CN206447796U - A kind of production system of 2,4 chlorophenesic acid - Google Patents
A kind of production system of 2,4 chlorophenesic acid Download PDFInfo
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- CN206447796U CN206447796U CN201720131051.7U CN201720131051U CN206447796U CN 206447796 U CN206447796 U CN 206447796U CN 201720131051 U CN201720131051 U CN 201720131051U CN 206447796 U CN206447796 U CN 206447796U
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- phenol
- chlorosulfuric acid
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- reaction device
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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
Abstract
The utility model provides a kind of production system of 2,4 chlorophenesic acids, including：Phenol chlorination reaction device, the phenol chlorination reaction device is provided with chlorosulfuric acid charging aperture, the outlet of phenol chlorinated exhaust and product exit；Chlorosulfuric acid synthesizer, the chlorosulfuric acid synthesizer is provided with tail gas charging aperture, chlorine feed mouth and discharging opening；The tail gas charging aperture is connected with the phenol offgas outlet of phenol chlorination reaction device；The discharging opening is connected with the chlorosulfuric acid charging aperture of phenol chlorination reaction device.Compared with prior art, the utility model uses successive reaction and recycling tail gas flow, high selectivity, low cost, the chlorophenesic acid of preparation 2,4 in high yield, and flow simple, available for industrialized production, there is larger economic value and social benefit.
Description
Technical field
The utility model belongs to chemical technology field, more particularly to one kind 2,4- chlorophenesic acids production system.
Background technology
2,4- chlorophenesic acids be used as solvent, agricultural chemicals and medicine intermediate, for synthesize nitrofen, 2,4-D, she compare phosphorus
(EPBP), malicious gram of scattered, Genit and medicine bithionol, the tens thousand of tons of annual requirement.
The production method of 2,4 dichloro phenol mainly has：Phenol direct chlorination method, mixed phenol chloridising, o-chlorphenol selection
Five kinds of chloridising, parachlorophenol chloridising and phenol catalytic chlorination process.
Phenol direct chlorination method is domestic and international traditional processing technology, and technique is simple, and cost is low, but is due to wherein by-product
2,6- chlorophenesic acid physical properties with 2,4- chlorophenesic acids due to closely and being difficult to separation causes product purity low, it is impossible to it is raw
The higher 2,4 dichloro phenol of output purity.
Selective highest and most easy industrializing implementation includes following method in existing report：
Department of chemistry of Shandong University is industrially to produce the accessory substance o-chlorphenol during parachlorophenol as raw material, with anhydrous
Alchlor and diphenyl sulfide make catalyst, and chlorinating agent is done with chlorosulfuric acid, and chlorination reaction is carried out in 15 ± 2 DEG C of temperature ranges,
The content of 2,4- chlorophenesic acids is up to more than 95% in product, and remaining is 2,6- chlorophenesic acids.
Phenol leads to chlorine under iron catalysis, is made in 80 DEG C~100 DEG C chlorinations, but reaction temperature is too high.Reaction equation is such as
Under：
According to data introduction, the presence of copper, the yield of contraposition can be significantly increased by being particularly combined the presence of mantoquita.Qingdao
Research institute of Tianyuan chemical inc has carried out the selection of catalyst and reaction condition according to above-mentioned data, has achieved rank
Section property achievement, it directly synthesizes purity and has reached 94% or so.
Publication No. CN105777499A Chinese patent discloses one kind with chlorosulfuric acid plus composite catalyst controlled syntheses
2,4- chlorophenesic acids and 2, the method for 4,6- trichlorophenol, 2,4,6,-Ts, mention can chlorination obtain 98% 2,4- chlorophenesic acids, but be due to
Using expensive chlorosulfuric acid, while below using Crystallization Separation is melted, necessarily causing eutectic site catalyst class material and chlorine
The material mixing of oxidation stain causes product appearance poor into target product during change, and containing certain impurity, influence subsequently makes
With making the presence of certain difficulty during industrializing implementation.
Utility model content
In view of this, the technical problems to be solved in the utility model is the production system for providing one kind 2,4- chlorophenesic acids
System, the production system can be produced continuously.
