CN1025024C - Method and equipment for continuous prodn. of halogeno-benzene - Google Patents
Method and equipment for continuous prodn. of halogeno-benzene Download PDFInfo
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- CN1025024C CN1025024C CN89107855A CN89107855A CN1025024C CN 1025024 C CN1025024 C CN 1025024C CN 89107855 A CN89107855 A CN 89107855A CN 89107855 A CN89107855 A CN 89107855A CN 1025024 C CN1025024 C CN 1025024C
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- benzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
To produce the title substance by using a continuous reactor of a closed structure which is divided by partition walls into a plurality of reaction zones and provided with pass openings on the walls so that the reaction mixture of benzene, a catalyst and halogen can flow through the zones in zigzag in turn and a separator. In the continuous reactor 1 which is divided by partition walls 5, a mixture containing, for example, benzene, 1.5wt.% of antimony chloride, as a catalyst and 200ppm of thioglycolic acid is introduced and chlorine is introduced from each inlet 3 of from the first to the third reaction zones to conduct the reaction at 38 to 42 deg.C, as the reaction mixture is passed through the pass openings 6. Then, antimony chloride is filtered off with a catalyst separator, the remaining is cooled down to -5 deg.C with a cooler to crystallize out p-dichlorobenzene, which is centrifuged from liquid substance. The reaction mixture can pass through an extended flow path, thus the subject substance can be obtained in high yield at a high production rate and hazardous substance does not leak out of the reactor, because it has a closed structure.
Description
The present invention relates to the manufacture method and the equipment thereof of halogeno-benzene, particularly a kind of can continuous production halogeno-benzene method and use the continuous manufacturing apparatus that comprises flow reactor of this method.
Halogeno-benzene such as santochlor had purposes widely in fields such as the intermediate of insect-proof agent, reodorant, Synthetic Organic Chemistry and synthetic resins raw materials in the past.
In general, the conversion unit of halogeno-benzenes such as santochlor adopts the intermittent reaction groove, and, remove catalyzer after the reaction, various devices such as the separation and purification of halogeno-benzene all are to install independently respectively, are not successive.Thereby the manufacture method of using the halogeno-benzene of these equipment is charging by batches and reaction.In addition, the variety of processes such as separation and purification of removing catalyzer and halogeno-benzene also can only be carried out respectively.
As mentioned above, the producing apparatus of halogeno-benzenes such as the santochlor in past is to use the intermittent reaction groove, so speed of response is fast inadequately, and can't continuous production.In addition, remove catalyzer after the reaction, aftertreatments such as the separation and purification of halogeno-benzene also can't serialization, so the variety of processes operating efficiency is poor, production rate and product yield isoproductivity are also very poor.In addition, objectionable impuritiess such as the halogenide of each operation have leakage, can't avoid the pollution of operating environment.
Purpose of the present invention just provides the flow reactor of the halogeno-benzenes such as santochlor that can solve these problems of the prior art and uses the apparatus for continously production and the method for this equipment.
In addition, said benzene is meant benzene or alkylbenzene among the present invention, and halogeno-benzene is meant benzene and the alkylbenzene that contains one or more halogen group.
The inventor is by to being that the manufacturing of the halogeno-benzenes such as santochlor of raw material is conscientiously studied with benzene and halogenide, invented new-type reactor with ad hoc structure, producing apparatus and use the method for this equipment continuous production halogeno-benzene, can make the good halogeno-benzenes such as santochlor of productivity that do not pollute operating environment thus continuously, with and finish flow reactor, continuous manufacturing apparatus and the method for continuous production of the halogeno-benzene relevant with the present invention.
