CN109574882A - A kind of preparation method of p-methyl benzenesulfonic acid - Google Patents
A kind of preparation method of p-methyl benzenesulfonic acid Download PDFInfo
- Publication number
- CN109574882A CN109574882A CN201710895183.1A CN201710895183A CN109574882A CN 109574882 A CN109574882 A CN 109574882A CN 201710895183 A CN201710895183 A CN 201710895183A CN 109574882 A CN109574882 A CN 109574882A
- Authority
- CN
- China
- Prior art keywords
- reaction
- methyl benzenesulfonic
- benzenesulfonic acid
- preparation
- toluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of p-methyl benzenesulfonic acid, belong to organic synthesis field.Toluene is pumped into falling liquid film micro-structured reactor through constant flow pump, with the SO being passed through3/N2Gaseous mixture haptoreaction, the material after reaction are then passed into the reaction tube of microchannel that the reaction was continued obtains reaction product, and tail gas is absorbed with lye.This process employs advantage of the falling liquid film micro-structured reactor in terms of heat and mass, without adding catalysts and solvents, do not generate spent acid, the serialization preparation of p-methyl benzenesulfonic acid can be realized in a relatively short period of time, it is low with installation cost, technique is continuously controllable, and product purity is high, it is easy to accomplish the advantages that industrialization.
Description
Technical field
The present invention relates to a kind of preparation method of p-methyl benzenesulfonic acid more particularly to a kind of utilization falling liquid film micro-structured reactor are fast
The fast method for continuously preparing p-methyl benzenesulfonic acid, belongs to organic synthesis field.
Background technique
P-methyl benzenesulfonic acid is the intermediate feed of the industrial processes such as pesticide, medicine, dyestuff and organic synthesis, extensively
Applied to the curing agent of resin, the catalyst of additive and organic synthesis is prepared, as a super acids and the concentrated sulfuric acid one
Sample is effective, but effect is more preferable, because oxidation and coking equal side reactions does not occur in it, obtained product purity is high, of light color,
Applied in the reaction such as esterification, acetal, dehydration, alkylation, polymerization and depolymerization;Followed by used in organic synthesis as raw material
In products such as production toluenesulfonamide, paracresol;In addition p-methyl benzenesulfonic acid or phenolic resin, epoxy resin, coating, dyestuff
Etc. important additive.
The production method of country's p-methyl benzenesulfonic acid is mainly toluene Direct Sulfonation method at present, and sulfonating agent has sulfuric acid, three oxidations
Sulphur, chlorosulfonic acid can be divided into gas phase xanthation method and liquid phase sulfonation method according to the state of toluene when sulfonation.Wherein, concentrated sulfuric acid liquid phase
Sulfonating toluene is more universal at home, and scale of investment is smaller, but in the finished product of the method, and p-methyl benzenesulfonic acid content is low (general
Below 95%), free acid it is high, be far from satisfying the needs of various aspects.M-toluene sulfonic acid in the finished product that this method obtains
Amount is difficult to purify 1% or so due to similar with p-methyl benzenesulfonic acid property.In addition, this method can generate a large amount of spent acid, with state
The reinforcement of the environmentally friendly dynamics of family, associated production producer are gradually shut down.SO3Direct Sulfonation method prepare p-methyl benzenesulfonic acid can solve it is useless
The problem of acid generates, still, due to SO3Active high, reaction process is difficult to control, and mass transfer, the heat-transfer effect of traditional reactor have
Limit, being easy to produce hot-spot is difficult to ensure product quality.A large amount of spent acid and SO are generated in order to solve sulfuric acid sulfonation3Sulfonation is anti-
The problems such as should being difficult to control, it is proposed that the SO in falling liquid film micro-structured reactor3Direct Sulfonation prepares p-methyl benzenesulfonic acid, utilizes drop
Advantage of the film micro-structured reactor in terms of heat and mass improves toluene sulfonation selectivity.