The utility model additionally provides the production system of one kind 2,4- chlorophenesic acids, including：
Phenol chlorination reaction device, the phenol chlorination reaction device is provided with chlorosulfuric acid charging aperture, phenol chlorinated exhaust
Outlet and product exit；
Chlorosulfuric acid synthesizer, the chlorosulfuric acid synthesizer is provided with tail gas charging aperture, chlorine feed mouth and discharging opening；
The tail gas charging aperture is connected with the phenol offgas outlet of phenol chlorination reaction device；The discharging opening and phenol chlorination reaction
The chlorosulfuric acid charging aperture of device is connected.
It is preferred that, in addition to gas cleaning plant；The phenol chlorinated exhaust outlet of the phenol chlorination reaction device passes through
Gas cleaning plant is connected with the tail gas charging aperture of the chlorosulfuric acid synthesizer.
It is preferred that, in addition to rectifying column, the product exit of the phenol chlorination reaction device is connected with the rectifying column.
It is preferred that, in addition to the vacuum extractor being connected with the phenol chlorination reaction device.
The utility model provides the production system of one kind 2,4- chlorophenesic acids, including：Phenol chlorination reaction device, it is described
Phenol chlorination reaction device is provided with chlorosulfuric acid charging aperture, the outlet of phenol chlorinated exhaust and product exit；Chlorosulfuric acid synthesizer,
The chlorosulfuric acid synthesizer is provided with tail gas charging aperture, chlorine feed mouth and discharging opening；The tail gas charging aperture and phenol chlorine
The phenol offgas outlet for changing reaction unit is connected；The discharging opening is connected with the chlorosulfuric acid charging aperture of phenol chlorination reaction device
It is logical.Compared with prior art, the utility model uses successive reaction and recycling tail gas flow, high selectivity, low cost, in high yield
Preparation 2,4- chlorophenesic acids, and flow is simple, available for industrialized production, there is larger economic value and social benefit.
Brief description of the drawings
The structural representation of the production system for the 2,4 dichloro phenol that Fig. 1 provides for the utility model.
Embodiment
Below in conjunction with the utility model embodiment, the technical scheme in the utility model embodiment is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the utility model, rather than whole embodiments.
Based on the embodiment in the utility model, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of the utility model protection.
The utility model provides the production system of one kind 2,4- chlorophenesic acids, including：Phenol chlorination reaction device, it is described
Phenol chlorination reaction device is provided with chlorosulfuric acid charging aperture, the outlet of phenol chlorinated exhaust and product exit；Chlorosulfuric acid synthesizer,
The chlorosulfuric acid synthesizer is provided with tail gas charging aperture, chlorine feed mouth and discharging opening；The tail gas charging aperture and phenol chlorine
The phenol offgas outlet for changing reaction unit is connected；The discharging opening is connected with the chlorosulfuric acid charging aperture of phenol chlorination reaction device
It is logical.
According to the utility model, the production system preferably also includes gas cleaning plant；The phenol chlorination reaction device
Phenol chlorinated exhaust outlet be connected by gas cleaning plant with the tail gas charging aperture of the chlorosulfuric acid synthesizer.
According to the utility model, the production system preferably also includes rectifying column；The product of the phenol chlorination reaction device
Outlet is connected with the rectifying column.
The production system that the utility model is provided preferably also includes vacuum extractor；The vacuum extractor and the phenol
Chlorination reaction device is connected.
The structural representation of the production system for the 2,4 dichloro phenol that Fig. 1 provides for the utility model.
The utility model provides a kind of method that above-mentioned production system of application produces 2,4- chlorophenesic acids, including：S1) will
Initiator, phenol are mixed with catalyst, reaction, obtain phenol chlorinated exhaust and reaction solution；The initiator is chlorosulfuric acid；S2)
By the phenol chlorinated exhaust and chlorine hybrid reaction, chlorosulfuric acid is obtained；S3) chlorosulfuric acid is mixed with reaction solution, reacted,
Obtain phenol chlorinated exhaust and 2,4 dichloro phenol.