Flow reactor of the present invention comprises: the reaction of high order zone of the airtight construction of being separated by baffle region; The importing that is arranged on first conversion zone in the reaction of high order zone contains the opening for feed of the stock liquid of benzene and catalyzer; The importing that is arranged on first step conversion zone in the reaction of high order zone contains the opening for feed of the stock liquid of benzene and catalyzer; The importing that is arranged at least one conversion zone in reaction of high order zone contains the opening for feed of the unstripped gas of halogen; Be arranged on and connect different positions on the interregional dividing plate of reaction of high order, be the connected entrance of the flow direction that changes the reaction solution of forming by stock liquid and unstripped gas successively; Be arranged on the reaction solution discharge port on the end reaction zone in the reaction of high order zone.
In addition, the present invention is that to couple together with following equipment be the halogeno-benzene apparatus for continously production of feature, and these equipment comprise: the flow reactor of above-mentioned halogeno-benzene; Isolate the catalyst separating machine of catalyzer in the Generation Liquid that contains halogeno-benzene that from this flow reactor, gets; Having separated the refrigerative refrigerating unit in addition of the Generation Liquid behind the catalyzer; And the halogeno-benzene of separating out from cooled Generation Liquid carries out isolating tripping device.
In addition, the present invention is that method for continuous production with following halogeno-benzene is a feature, that is: stock liquid that contains benzene and catalyzer and the unstripped gas that contains halogen are imported the flow reactor of being made up of the reaction of high order zone, make it to change flow direction and reaction, generate halogeno-benzene, from contain the Generation Liquid that generates halogeno-benzene, isolate catalyzer, then, the Generation Liquid cooling that separated catalyzer, isolate halogeno-benzene.
Description of drawings is as follows:
Fig. 1 is the sectional view of the flow reactor of halogeno-benzene of the present invention.
Fig. 2 is the schema of the apparatus for continously production of halogeno-benzene of the present invention.
1. flow reactor;
1-1. the 1st conversion zone;
1-2. the 2nd conversion zone;
1-3. the 3rd conversion zone;
1-4. the 4th conversion zone;
2. stock liquid enters the mouth;
3. unstripped gas enters the mouth;
4. agitator;
5. dividing plate;
6. connected entrance;
7. outlet;
8. catalyst separating machine;
9. refrigerating unit;
10. tripping device.
Below, in connection with the flow reactor of accompanying drawing with regard to halogeno-benzene of the present invention, continuous manufacturing apparatus and method for continuous production are done and are specified;
The flow reactor of halogeno-benzene of the present invention, as shown in Figure 1, to have the reaction of high order zone that is separated by dividing plate 5, such as by 1-the 4th conversion zone (closed structure of 1-1～1-4) form, top at the 1st conversion zone, be contain benzene and catalyst material liquid enter 2, at least at a conversion zone, (entrance 3 that ammonia etc. contains the unstripped gas of halogen has been installed on the top of 1-1～1-3) such as at the 1-3 conversion zone, on the diverse location of the dividing plate of each conversion zone adjacency, be provided with the connected entrance 6 that reactant liquor that above-mentioned raw materials liquid and unstripped gas are formed passes through, these connected entrances make reactant liquor change direction successively and flow. In addition, in conversion zone, agitator 4 is set preferably, stirring reaction liquid on last conversion zone 1-4, arranges reactant liquor outlet 7.
Whether the size of each above-mentioned conversion zone and shape be identical, suitably selected by feed(raw material)inlet number, position and reaction condition etc.
Above-mentioned material liquid entrance can be arranged on first conversion zone, or according to circumstances is arranged on other zone. Should whether can obtain entry position and the number that the highest yield and high selectivity are selected above-mentioned raw materials gas according to the halogeno-benzene that generates in addition.
In addition, connected entrance should make the mobile distance of reactant liquor as far as possible long, to play the effect of abundant contact and stirring, makes the reaction acceleration, therefore, can be on the diverse location of comes in abutment on spacer, suitably selected shape and size arrange connected entrance.
Agitator can suitably be arranged in one or all conversion zones, and its number is not particularly limited, and number is more many, and mixing effect is more good. In addition, the stirring vane of agitator is preferably disposed near the connected entrance, to increase mixing effect.