Summary of the invention
The purpose of the invention is to overcome sulfuric acid sulfonation to generate a large amount of spent acid and SO3What sulfonating reaction was difficult to control lacks
Point provides a kind of method for continuously preparing p-methyl benzenesulfonic acid using advantage of the falling liquid film micro-structured reactor in sulfonating reaction.
A kind of technical solution of the present invention: preparation method of p-methyl benzenesulfonic acid, which is characterized in that include the following steps,
(1) toluene is pumped into falling liquid film micro-structured reactor through constant flow pump, water-bath outer circulation controls reaction temperature, and is passed through
SO3/N2Gaseous mixture haptoreaction；
(2) material after reacting, which is then passed into the reaction tube of microchannel, carries out aging, and water bath with thermostatic control controls aging temperature, aging
After obtain reacting coarse product；
(3) crude product is collected to obtain product liquid through gas-liquid separation, and tail gas is absorbed with lye.
Generally, in the step (1), SO3/N2SO in gaseous mixture3Volumetric concentration be 1%-40%.
In the step (1), SO3Molar ratio with toluene is 0.2:1-1:1.
In the step (1), the reaction temperature of water-bath outer circulation control is 0-90 DEG C.
In the step (1), toluene residence time in falling liquid film micro-structured reactor is 0.1-20s.
In the step (2), microchannel tube inner diameter is 0.2-6mm；Material after reaction is in the reaction tube of microchannel
Residence time is 0.5-1000s.
In the step (2), the aging reaction temperature of water bath with thermostatic control control is 0-95 DEG C.
The method of the present invention is not necessarily to add catalyst during the preparation process, and the reaction time is short, and simple process does not generate the three wastes,
Production cost is low；And can be realized continuous preparation of the p-methyl benzenesulfonic acid in microreactor, product purity is high, and there is no amplification effects
It answers, it is easy to accomplish industrialized production.
Detailed description of the invention
The device flow diagram of p-methyl benzenesulfonic acid is prepared in embodiment illustrated in fig. 1.
In figure, 1- toluene；2-SO3/N2Gaseous mixture；3- constant flow pump；4- falling liquid film micro-structured reactor；5- water-bath outer circulation；6-
Microchannel reaction tube；7- water bath with thermostatic control；8- collection of products bottle；9- lye absorption bottle.
Specific embodiment
The reaction unit flow chart of following embodiment is shown in Fig. 1, react generation tail gas absorbed with lye after discharge, reaction produce
The purity of object uses gas chromatographic analysis.
Embodiment 1
By toluene and SO3/N2Gaseous mixture is each led into falling liquid film micro-structured reactor (Mainz, Germany microtechnology research institute)
Reaction, SO3Molar ratio with toluene is 0.3:1, SO3/N2SO in gaseous mixture3Concentration be 20%, water-bath outer circulation control reaction
25 DEG C of temperature level, liquid phase reactor object residence time in falling liquid film micro-structured reactor is 8s.Material after reaction is then passed into
Internal diameter is in the microchannel reaction tube of 1mm, and it is 45 DEG C that water bath with thermostatic control, which controls aging temperature, and continuation aging reaction obtains reaction and produces
Object, reaction mixture residence time in the reaction tube of microchannel is 500s.Collecting reaction product after gas-liquid separation, tail gas lye
It absorbs.Gas chromatographic analysis product composition, toluene conversion 45%, p-methyl benzenesulfonic acid yield 91.3%, m-toluene sulfonic acid yield
1.2%, o-toluene sulfonic acid yield 2.9%.
Embodiment 2
By toluene and SO3/N2Gaseous mixture is each led into falling liquid film micro-structured reactor (Mainz, Germany microtechnology research institute)
Reaction, SO3Molar ratio with toluene is 0.5:1, SO3/N2SO in gaseous mixture3Concentration be 35%, water-bath outer circulation control reaction
45 DEG C of temperature level, liquid phase reactor object residence time in falling liquid film micro-structured reactor is 12s.Material after reaction is then passed into
Internal diameter is in the microchannel reaction tube of 0.8mm, and it is 55 DEG C that water bath with thermostatic control, which controls aging temperature, and continuation aging reaction obtains reaction and produces
Object, reaction mixture residence time in the reaction tube of microchannel is 2000s.Collecting reaction product after gas-liquid separation, tail gas alkali
Liquid absorbs.Gas chromatographic analysis product composition, toluene conversion 41%, p-methyl benzenesulfonic acid yield 89.5%, m-toluene sulfonic acid are received
Rate 1.2%, o-toluene sulfonic acid yield 3.1%.