Initiator, phenol are mixed with catalyst；The mass ratio of the initiator and phenol is preferably 1：(20~50), more
Preferably 1：(30~50), are further preferably 1：(40~50), most preferably 1:40；The catalyst is that those skilled in the art are ripe
The catalyst known, it is preferably composite catalyst to have no in special limitation, the utility model；The composite catalyst is preferred
For thio-ether type compounds and metal salt；The thio-ether type compounds are compound well known to those skilled in the art, are had no
It is preferably the one or more in dimethyl sulphide, diphenyl sulfide and isopropyl ether in special limitation, the utility model；The metal salt
For metal salt well known to those skilled in the art, it is preferably titanium tetrachloride, three to have no in special limitation, the utility model
Aluminium chloride and the one or more in ferric trichloride；The mol ratio of the thio-ether type compounds and metal salt is preferably 1：(2~
10), more preferably 1：(4~10), are further preferably 1：(5~9), are further preferably 1：(6~8), most preferably 1:7.66.
After mixing, reaction obtains phenol chlorinated exhaust and reaction solution；The temperature of the reaction is preferably 30 DEG C~60 DEG C.
According to the utility model, after the phenol chlorinated exhaust preferably purified processing, with chlorine hybrid reaction, sulphur is obtained
Acyl chlorides；The mol ratio of the chlorinated phenol tail gas and chlorine is preferably 1：(0.9~1.1)；The temperature of the hybrid reaction is preferred
For -20 DEG C~10 DEG C, more preferably -10 DEG C~10 DEG C.
Phenol chlorinated exhaust also generates hydrogen chloride fixed gas with chlorine hybrid reaction while chlorosulfuric acid is generated, in this reality
Absorbed with water is preferably used in new, can obtain hydrochloric acid solution and can also directly compress compression hydrogen chloride gas is made, realized
Resource is utilized to greatest extent.
Chlorosulfuric acid is mixed with reaction solution, reacted；The reaction temperature is preferably 30 DEG C~60 DEG C.
In the utility model, this step is preferably specially：
The chlorosulfuric acid is mixed with reaction solution, reacts, obtains phenol chlorinated exhaust and reacted solution；
By the phenol chlorinated exhaust and chlorine reaction, chlorosulfuric acid is obtained；
The chlorosulfuric acid is mixed with reacted solution, reacts, repeats the above steps, to reacted Phenol in Aqueous Solution
When content is less than or equal to 0.1%, reaction terminates.
According to the utility model, after reaction terminates, preferably first carry out by vacuumizing, remove fixed gas, then will removing
Reaction solution after fixed gas carries out rectifying, obtains 2,4- chlorophenesic acids.
The fixed gas of removing includes hydrochloric acid and sulfur dioxide, preferably by itself and chlorine reaction, obtains chlorosulfuric acid；It is anti-with chlorine
Fixed gas after answering.
The utility model continuously generates sulfonyl by initial chlorizated raw material of chlorine with the sulfur dioxide in phenol chlorinated exhaust
Chlorine, chlorosulfuric acid is continuously added in reaction solution, finally gives 2,4- chlorophenesic acids, and the utility model is returned using successive reaction and tail gas
With flow, high selectivity, low cost, preparation 2 in high yield, 4- chlorophenesic acids, and flow are simple, available for industrialized production,
There is larger economic value and social benefit.
In order to further illustrate the utility model, one kind 2, the 4- dichloros provided with reference to embodiments the utility model
The production method and production system of phenol are described in detail.
Reagent used is commercially available in following examples.
Embodiment 1
Phenol 4000kg is added into the 8000L chlorination tanks for the recycling tail gas device that supporting phenol is reclaimed and is dried, unlatching is stirred
Mix, then add dimethyl sulphide 0.4kg, ferric trichloride 8kg, Quan Ronghou, keeping temperature is 40 DEG C, start that chlorosulfuric acid is added dropwise
100kg does not use fresh chlorosulfuric acid subsequently as initiator.When chlorosulfuric acid is added dropwise, have containing sulfur dioxide and hydrogen chloride
Tail gas overflow, pass through tail gas clean-up and retracting device, the mixed gas wherein dioxy of sulfur dioxide and hydrogen chloride after purification
The mol ratio for changing sulphur and hydrogen chloride is 1：1.Chlorosulfuric acid synthesis procedure is transported to after being measured by flowmeter.