More than such structure, can make reaction solution that halogens such as benzene and chlorine form in long mobile distance, fully contact can be carried out reaction apace in short time.In addition, closed structure can make by product, contains the total overall reaction resultant of hydrogen halide such as hydrogenchloride, delivers to continuously in the subsequent disposal operation, and hydrogen can keep the good working environment of a no poisonous gas leakage.
Below, 2 continuous manufacturing apparatus with regard to halogeno-benzene of the present invention in conjunction with the accompanying drawings are specifically described.
The continuous manufacturing setting of the halogeno-benzene relevant with the present invention is coupled together by following equipment and to constitute as shown in Figure 2: above-mentioned flow reactor 1; In this flow reactor, benzene and halide reaction obtain containing the Generation Liquid of halogeno-benzene, from then on isolate the catalyst separating machine 8 of catalyzer in the Generation Liquid; Having separated the Generation Liquid refrigerative refrigerating unit 9 behind the catalyzer; By separating out halogeno-benzene in the refrigerative Generation Liquid, used tripping device 10 during as santochlor.
Above-mentioned catalyst separating machine, used catalyzer filter when separating the such solid catalyst of antimony chloride, such catalyzer filter has been installed the wire netting with certain pore size, and this wire netting can not make catalyzer pass through, thereby can remove catalyst separating from Generation Liquid.
Above-mentioned refrigerating unit in order to separate out as santochlor from separated the Generation Liquid behind the catalyzer, has adopted to be cooled to-refrigerating unit of 5-0 ℃.
In addition, comparatively it is desirable to continuous centrifuge in the tripping device.
The continuous manufacturing apparatus of the halogeno-benzene of being made up of said structure can be made halogeno-benzene continuously, and production rate is fast, the yield height, and do not have the pollution of the Working environment that causes because of leakages such as halides.
The continuous manufacturing apparatus of the halogeno-benzene of the invention described above, also can with the refining plant of the halogeno-benzene that obtains from above-mentioned tripping device, from the purified halogeno-benzene, isolate the tripping device of moisture, and will be from then on the halogeno-benzene that obtains of tripping device carry out exsiccant drying installation etc. and couple together use.
Above-mentioned refining plant is employed to be the multistage groove that can carry out washing, washing and add such as medicine anti-solid agent continuously.In addition, above-mentioned dried machine is dry adopt be, as for santochlor, its crystallization is placed on the travelling belt of wire netting system, move continuously, blow warm braw by the below and make it the exsiccant drying machine.
Be the method for continuous production of halogeno-benzene of the present invention below.With the santochlor is example, and its method for continuous production is specifically described.
The employed benzene of the raw material of santochlor, usefulness be common synthesis material benzene, and also it doesn't matter to have mixed chlorobenzene.What chlorine used is the synthetic raw gas of common usefulness, and just above-mentioned raw materials can not contain the impurity that reduces catalyst activity.
Catalyzer can use the antimony chloride of knowing, Lewis acid or zeolites such as ferrous chloride, and among the present invention, the mixed catalyst of comparatively ideal antimony chloride and Thiovanic acid.The blending ratio of antimony chloride and Thiovanic acid common 1: 0.0008(weight).Comparatively ideal is 1: 0.001.The addition of whole catalyzer is the 1-2%(weight of benzene consumption normally), comparatively ideal is 1.5-1.6%.Benzene and chlorine add the ratio of reactor, are generally 1: 4 mol ratio.It is desirable to 1: 4.2.
Use such raw material, by above-mentioned continuous manufacturing apparatus, the method for making santochlor continuously is as follows.
The 1st conversion zone by above-mentioned flow reactor adds the stock liquid of being made up of benzene and catalyzer, at least at a conversion zone, adds chlorine as the 1st conversion zone or the 1st and the 2nd later each upper entrance of any conversion zone.The reaction solution that obtains flows downward at the 1st conversion zone, upwards flow at the 2nd conversion zone, change its flow direction successively at after this conversion zone like this, formation reaction solution stream, stirring makes it to flow to the end reaction zone, reaction promptly generates santochlor, the catalyst separating process below the liquid exit in end reaction zone is delivered to.In the catalyst separating process, the catalyzer that contains antimony chloride etc. is separated with ways such as filtrations from the Generation Liquid that contains santochlor.Then,, separate out santochlor, again santochlor is separated separating the Generation Liquid cooling of catalyzer.
