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529881A (en) * | 2018-11-12 | 2019-03-29 | 刘晓菊 | A kind of preparation method for treating Parkinson medicinal intermediate 5- nitro vanillic acid |
| CN111635318A (en) * | 2020-06-14 | 2020-09-08 | 盐城师范学院 | Application of silicon dioxide-based sulfonic acid in improving p/o value of toluene mononitration |
| CN111729673A (en) * | 2020-06-14 | 2020-10-02 | 盐城师范学院 | Application of silicon dioxide-based sulfonic acid in toluene nitration reaction |
| CN111635318B (en) * | 2020-06-14 | 2023-07-07 | 盐城师范学院 | Application of silica-based sulfonic acid in improving p/o value of toluene mononitration reaction |
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