In chlorosulfuric acid synthesizer, according to the tail gas mole of flow measurement, it is with gaseous mixture mol ratio according to chlorine
1:1 ratio, which enters, carries out chlorosulfuric acid synthesis in chlorosulfuric acid synthesis reactor, it is 10 DEG C to control temperature of reactor.Generated after synthesis
The fixed gas of liquid chlorosulfuric acid and containing hydrogen chloride.The fixed gas is driving to be introduced originally into water absorption, produces 30% hydrochloric acid solution.
The chlorosulfuric acid of generation, is transferred to phenol chloride process, is added dropwise to phenol chlorination tank, and the generation that can continue contains titanium dioxide
The tail gas of sulphur, the tail gas hybrid reaction regeneration chlorosulfuric acid lasting with chlorine.So repeatedly, detection phenol contains in kettle to be chlorinated
Amount is at 0.1%, and reaction terminates.Stop that chlorosulfuric acid is added dropwise.And then stop being passed through chlorine to system.
It is 99% 2,4 dichloro phenol and the mixture 7150kg of catalyst that content is obtained in chlorination tank.
By obtained 2,4- chlorophenesic acids and the mixture of catalyst, de- fixed gas is first depressurized, the fixed gas of abjection is transferred to
Hydrogen chloride absorption, obtains aqueous hydrochloric acid solution.Phenol after depickling is transferred to rectifying column, by rectifying, from the 2 of overhead extraction high-quality,
4- chlorophenesic acid 6910kg, appearance colorless liquid (60 DEG C), content 99.54%, yield 99.42%.
Embodiment 2
Phenol 4000kg is added into the 8000L chlorination tanks for the recycling tail gas device that supporting phenol is reclaimed and is dried, unlatching is stirred
Mix, then add diphenyl sulfide 1kg, ferric trichloride 8kg, Quan Ronghou, keeping temperature is 50 DEG C, start that chlorosulfuric acid 150kg works are added dropwise
For initiator, fresh chlorosulfuric acid is not used subsequently.When chlorosulfuric acid is added dropwise, has the tail gas containing sulfur dioxide and hydrogen chloride and overflow
Go out, by tail gas clean-up and retracting device, the mixed gas wherein sulfur dioxide and chlorine of sulfur dioxide and hydrogen chloride after purification
The mol ratio for changing hydrogen is 1：1.Chlorosulfuric acid synthesis procedure is transported to after being measured by flowmeter.
In chlorosulfuric acid synthesizer, according to the tail gas mole of flow measurement, it is with gaseous mixture mol ratio according to chlorine
1.05:1 ratio, which enters, carries out chlorosulfuric acid synthesis in chlorosulfuric acid synthesis reactor, it is -10 DEG C to control temperature of reactor.After synthesis
Generate the fixed gas of liquid chlorosulfuric acid and containing hydrogen chloride.The fixed gas is driving to be introduced originally into water absorption, produces 30% hydrochloric acid
Solution.
The chlorosulfuric acid of generation, is transferred to phenol chloride process, is added dropwise to phenol chlorination tank, and the generation that can continue contains titanium dioxide
The tail gas of sulphur, the tail gas hybrid reaction regeneration chlorosulfuric acid lasting with chlorine.So repeatedly, detection phenol contains in kettle to be chlorinated
Amount is at 0.1%, and reaction terminates.Stop that chlorosulfuric acid is added dropwise.And then stop being passed through chlorine to system.
It is 99% 2,4 dichloro phenol and the mixture 7155kg of catalyst that content is obtained in chlorination tank.
By obtained 2,4- chlorophenesic acids and the mixture of catalyst, de- fixed gas is first depressurized, the fixed gas of abjection is transferred to
Hydrogen chloride absorption, obtains aqueous hydrochloric acid solution.Phenol after depickling is transferred to rectifying column, by rectifying, from the 2 of overhead extraction high-quality,
4- chlorophenesic acid 6917kg, appearance colorless liquid (60 DEG C), content 99.23%, yield 99.46%.