Then, above-mentioned resulting santochlor is made with extra care again, handle separate and drying etc. continuously.
In the above-mentioned refinement treatment process, as for santochlor, can carry out medicine and wash, wash and add processing such as anti-solid agent.It is 0.05%(weight 1: 1 the mixture (weight ratio) of ethyl lactate and sulfuric acid or phosphate ester salt or phosphate ester salt and sulfonate that medicine is washed) the aqueous solution add santochlor, stir and make it to mix.Then, after washing by deionized water, add anti-solid agent, mix.It is by the 0.05%(weight of interpolation as 2-methyl ethanol or Racemic glycidol that anti-solid agent is handled) the aqueous solution carry out.At this moment, stirring velocity is about 1000-1500rpm usually, and temperature is about 25-35 ℃.
To carry out the liquid after the above-mentioned refinement treatment, deliver to separating centrifuge, santochlor will be separated from water.
Then, use warm wind (about 50 ℃) that the santochlor after separating is dried to product.
In addition, in above-mentioned method for continuous production, can with the alkyl substituted benzene raw material equally, make haloalkyl benzene such as chloro alkylbenzene.
Below, with embodiment the present invention is described, but the present invention is not limited in these embodiment.
Embodiment
As shown in Figure 1, the continuous manufacturing apparatus of the 8000L that use is made up of 1-the 4th conversion zone, containing 1.5%(weight) when importing the 1st conversion zone continuously with the speed of 640kg/hr, chlorine is blown into the reaction solution from each inlet of 1-3 conversion zone reacts as the antimony chloride of catalyzer and the benzene mixed solution that contains the 2000ppm Thiovanic acid.At this moment, the charge ratio of benzene and chlorine is 1: 4 mol ratio, and temperature of reaction is 38-42 ℃, carries out continuously 4 hours.From the resultant that obtains, behind the filtering separation antimony chloride catalyzer, be cooled to-5 ℃, separate out santochlor, santochlor is separated from the liquid object that contains orthodichlorobenzene by separating centrifuge.Santochlor after the separation is delivered to refining plant, at its 1st groove, uses 0.05% aqueous solution of 1: 1 the mixture (weight) of Laurate ethyl and sulfuric acid to be medicament, and per minute adds 300L, mixes washing.In the 2-3 groove, add deionized water, mix flushing.At the 4th groove, add the 0.05%(weight of 2-methyl ethanol) the anti-solid agent of aqueous solution conduct, mix processing.Then, the water that contains santochlor after handling is delivered to separating centrifuge, santochlor is separated from water, by the continuous drier drying, obtain santochlor 3500kg, this output is equivalent to calculate with benzene feedstock the 72%(weight of theoretical yield), and the yield of orthodichlorobenzene is a 25%(weight).
Comparative Examples
Use the batch reactor of 8000L capacity, the add-on of benzene be can be regarded as be equivalent to 4 hours total amounts among the embodiment, i.e. 2560kg, others and embodiment are just the same, test with this understanding.
Consequently: obtain santochlor 3500kg, yield is a 72%(weight), about 5 hours of reaction times.
From stating the result, the method for continuous production of santochlor of the present invention is than the reaction times shortening about 20% of discontinuous method.
As mentioned above, the flow reactor of santochlor of the present invention has the new-type ad hoc structure of forming by the separated reaction of high order of dividing plate zone between conversion zone, the reaction solution of forming by halogenide such as benzene and chlorine, in the flowing of long distance, contacted fully and stirred, make it and to react continuously.
In addition, this flow reactor has closed structure, so objectionable impuritiess such as halogenide can not leaked.