Embodiment 3
By toluene and SO3/N2Gaseous mixture is each led into falling liquid film micro-structured reactor (Mainz, Germany microtechnology research institute)
Reaction, SO3Molar ratio with toluene is 0.7:1, SO3/N2SO in gaseous mixture3Concentration be 10%, water-bath outer circulation control reaction
75 DEG C of temperature level, liquid phase reactor object residence time in falling liquid film micro-structured reactor is 3s.Material after reaction is then passed into
Internal diameter is in the microchannel reaction tube of 2mm, and it is 85 DEG C that water bath with thermostatic control, which controls aging temperature, and continuation aging reaction obtains reaction and produces
Object, reaction mixture residence time in the reaction tube of microchannel is 400s.Collecting reaction product after gas-liquid separation, tail gas lye
It absorbs.Gas chromatographic analysis product composition, toluene conversion 37%, p-methyl benzenesulfonic acid yield 89.7%, m-toluene sulfonic acid yield
2.2%, o-toluene sulfonic acid yield 2.9%.
Embodiment 4
By toluene and SO3/N2Gaseous mixture is each led into falling liquid film micro-structured reactor (Mainz, Germany microtechnology research institute)
Reaction, SO3Molar ratio with toluene is 0.7:1, SO3/N2SO in gaseous mixture3Concentration be 15%, water-bath outer circulation control reaction
35 DEG C of temperature level, liquid phase reactor object residence time in falling liquid film micro-structured reactor is 10s.Material after reaction is then passed into
Internal diameter is in the microchannel reaction tube of 1mm, and it is 65 DEG C that water bath with thermostatic control, which controls aging temperature, and continuation aging reaction obtains reaction and produces
Object, reaction mixture residence time in the reaction tube of microchannel is 1000s.Collecting reaction product after gas-liquid separation, tail gas alkali
Liquid absorbs.Gas chromatographic analysis product composition, toluene conversion 42%, p-methyl benzenesulfonic acid yield 93.3%, m-toluene sulfonic acid are received
Rate 1.5%, o-toluene sulfonic acid yield 3.4%.
Embodiment 5
By toluene and SO3/N2Gaseous mixture is each led into falling liquid film micro-structured reactor (Mainz, Germany microtechnology research institute)
Reaction, SO3Molar ratio with toluene is 0.4:1, SO3/N2SO in gaseous mixture3Concentration be 30%, water-bath outer circulation control reaction
70 DEG C of temperature level, liquid phase reactor object residence time in falling liquid film micro-structured reactor is 17s.Material after reaction is then passed into
Internal diameter is in the microchannel reaction tube of 3mm, and it is 75 DEG C that water bath with thermostatic control, which controls aging temperature, and continuation aging reaction obtains reaction and produces
Object, reaction mixture residence time in the reaction tube of microchannel is 100s.Collecting reaction product after gas-liquid separation, tail gas lye
It absorbs.Gas chromatographic analysis product composition, toluene conversion 40%, p-methyl benzenesulfonic acid yield 90.8%, m-toluene sulfonic acid yield
2.8%, o-toluene sulfonic acid yield 3.7%.
Claims (7)
1. a kind of preparation method of p-methyl benzenesulfonic acid, which comprises the following steps:
(1) toluene is added in falling liquid film micro-structured reactor, reaction temperature is controlled, with the SO being passed through3/N2Gaseous mixture contact is anti-
It answers；
(2) material after reacting, which is then passed into the reaction tube of microchannel, carries out aging, controls aging temperature, obtains after aging anti-
Answer crude product；
(3) crude product is collected to obtain product liquid through gas-liquid separation, and tail gas is absorbed with lye.
2. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (1), SO3/N2It is mixed
Close SO in gas3Volumetric concentration be 1%-40%.
3. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (1), SO3With toluene
Molar ratio be 0.2:1-1:1.
4. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (1), followed outside water-bath
The reaction temperature of ring control is 0-90 DEG C.
5. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (1), toluene is dropping
The residence time is 0.1-20s in film micro-structured reactor.
6. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (2), microchannel plate
Answering bore is 0.2-6mm；Material after the reaction residence time in the reaction tube of microchannel is 0.5-1000s.
7. the preparation method of p-methyl benzenesulfonic acid as described in claim 1, which is characterized in that in the step (2), water bath with thermostatic control
The aging reaction temperature of control is 0-95 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710895183.1A CN109574882A (en) | 2017-09-28 | 2017-09-28 | A kind of preparation method of p-methyl benzenesulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710895183.1A CN109574882A (en) | 2017-09-28 | 2017-09-28 | A kind of preparation method of p-methyl benzenesulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109574882A true CN109574882A (en) | 2019-04-05 |
Family
ID=65912662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710895183.1A Pending CN109574882A (en) | 2017-09-28 | 2017-09-28 | A kind of preparation method of p-methyl benzenesulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109574882A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170896A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of N-ethyl-N- (3' -sulfonic acid) benzylaniline |
| CN111620797A (en) * | 2020-06-12 | 2020-09-04 | 河北建新化工股份有限公司 | Method for synthesizing m-nitrobenzenesulfonic acid by adopting micro-channel continuous flow reactor |
| CN113896660A (en) * | 2021-11-30 | 2022-01-07 | 湖北师范大学 | Micro-channel continuous sulfonation synthesis method of ultraviolet absorbent BP-4 |
| CN114192087A (en) * | 2021-12-16 | 2022-03-18 | 太原理工大学 | Gas-liquid micro-sulfonation system and method for synthesizing anionic surfactant |
| CN115772101A (en) * | 2022-11-26 | 2023-03-10 | 上海势润电子材料有限公司 | Purification process of electronic grade p-toluenesulfonic acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10246626A1 (en) * | 2002-10-07 | 2004-04-15 | Basf Ag | Selective halogenation of alkyl aromatic compounds, useful as intermediates for the production of plant protection agents, comprises insertion of halogenating agents in a micro-reactor under photochemical induction |
| CN101508660A (en) * | 2009-03-31 | 2009-08-19 | 南京工业大学 | Preparation method of alpha-sulfonic acid fatty acid ester |
| CN101693678A (en) * | 2009-10-27 | 2010-04-14 | 南京工业大学 | Process for preparing alpha-sulfo fatty acid methyl ester sodium salt |
| CN102070496A (en) * | 2010-12-24 | 2011-05-25 | 南京工业大学 | Preparation method of alpha-sulfo fatty acid methyl ester salt |
| 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 |
| CN104876839A (en) * | 2015-04-23 | 2015-09-02 | 中国日用化学工业研究院 | Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation |
-
2017
- 2017-09-28 CN CN201710895183.1A patent/CN109574882A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10246626A1 (en) * | 2002-10-07 | 2004-04-15 | Basf Ag | Selective halogenation of alkyl aromatic compounds, useful as intermediates for the production of plant protection agents, comprises insertion of halogenating agents in a micro-reactor under photochemical induction |
| CN101508660A (en) * | 2009-03-31 | 2009-08-19 | 南京工业大学 | Preparation method of alpha-sulfonic acid fatty acid ester |
| CN101693678A (en) * | 2009-10-27 | 2010-04-14 | 南京工业大学 | Process for preparing alpha-sulfo fatty acid methyl ester sodium salt |
| CN102070496A (en) * | 2010-12-24 | 2011-05-25 | 南京工业大学 | Preparation method of alpha-sulfo fatty acid methyl ester salt |