Embodiment 3
Phenol 4000kg is added into the 8000L chlorination tanks for the recycling tail gas device that supporting phenol is reclaimed and is dried, unlatching is stirred
Mix, then add diphenyl sulfide 0.6kg, titanium tetrachloride 7kg, Quan Ronghou, keeping temperature is 60 DEG C, start that chlorosulfuric acid 100kg is added dropwise
As initiator, fresh chlorosulfuric acid is not used subsequently.When chlorosulfuric acid is added dropwise, the tail gas containing sulfur dioxide and hydrogen chloride is had
Overflow, by tail gas clean-up and retracting device, the mixed gas wherein sulfur dioxide of sulfur dioxide and hydrogen chloride after purification with
The mol ratio of hydrogen chloride is 1：1.Chlorosulfuric acid synthesis procedure is transported to after being measured by flowmeter.
In chlorosulfuric acid synthesizer, according to the tail gas mole of flow measurement, it is with gaseous mixture mol ratio according to chlorine
1.1:1 ratio, which enters, carries out chlorosulfuric acid synthesis in chlorosulfuric acid synthesis reactor, it is -10 DEG C to control temperature of reactor.After synthesis
Generate the fixed gas of liquid chlorosulfuric acid and containing hydrogen chloride.The fixed gas is driving to be introduced originally into water absorption, produces 30% hydrochloric acid
Solution.
The chlorosulfuric acid of generation, is transferred to phenol chloride process, is added dropwise to phenol chlorination tank, and the generation that can continue contains titanium dioxide
The tail gas of sulphur, the tail gas hybrid reaction regeneration chlorosulfuric acid lasting with chlorine.So repeatedly, detection phenol contains in kettle to be chlorinated
Amount is at 0.05%, and reaction terminates.Stop that chlorosulfuric acid is added dropwise.And then stop being passed through chlorine to system.
It is 99% 2,4 dichloro phenol and the mixture 7140kg of catalyst that content is obtained in chlorination tank.
By obtained 2,4- chlorophenesic acids and the mixture of catalyst, de- fixed gas is first depressurized, the fixed gas of abjection is transferred to
Hydrogen chloride absorption, obtains aqueous hydrochloric acid solution.Phenol after depickling is transferred to rectifying column, by rectifying, from the 2 of overhead extraction high-quality,
4- chlorophenesic acid 6913kg, appearance colorless liquid (60 DEG C), content 99.37%, yield 99.5%.
Claims (4)
1. one kind 2, the production system of 4- chlorophenesic acids, it is characterised in that including：
Phenol chlorination reaction device, the phenol chlorination reaction device is provided with chlorosulfuric acid charging aperture, the outlet of phenol chlorinated exhaust
With product exit；
Chlorosulfuric acid synthesizer, the chlorosulfuric acid synthesizer is provided with tail gas charging aperture, chlorine feed mouth and discharging opening；It is described
Tail gas charging aperture is connected with the phenol offgas outlet of phenol chlorination reaction device；The discharging opening and phenol chlorination reaction device
Chlorosulfuric acid charging aperture be connected.
2. production system according to claim 1, it is characterised in that also including gas cleaning plant；The phenol chlorination
The tail gas charging aperture phase that the phenol chlorinated exhaust outlet of reaction unit passes through gas cleaning plant and the chlorosulfuric acid synthesizer
Connection.
3. production system according to claim 1, it is characterised in that also including rectifying column, the phenol chlorination reaction dress
The product exit put is connected with the rectifying column.
4. production system according to claim 1, it is characterised in that also including being connected with the phenol chlorination reaction device
Logical vacuum extractor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201720131051.7U CN206447796U (en) | 2017-02-13 | 2017-02-13 | A kind of production system of 2,4 chlorophenesic acid |
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| CN201720131051.7U CN206447796U (en) | 2017-02-13 | 2017-02-13 | A kind of production system of 2,4 chlorophenesic acid |
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| CN206447796U true CN206447796U (en) | 2017-08-29 |
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