CN104876839A - Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation - Google Patents
Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation Download PDFInfo
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- CN104876839A CN104876839A CN201510198025.1A CN201510198025A CN104876839A CN 104876839 A CN104876839 A CN 104876839A CN 201510198025 A CN201510198025 A CN 201510198025A CN 104876839 A CN104876839 A CN 104876839A
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- gas
- air
- mixed gas
- toluene
- methylbenzene
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Abstract
The invention relates to a process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation. The process comprises the following steps: diluting gas SO3 with dry air having a dew point of less than or equal to -50 DEG C into air/SO3 mixed gas; feeding raw material methylbenzene into a sulfonation device; after methylbenzene stably flows in the sulfonation device, feeding the air/SO3 mixed gas into the sulfonation device so that turbulent air/SO3 mixed gas and methylbenzene forming a film on the inner wall of a vertical tube are converged and flow down together to finish the reaction; adjusting a gas-liquid ratio according to the molar ratio of the air/SO3 mixed gas to methylbenzene being 1:(1.05-3.0) so that the reaction becomes stable; and feeding the product generated at the bottom of the sulfonation device into an aging tank for aging by a gas-liquid separator; after aging is finished, performing reduced-pressure distillation on the product to remove surplus methylbenzene, thus obtaining the target product p-toluenesulfonic acid. The process has the advantages that large-scale industrialization can be realized and the cost is low.
Description
Technical field
The invention belongs to a kind of gas phase SO
3membrane-type sulfonation prepares the technique of tosic acid.
Technical background
Tosic acid is a kind of very important organic chemical industry's intermediate, is widely used in medicine, agricultural chemicals, the stablizer of polyreaction and the catalyzer of organic synthesis (ester class etc.), coating intermediate and resin curing agent etc., is also used as electroplating intermediate.Such as, CLT acid Year's consumption crosses ten thousand tons in the world, and tosic acid is the important intermediate that CLT acid is produced.
The usual toluene of tosic acid does raw material, obtains through process for sulfonation route.Industrial mainly employing concentrated acid sulfonation method at present, its advantage is that operational path is skillful, can obtain stable tosic acid, and the excessive vitriol oil can be used as again the solvent of product, makes product be easy to conveying; Shortcoming is that concentrated acid sulfonation activity is lower, needs the excessive vitriol oil and higher temperature and longer time to complete reaction.Product needs again to be separated with the excessive vitriol oil, produces a large amount of spent acid after being separated, high, the consuming time length of energy consumption and pollute large.Chinese patent CN 101845004 A announces a kind of concentrated acid sulfonation technique, toluene is heated to boiling, dropwise the vitriol oil is dripped in reaction, the built agent crystallization filtration drying that 50-70 DEG C adds people's water and ethanol composition is cooled to after having reacted, then continuous heating backflow, the moisture in reaction solution is taken out of with toluene vapor, 30-70min is finally also needed to complete reaction, whole process is comparatively loaded down with trivial details, and the time is longer, and energy consumption is high; Chinese patent CN 103936636 A announces a kind of liquid SO
3process for sulfonation, the reactor of use is special, and liquid SO
3in buying, transport and use procedure, danger coefficient is high; Chinese patent CN 101302176 A discloses a kind of gas phase SO
3process for sulfonation produces the method for tosic acid, and tosic acid content reaches 95%.Reaction is carried out in a kettle., and the reaction times is longer, and rear continuation of having ventilated reaction 5-10min, then intensification 20-30 DEG C is carried out reaction 30-40min.Add water after reaction terminates and be separated location agent 4-methyldiphenyl sulfone or 4,4-diphenylsulfone dimethyl, also need drying after separation, remove unnecessary moisture.Reaction process is more, is difficult to realize continuous prodution, and the reaction times is longer, SO
3consume large, vent gas treatment workload is comparatively large, and whole production cost is higher, is not suitable for mass-producing continuous seepage.
Summary of the invention
One is the object of the present invention is to provide to realize heavy industrialization, a kind of gas phase SO that cost is low
3membrane-type sulfonation prepares the technique of tosic acid.
Sulphonator principle of work is as follows:
Multitube falling film sulfonation reactor is formed by the unit pipes parallel combinations of different quantities, the corresponding increase and decrease because design output is different of unit pipes quantity.The feature of Multi-tube film sulfonator is organism uniformly distributing in the reaction tubes of the arrangement in tubulation, falls along inside pipe wall film-like, with and flow and under air/SO
3mixed gas contacts, and rapidly sulfonation reaction occurs, releases a large amount of heat simultaneously, and this reaction heat, through the removing of shell side recirculated cooling water, keeps constant temperature of reaction, and reaction and heat exchange complete simultaneously.The pressure drop of reactor is less, relatively simple for structure.Reactor is made up of stainless steel, heat exchange and corrosion resistance strong.