| 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 |
| CN104876839A (en) * | 2015-04-23 | 2015-09-02 | 中国日用化学工业研究院 | Process for preparing p-toluenesulfonic acid through gas phase SO3 film sulfonation |
Non-Patent Citations (2)
| Title |
|---|
| GHADA H. AL-ANSARY ET AL: "Molecular design and synthesis of HCV inhibitors based on thiazolone scaffold", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 * |
| 陈彦全等: "微反应器中甲苯液相SO3磺化工艺研究", 《化学反应工程与工艺》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170896A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of N-ethyl-N- (3' -sulfonic acid) benzylaniline |
| CN111620797A (en) * | 2020-06-12 | 2020-09-04 | 河北建新化工股份有限公司 | Method for synthesizing m-nitrobenzenesulfonic acid by adopting micro-channel continuous flow reactor |
| CN111620797B (en) * | 2020-06-12 | 2022-08-09 | 河北建新化工股份有限公司 | Method for synthesizing m-nitrobenzenesulfonic acid by adopting micro-channel continuous flow reactor |
| CN113896660A (en) * | 2021-11-30 | 2022-01-07 | 湖北师范大学 | Micro-channel continuous sulfonation synthesis method of ultraviolet absorbent BP-4 |
| CN114192087A (en) * | 2021-12-16 | 2022-03-18 | 太原理工大学 | Gas-liquid micro-sulfonation system and method for synthesizing anionic surfactant |
| CN115772101A (en) * | 2022-11-26 | 2023-03-10 | 上海势润电子材料有限公司 | Purification process of electronic grade p-toluenesulfonic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109574882A (en) | A kind of preparation method of p-methyl benzenesulfonic acid | |
| CN109912462B (en) | Method for synthesizing dodecylbenzene sulfonic acid in circulating microreactor | |
| CN102827042B (en) | Chiral synthesis method of florfenicol | |
| CN111018715A (en) | Microchannel synthesis method of dinitrobenzene | |
| CN112679358A (en) | Method for continuously preparing 3, 5-dinitrobenzoic acid by using microchannel reactor | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| WO2016184038A1 (en) | Method for preparing cyclohexene oxide using micro-flow field reaction technology | |
| CN107311868A (en) | A kind of method for preparing p-tert-butyl benzoic acid methyl esters | |
| CN109180437A (en) | The method that cumyl hydroperoxide decomposition prepares phenol in tubular type continuous flow reactor | |
| CN103896737A (en) | Method for preparing propargyl alcohol by utilizing microstructure reactor | |
| CN102068945B (en) | Reactive distillation device and method for separating and purifying methylal | |
| CN103980286A (en) | Method and device for continuously producing isosorbide | |
| CN113584099B (en) | Method for preparing dihydrocoumarin or derivative thereof by adopting micro-flow field reaction technology | |
| CN103694169B (en) | Micro passage reaction is utilized to synthesize the method for 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof | |
| CN110642678A (en) | Method for preparing 2, 5-dichlorophenol by continuously oxidizing p-dichlorobenzene | |
| CN117986162A (en) | Preparation method of ethyl sulfonyl chloride | |
| CN203890273U (en) | Pilot test reaction device suitable for preparing higher methyl acrylate | |
| CN100569726C (en) | The synthesis technique of mesitylene carboxylic acid | |
| CN112574006A (en) | Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol | |
| CN110746326A (en) | Method for continuously producing hydroxyethyl sulfonic acid | |
| CN110270371A (en) | A kind of Benzylation reaction method of lignin-base solid acid catalysis | |
| CN105503610A (en) | Method for preparing o-nitro anisole by using micro-channel reaction apparatus | |
| CN114539030B (en) | Method for preparing 2,2' -dihydroxy-3, 3', 5' -tetra-tert-butyl biphenyl by utilizing microchannel reactor | |
| CN112851605B (en) | Method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural | |
| CN105439823A (en) | Method for synthesizing 3-methyl-3-butene-1-ol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190405 |
|
| RJ01 | Rejection of invention patent application after publication |