Continuous manufacturing apparatus last flow reactor couples together uses halogenide such as benzene and chlorine, reacts continuously as described above, and catalyst separating, operating process such as cooling and resultant separation can be made halogeno-benzenes such as santochlor continuously.
Thereby, use the method for continuous production of the halogeno-benzene of the present invention of above flow reactor and continuous manufacturing apparatus, the reaction solution that halogenide such as benzene and chlorine are formed is fully contacted and mixing effect in long mobile distance, make it successive reaction, can high yield, make halogeno-benzene continuously apace.In addition, because be closed structure,, can improve Working environment so objectionable impuritiess such as halogenide can not leaked.
Claims (2)
1, a kind of method for continuous production of halogeno-benzene, it is characterized in that: stock liquid that contains benzene and catalyzer and the unstripped gas that contains halogen are imported the continuous reaction apparatus of forming by the reaction of high order zone, described continuous reaction apparatus comprises: the reaction of high order zone of the closed structure that is separated by dividing plate, be arranged on the opening for feed that supplies to introduce the stock liquid that contains benzene and catalyzer of first conversion zone in the reaction of high order zone, be arranged on the opening for feed at least one conversion zone for introducing halogen unstripped gas, be arranged between the reaction of high order zone every last different positions and the reaction solution of being made up of above-mentioned raw materials liquid and unstripped gas is changed successively flow to the mobile connected entrance, be arranged on the discharge port of the reaction solution on the end reaction zone in the staged reactor; Change flow direction and reaction generation halogeno-benzene, from the Generation Liquid that contains halogeno-benzene, isolate catalyzer, then this was separated Generation Liquid cooling of catalyzer, and the halogeno-benzene of separating out is separated, thereby obtain the halogeno-benzene product.
2, a kind of apparatus for continously production of halogeno-benzene is characterized in that: this apparatus for continously production comprises: the continuous reaction apparatus of halogeno-benzene; From the Generation Liquid that contains halogeno-benzene that device obtains thus, isolate the separating machine of catalyzer; The Generation Liquid refrigerative refrigerating unit of isolating behind the catalyzer; The tripping device of the halogeno-benzene that separation is separated out from cooled Generation Liquid;
Continuous reaction apparatus comprises: the reaction of high order zone of the closed structure that is separated by dividing plate; Be arranged on the opening for feed that supplies to introduce the stock liquid that contains benzene and catalyzer in the first reaction zone zone in the reaction of high order zone; Be arranged on the opening for feed at least one conversion zone for introducing halogen unstripped gas; Be arranged between the reaction of high order zone every last different positions and the reaction solution of being made up of above-mentioned raw materials liquid and unstripped gas is changed successively flow to the mobile connected entrance; Be arranged on the discharge port of the reaction solution on the end reaction zone in the staged reactor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1149506A JPH0317036A (en) | 1989-06-14 | 1989-06-14 | Continuous reactor for halogenated benzenes and continuous production system and process using the same |
| JP149506/89 | 1989-06-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048029A CN1048029A (en) | 1990-12-26 |
| CN1025024C true CN1025024C (en) | 1994-06-15 |
Family
ID=15476633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89107855A Expired - Fee Related CN1025024C (en) | 1989-06-14 | 1989-10-17 | Method and equipment for continuous prodn. of halogeno-benzene |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0317036A (en) |
| CN (1) | CN1025024C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5375024B2 (en) * | 2008-10-24 | 2013-12-25 | 東ソー株式会社 | Method for producing paradichlorobenzene |
| CN102361841B (en) * | 2009-03-26 | 2014-04-09 | 月岛机械株式会社 | Process for production of p-dichlorobenzene |
| JP5658865B2 (en) * | 2009-04-21 | 2015-01-28 | 月島機械株式会社 | Method for producing paradichlorobenzene |
-
1989
- 1989-06-14 JP JP1149506A patent/JPH0317036A/en active Pending
- 1989-10-17 CN CN89107855A patent/CN1025024C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1048029A (en) | 1990-12-26 |
| JPH0317036A (en) | 1991-01-25 |
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