Reaction principle of the present invention is as follows:
The concrete preparation technology of the present invention is as follows:
Gas SO
3air/SO that dry air dilution through dew point≤-50 DEG C is volumetric concentration 3-10%
3mixed gas, is cooled to 10-60 DEG C; The excessive incision sulphonator of raw material toluene first will being preheated to 10-60 DEG C, treats that the flowing stable in sulphonator of toluene has been opened, by the SO set
3air/SO that gas is dense
3mixed gas incision sulphonator, forms the air/SO of turbulent flow
3mixed gas with tubulation inwall film forming toluene and flow and under complete reaction, then press air/SO
3mixed gas and toluene mole ratio 1:1.05-3.0 regulate vapour-liquid ratio, react and tend towards stability, after this product under sulphonator is squeezed into digestion tank through gas-liquid separator, aging insulation 20-30min at 30-60 DEG C after vapour-liquid ratio adjustment 30min-1h.Aging complete after by product at reduced pressure distillation removing unnecessary toluene, obtain product tosic acid.
The present invention compared with prior art tool has the following advantages:
1, reacting replacing heat is efficient, and purity is high;
2, reaction is efficient, completes reaction instantaneously;
3, output can be controlled by tubulation quantity, and single pipe also can have the feedstock amount elasticity of 70-130%;
4, produce without spent acid, SO a small amount of in tail gas
2and SO
3remove by tail gas absorbing system;
5, production safety and human input is few, can realize omnidistance computer control;
6, can react with next step and realize continuous prodution.
Embodiment
Embodiment 1-6 is as follows:
Gas SO
3dry air through dew point≤-50 DEG C dilutes, and obtains air/SO that volumetric concentration is 3-10%
3mixed gas, is cooled to 10-60 DEG C;
The excessive incision sulphonator of raw material toluene first will being preheated to 10-60 DEG C, treats that the flowing stable in sulphonator of toluene has been opened, by the SO set
3air/SO that gas is dense
3mixed gas incision sulphonator, forms the air/SO of turbulent flow
3mixed gas with tubulation inwall film forming toluene and flow and under complete reaction, then press air/SO
3mixed gas and toluene mole ratio 1:1.05-3.0 regulate vapour-liquid ratio, react and tend towards stability, after this product under sulphonator is squeezed into digestion tank through gas-liquid separator, aging insulation 20-30min at 30-60 DEG C after vapour-liquid ratio adjustment 30min-1h.Aging complete after by product at reduced pressure distillation removing unnecessary toluene, obtain product tosic acid.
In concrete preparation condition and product, tosic acid purity is as shown in the table:
Above-described embodiment is only and technical conceive of the present invention and feature is described, its object is to allow the technician being familiar with technique can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (1)
1. a gas phase SO
3membrane-type sulfonation prepares the technique of tosic acid, it is characterized in that comprising following preparation process:
Gas SO
3air/SO that dry air dilution through dew point≤-50 DEG C is volumetric concentration 3-10%
3mixed gas, is cooled to 10-60 DEG C; The excessive incision sulphonator of raw material toluene first will being preheated to 10-60 DEG C, treats that the flowing stable in sulphonator of toluene has been opened, by the SO set
3air/SO that gas is dense
3mixed gas incision sulphonator, forms the air/SO of turbulent flow
3mixed gas with tubulation inwall film forming toluene and flow and under complete reaction, then press air/SO
3mixed gas and toluene mole ratio 1:1.05-3.0 regulate vapour-liquid ratio, react and tend towards stability, after this product under sulphonator is squeezed into digestion tank through gas-liquid separator, aging insulation 20-30min at 30-60 DEG C after vapour-liquid ratio adjustment 30min-1h;
Aging complete after by product at reduced pressure distillation removing unnecessary toluene, both product tosic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198025.1A CN104876839A (en) | 2015-04-23 | 2015-04-23 | Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198025.1A CN104876839A (en) | 2015-04-23 | 2015-04-23 | Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation |
