CN102381930B - Method for producing p-chorotoluene by using element selenium as catalyst - Google Patents
Method for producing p-chorotoluene by using element selenium as catalyst Download PDFInfo
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- CN102381930B CN102381930B CN201110246100.9A CN201110246100A CN102381930B CN 102381930 B CN102381930 B CN 102381930B CN 201110246100 A CN201110246100 A CN 201110246100A CN 102381930 B CN102381930 B CN 102381930B
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Abstract
The invention provides a method for producing p-chorotoluene by using the element selenium as a catalyst, comprising the following steps of: using a selenium-containing organic compound as a catalyst, performing a liquid phase ring chlorination reaction between toluene and chlorine, followed by aeration after the reaction, removing residual chlorine and hydrogen chloride gas in the reaction solution, rectifying to obtain o-chlorotoluene, and carrying out melt crystallization on the enriched p-chorotoluene to obtain the high-purity p-chorotoluene. By the adoption of the method, the yield of p-chorotoluene is raised; the catalyst with a stable structure can be repeatedly applied; the technology and equipment are simple; the production cost is low; and there is no pollution to the environment.
Description
Technical field
The invention belongs to chemical field, specifically a kind of elemental selenium of using is as the method for Catalyst Production parachlorotoluene.
Background technology
Toluene(mono)chloride comprises parachlorotoluene and ortho-chlorotolu'ene, is the important Organic Chemicals of a class, is widely used in the meticulous Organic chemical products such as agricultural chemicals, medicine, dyestuff.Wherein the purposes of parachlorotoluene is wider, and cost ratio ortho-chlorotolu'ene is high.
Toluene(mono)chloride is generally all produced by toluene ring chlorination reaction, but with common Louis's acid as catalyst, in the resulting monochlorotoluene of toluene ring chlorination, major part is ortho-chlorotolu'ene, and the content of parachlorotoluene is only at 30%-40%.Because the purposes of parachlorotoluene exists more than ortho-chlorotolu'ene, for this reason, must select a kind of catalyzer that can improve ring chlorination reaction ratio, to improve the ratio of parachlorotoluene in toluene ring chlorination reaction.Wherein prevailing method is when using Lewis acid for Primary Catalysts, adds SULPHUR POWDER or inorganic sulfide compound or organosulfur compound as promotor.Such as the people such as H.Wolfram (US4647709,1987), use butter of antimony as Primary Catalysts, with 1,3,7,9-tetrachloro-2,8-dimethyl fen thiophene, as promotor, encircles chlorination reaction with chlorine to toluene, and the ratio of parachlorotoluene/ortho-chlorotolu'ene has reached 1.67.
Having also had a plurality of patent reports in addition uses zeolite molecular sieve as Primary Catalysts, utilize its space behavior to increase the selectivity of encircling chlorination reaction, United States Patent (USP) (US4724269 wherein, 1988) reported that with zeolite L molecular sieve be Primary Catalysts, the chloro fat alcohol of having take containing 2-3 carbon atom is co-catalyst, toluene carries out chlorination reaction at not higher than the temperature of mixture boiling point, by gas-chromatography, control reaction end, the transformation efficiency 88.6% of toluene, parachlorotoluene/ortho-chlorotolu'ene=3.36, yet prove by experiment, although neighbour is come to want high with respect to other catalyzer, but the m-chlorotoluene in product has reached 0.8%-1.2%, be difficult to obtain high-purity parachlorotoluene, catalyst regeneration used utilizes difficulty, production cost is increased, so can not be used widely in industrialization.
Chinese patent (CN261068A, 1999; CN1257059A, 1999; CN1903814A) also zeolite molecular sieve is applied in toluene chlorination and carried out comparatively detailed research work.Ratio to ortho position also has greatly improved.But all exist the problem of industrial applications difficulty.
Summary of the invention
The method that the object of this invention is to provide the high-purity parachlorotoluene of a kind of practicable production, its key be application containing the organic composite catalyzer of selenium, improve on the one hand the ratio to ortho position, by the reusing of catalyzer, reduce production costs on the other hand.
A kind of elemental selenium of using of the present invention is as the method for Catalyst Production parachlorotoluene, it is characterized in that: with a kind of organic compound containing selenium as catalyzer, make toluene and chlorine carry out liquid phase ring chlorination reaction, after reacting completely, aeration, removes the chlorine and the hydrogen chloride gas that remain in reaction solution, and reaction solution is after separating unreacted toluene and a small amount of toluene dichloride, through rectifying, obtain ortho-chlorotolu'ene, then the parachlorotoluene of enrichment is obtained to highly purified parachlorotoluene through fusion-crystallization.