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| CN104876839A true CN104876839A (en) | 2015-09-02 |
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| CN201510198025.1A Pending CN104876839A (en) | 2015-04-23 | 2015-04-23 | Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431994A (en) * | 2016-09-09 | 2017-02-22 | 江南大学 | Method for preparing alkyl dimethylbenzyl sulfobetaine by using SO3-containing air film type sulfonation |
| CN107089932A (en) * | 2017-05-26 | 2017-08-25 | 中国日用化学工业研究院 | The process for sulfonation and device of a kind of alkyl diphenyl ether |
| CN108586296A (en) * | 2018-05-16 | 2018-09-28 | 中国日用化学研究院有限公司 | A kind of method for continuously synthesizing of sodium p-nitrotoluene-2-sulfonic acid |
| CN109232327A (en) * | 2018-10-31 | 2019-01-18 | 浙江工业大学上虞研究院有限公司 | A kind of method that toluene sulfonation prepares p-methyl benzenesulfonic acid |
| CN109574882A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of preparation method of p-methyl benzenesulfonic acid |
| CN111138322A (en) * | 2019-12-27 | 2020-05-12 | 赞宇科技集团股份有限公司 | Production process of high-quality alkyl benzene sulfonic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036875A (en) * | 1974-06-05 | 1977-07-19 | Berol Kemi Ab | Process for the continuous sulphonation of alkyl aromatic hydrocarbons |
| CN101302176A (en) * | 2008-05-23 | 2008-11-12 | 南京晶美化学有限公司 | Method for preparing p-toluenesulfonic acid by gas-phase sulphonation of toluol with sulfur trioxide |
| CN101845004A (en) * | 2010-04-16 | 2010-09-29 | 苏州市兴业化工有限公司 | Method for preparing p-toluenesulfonic acid by toluene sulfonation |
| CN202290015U (en) * | 2011-08-03 | 2012-07-04 | 南京兰博化工设备制造有限公司 | Multi-tube film sulfonator |
| CN103936636A (en) * | 2013-01-23 | 2014-07-23 | 中国科学院大连化学物理研究所 | Method for preparing p-toluenesulfonic acid through toluene sulfonation |
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2015
- 2015-04-23 CN CN201510198025.1A patent/CN104876839A/en active Pending
Patent Citations (5)
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| US4036875A (en) * | 1974-06-05 | 1977-07-19 | Berol Kemi Ab | Process for the continuous sulphonation of alkyl aromatic hydrocarbons |
| CN101302176A (en) * | 2008-05-23 | 2008-11-12 | 南京晶美化学有限公司 | Method for preparing p-toluenesulfonic acid by gas-phase sulphonation of toluol with sulfur trioxide |
| CN101845004A (en) * | 2010-04-16 | 2010-09-29 | 苏州市兴业化工有限公司 | Method for preparing p-toluenesulfonic acid by toluene sulfonation |
| CN202290015U (en) * | 2011-08-03 | 2012-07-04 | 南京兰博化工设备制造有限公司 | Multi-tube film sulfonator |
| CN103936636A (en) * | 2013-01-23 | 2014-07-23 | 中国科学院大连化学物理研究所 | Method for preparing p-toluenesulfonic acid through toluene sulfonation |
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| 王笃政等: "对甲苯磺酸磺化反应器的研究进展", 《精细与专用化学品》 * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431994A (en) * | 2016-09-09 | 2017-02-22 | 江南大学 | Method for preparing alkyl dimethylbenzyl sulfobetaine by using SO3-containing air film type sulfonation |
| CN107089932A (en) * | 2017-05-26 | 2017-08-25 | 中国日用化学工业研究院 | The process for sulfonation and device of a kind of alkyl diphenyl ether |
| CN107089932B (en) * | 2017-05-26 | 2019-10-01 | 中国日用化学工业研究院 | A kind of process for sulfonation and device of alkyl diphenyl ether |
| CN109574882A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of preparation method of p-methyl benzenesulfonic acid |
| CN108586296A (en) * | 2018-05-16 | 2018-09-28 | 中国日用化学研究院有限公司 | A kind of method for continuously synthesizing of sodium p-nitrotoluene-2-sulfonic acid |
| CN108586296B (en) * | 2018-05-16 | 2021-08-10 | 中国日用化学研究院有限公司 | Continuous synthesis method of p-nitrotoluene-o-sulfonic acid |
| CN109232327A (en) * | 2018-10-31 | 2019-01-18 | 浙江工业大学上虞研究院有限公司 | A kind of method that toluene sulfonation prepares p-methyl benzenesulfonic acid |
| CN111138322A (en) * | 2019-12-27 | 2020-05-12 | 赞宇科技集团股份有限公司 | Production process of high-quality alkyl benzene sulfonic acid |
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Application publication date: 20150902 |
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