Described method, is characterized in that described catalyzer is a kind of organometallics containing selenium, iron, and wherein selenium is 1 ︰ 1.2 ~ 1.5 with the mol ratio of iron, and adds an a certain amount of benzyl chloride.
Described method, is characterized in that a benzyl chloride used is a benzyl chloride or adjacent chlorine one benzyl chloride or to chlorine one benzyl chloride or 3,4-dichloro, one benzyl chloride.
Described method, it is characterized in that catalyzer used content in toluene is 500-5000ppm, aforementioned proportion is to calculate with selenium contained in catalyzer, and this catalyzer also can be used in conjunction with Lewis acid, the preferred butter of antimony of described Lewis acid, iron trichloride, zinc chloride.
Described method, is characterized in that the temperature of described ring chlorination reaction is 20 ℃ ~ 110 ℃.The quantity of the chlorine that chlorination reaction adds is every mole of toluene 70-100g.
Described method, is characterized in that described ring chlorination reaction is to adopt the mode of tower chlorination or autoclave chlorination to carry out, and chlorination plant material is lass lining, and its aspect ratio is 1 ~ 15 ︰ 1.
Described method, is characterized in that the temperature of aeration is controlled at 100 ℃ ~ 150 ℃, and residual quantity during every batch of aeration is the 2-10% of whole material.
Described method, the catalyst residue that it is characterized in that chlorination reaction is in the still of every batch of aeration is residual, and directly cover is for chlorination reaction.
Described method, is characterized in that the number of times of applying mechanically of the catalyzer of chlorination reaction is 20-80 time.
Described method, the purification that it is characterized in that parachlorotoluene is the method that adopts fusion-crystallization, the temperature of its crystallization is at-30 ℃ ~ 10 ℃.
First the present invention is achieved in that, by mol ratio 1 ︰ 1.2 ~ 1.5, optimum proportion, is selenium powder and the iron powder of 1 ︰ 1, puts in reactor, then adds a benzyl chloride of two times of molar weights, controls temperature and is no more than 40 ℃, toward wherein passing into chlorine.When selenium powder and iron powder disappearance, in system, there is more oily matter, the transformation efficiency of toluene generally, when 60%-70%, can be confirmed as catalyzer and prepare.Then, using this as catalyzer, the ring chlorination reaction of catalysis toluene, after reaction finishes, aeration, removes chlorine and hydrogenchloride in reaction solution.Reaction solution falls unreacted toluene and many toluene(mono)chlorides through rectifying separation, then through rectifying, obtains ortho-chlorotolu'ene, and the parachlorotoluene of the content > 88% in tower reactor is entered in melting crystallizer, and separation obtains high-purity parachlorotoluene.
Content by above-mentioned prepared catalyzer and toluene with 50-5000ppm mixes, and more suitable ratio is 250-2500ppm, preferably 500-1500 ppm.The intake of chlorine is every mole of 70-110g
The inventive method, described rectifying separation is separated with rectifying tower, and the form of rectifying tower is packing tower, and filler is CY type net corrugated filling.
The present invention compared with prior art has the following advantages:
1, adopt the toluene ring chlorination reaction catalyzer containing selenium in the present invention, can improve 3 percentage points of parachlorotoluenes, to ortho position ratio, can remain on 55 ︰ more than 45.
2, adopt the toluene ring chlorination reaction catalyzer containing selenium in the present invention, can reduce toluene dichloride 2-3 percentage point, toluene dichloride can be controlled in 2.5%.
3, adopt the toluene ring chlorination reaction catalyzer containing selenium in the present invention, its structure and stable performance.In aeration process, be all enriched in still residual in, can apply mechanically 20-80 time and not change its catalytic performance.
4, the purification of parachlorotoluene of the present invention adopts fusion-crystallization method, per tonly can save purification costs 300-400 unit.
5, the inventive method technical process is simple and direct, and equipment is simple, and reaction is routinely without doing large change.Production process is controlled easily, and quality product is high, and production cost is low, adopts the present invention to produce toluene(mono)chloride, substantially free from environmental pollution.
Embodiment
In order to implement better the present invention, the present invention is further illustrated now to enumerate following embodiment, but the present invention is not limited to the scope of the cited embodiment of the inventor.
embodiment 1
The preparation of catalyzer and chlorination reaction
In the four-hole boiling flask of reflux exchanger, Chlorination tube, stirring, thermometer is housed, add iron powder 0.5g, selenium powder 0.8g and a benzyl chloride 0.7ml, then add toluene 400 ml.Under room temperature, start to pass into chlorine, control temperature and be no more than 40 ℃.Chlorine intake is 150-160 ml/min, and the time of passing into is about 6 hours, and now, iron powder and selenium powder all dissolve, and the transformation efficiency of toluene, between 60-70%, has relatively large oily matter to produce in reaction mass system.The above-mentioned catalyzer making is saved backup.
Get the above-mentioned catalyzer mixing 40 ml, (should after fully stirring, measure fast, in order to avoid catalyst sedimentation) add in addition the toluene that 400 ml are fresh, be placed in the four-hole boiling flask that reflux exchanger, Chlorination tube, stirring, thermometer are housed, control temperature and be no more than 55 ℃.In four-hole boiling flask, pass into chlorine, the logical chlorine time is about 7-8 hour, reaction end gas water and alkali liquor absorption.Chromatogram detects follows the tracks of its reaction end, when transformation efficiency > 99.0%, gets final product stopped reaction.
By the simple distillation in oil bath of above-mentioned reaction solution, steam organism, control oil bath temperature at 130 ℃, negative pressure-0.094Mpa, until there is no overhead product, now flask is approximately residual is 20-30 ml, toward wherein adding the toluene that 400 ml are fresh to dissolve, repeats introduce chlorine gas to make reaction and simple distillation operation above.The result of its reaction is as following table:
The result of table 1 chlorination reaction and apply mechanically test
| Apply mechanically number of times | Toluene (%) | Ortho position (%) | Between position (%) | Contraposition (%) | Dichloro (%) |
| 0 | 0.18 | 43.3 | 0.32 | 53.5 | 2.7 |
| 1 | 0.3 | 41.6 | 0.37 | 54.9 | 2.8 |
| 2 | 0.0 | 41.0 | 0.13 | 52.2 | 6.5 |
| 3 | 0.04 | 41.8 | 0.12 | 54.47 | 3.5 |
| 4 | 0.06 | 43.07 | 0.23 | 55.12 | 1.58 |
| 9 | 2.6 | 43.1 | 0.34 | 55.81 | 0.7 |
| 12 | 1.4 | 43.4 | 0.34 | 55.37 | 0.8 |
| 14 | 0 | 41.3 | 0.2 | 53.5 | 4.6 |
| 18 | 1.2 | 40.7 | 0.35 | 56.7 | 1.0 |
| 22 | 0.05 | 41.1 | 0.14 | 53.8 | 4.4 |
| 25 | 0.04 | 39.92 | 0.2 | 55.39 | 4.0 |
| 35 | 0.4 | 44.88 | 0.29 | 53.3 | 3.1 |
| 40 | 0.2 | 43.0 | 0.34 | 53.6 | 2.8 |
From the above embodiments, can find out, control suitable reaction end and can obtain encircling preferably chlorination result.
Embodiment 2
chlorination reaction
According to the experimental technique of embodiment 1, add in right amount the wherein a kind of of butter of antimony, iron trichloride, zinc chloride, consumption is at 0.05-0.1g, and the time of chlorination reaction can shorten to 5 hours.After testing, it is close with embodiment 1 to the ratio at ortho position, applies mechanically number of times and also can reach 20-80 time.
Embodiment 3
industrialized catalyzer preparation and chlorination reaction
In the 3000L reactor of reflux exchanger, Chlorination tube, stirring, thermometer is housed, add iron powder 4.0Kg, selenium powder 6.4Kg and a benzyl chloride 6.5L, then add toluene 1600 L.Pass into chlorine reaction and prepare the catalyzer of toluene ring chlorination reaction.Preparation method controls as embodiment 1.
At diameter 1.3m, in the reaction tower of high 12m, drop into dry toluene 10000 L, then drop into above-mentioned catalyzer 250 L, introduce chlorine gas to make reaction.Outer circulation is cooling, controls temperature and is no more than 55 ℃, chromatogram detection reaction terminal.Its result is: to ortho position, than 57:43, transformation efficiency is greater than 99.0%, and toluene dichloride is lower than 2.5%.
Above-mentioned catalyzer is after aeration, and the still of simple distillation is residual also can be applied mechanically 20-80 time.
Embodiment 4
the fusion-crystallization method high-quality parachlorotoluene of purifying
Toward adding in melting crystallizer, remove toluene and high boiling material, and the parachlorotoluene (content is greater than 92.0%) of collecting after part ortho-chlorotolu'ene puts into melting crystallizer, carry out crystallization, its result is as follows:
The experimental result of table 2 fusion-crystallization
| Interior temperature (℃) | Water temperature (℃) | Collecting amount Ml | Ortho position (%) | Between position (%) | Contraposition (%) |
| -7.2 | -14.8 | 14 | 2.0 | 6.4 | 91.6 |
| 0.1 | 5.9 | 66 | 4.59 | 15.02 | 80.39 |
| 1.7 | 7.5 | 40 | 2.8 | 9.5 | 87.7 |
| 4.0 | 7.3 | 60 | 1.5 | 4.8 | 93.7 |
| 4.9 | 7.6 | 90 | 0.94 | 3.1 | 95.92 |
| 5.6 | 8.0 | 60 | 0.63 | 2.05 | 97.05 |
| 6.3 | 8.0 | 80 | 0.38 | 1.26 | 98.36 |
| 6.7 | 8.0 | 40 | 0.21 | 0.72 | 99.1 |
| 6.7 | 8.8 | 30 | 0.13 | 0.46 | 99.4 |
| 7.0 | 10 | 220 | 0.09 | 0.19 | 99.72 |
Crystallizer size in upper table is 700 ml, and it is ortho-chlorotolu'ene 1.5% that the material of input forms, m-chlorotoluene 3.6%, parachlorotoluene 94.9%.According to test, need to specially prepare.
The present invention only lifts the above embodiments, all documents that the present invention mentions all in this application as a reference, just as each piece of document, quoted separately as a reference, in addition should understand, after having read above-mentioned teachings of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Claims (5)
1. one kind is used elemental selenium as the method for Catalyst Production parachlorotoluene, it is characterized in that: use a kind of catalyzer, make toluene and chlorine carry out liquid phase ring chlorination reaction, after reacting completely, aeration, remove the chlorine and the hydrogen chloride gas that remain in reaction solution, reaction solution is after separating unreacted toluene and a small amount of toluene dichloride, through rectifying, obtain ortho-chlorotolu'ene, then the parachlorotoluene of enrichment is obtained to highly purified parachlorotoluene through fusion-crystallization, the preparation method of described catalyzer is as follows: by selenium powder and the iron powder of mol ratio 1 ︰ 1.2 ~ 1.5, put in reactor, then a benzyl chloride that adds two times of molar weights, control temperature and be no more than 40 ℃, toward wherein passing into chlorine, when selenium powder and iron powder disappearance, in system, there is more oily matter, the transformation efficiency of toluene is generally when 60%-70%, can confirm as catalyzer has prepared, catalyzer used content in toluene is 500-5000ppm, aforementioned proportion is to calculate with selenium contained in catalyzer, the temperature of described ring chlorination reaction is 20 ℃ ~ 100 ℃, the quantity of the chlorine that ring chlorination reaction adds is every mole of toluene 70-100g, the temperature of aeration is controlled at 100 ℃ ~ 150 ℃, residual quantity during every batch of aeration is the 2-10% of whole material, the catalyst residue of ring chlorination reaction is in the still of every batch of aeration is residual, directly cover is used for encircling chlorination reaction, the number of times of applying mechanically of the catalyzer of ring chlorination reaction is 20-80 time.
2. the method for claim 1, is characterized in that a benzyl chloride used can replace with adjacent chlorine one benzyl chloride or to chlorine one benzyl chloride or 3,4-dichloro, one benzyl chloride.
3. the method for claim 1, is characterized in that, this catalyzer also can be used in conjunction with Lewis acid.
4. the method for claim 1, is characterized in that described ring chlorination reaction is to adopt the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, and ring chlorination plant material is lass lining, and its aspect ratio is 1 ~ 15 ︰ 1.
5. the method for claim 1, the purification that it is characterized in that parachlorotoluene is the method that adopts fusion-crystallization, the temperature of its crystallization is at-30 ℃ ~ 10 ℃.
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| 胡彦.混氯甲苯的结晶分离.《扬州师院自然科学学报》.1986,(第1期),66-73. |
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Effective date of registration: 20191115 Address after: 312369 No.8, Beitang East Road, Shangyu economic and Technological Development Zone, Hangzhou Bay, Shaoxing City, Zhejiang Province Patentee after: Wei Zhejiang Huaxin materials Limited by Share Ltd Address before: 322109, No. 128, industrial road, Weishan Town, Jinhua, Zhejiang, Dongyang Patentee before: Zhejiang Weihua Chemical Co., Ltd. |
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