CN106883103A - A kind of preparation method of 2,4 chlorophenesic acid - Google Patents
A kind of preparation method of 2,4 chlorophenesic acid Download PDFInfo
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- CN106883103A CN106883103A CN201710277943.2A CN201710277943A CN106883103A CN 106883103 A CN106883103 A CN 106883103A CN 201710277943 A CN201710277943 A CN 201710277943A CN 106883103 A CN106883103 A CN 106883103A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/26—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms
- C07C39/27—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms all halogen atoms being bound to ring carbon atoms
- C07C39/30—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms all halogen atoms being bound to ring carbon atoms the halogen being two chlorine atoms
Abstract
The present invention relates to a kind of preparation method of 2,4 chlorophenesic acids, it includes：With phenol and chlorine as raw material, under the catalytic action of phosphorus pentachloride, 2,4 chlorophenesic acids are obtained by chlorination reaction.The present invention is by using phosphorus pentachloride as catalyst, the heat produced in itself using chlorination reaction, whole chlorination process temperature control is carried out in suitable scope by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water, the energy is not only saved, and prepared 2 of content more than 98%, 4 chlorophenesic acids, and its chlorinated impurities 2,6 chlorophenesic acid contents are less than 0.90wt%, 2,4,6 trichlorophenol, 2,4,6 ,-T contents are less than 1.30wt%, the content of impurities such as o-chlorphenol, parachlorophenol and 2,4,5 trichlorophenol, 2,4,6,-Ts are less than 0.25wt%；The 2 of the content, 4 chlorophenesic acids can directly be used as the raw material for preparing the D active compounds of more than content 96wt% 2,4 without distillation or rectifying purifying, so as to reduce energy consumption.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of phenol catalytic chlorination prepares the side of chlorinated phenol
Method, more particularly to a kind of method that phenol catalytic chlorination prepares 2,4- chlorophenesic acids.
Background technology
2,4- chlorophenesic acids are medical industry, pesticide industry, important intermediate in Auxiliaries Industry, and annual requirement is 80,000
More than ton, it can be used to producing anthelmintic bithionol, pesticide herbicide 2,4-D and its series derivates with used as pesticides,
A series of materials such as Chu Cao Ji Evil humulones, insecticide phenol line phosphorus, nitrofen, mould inhibitor TCS, wherein in pesticide herbicide 2,4-D
And its with the application in the series derivates of used as pesticides be maximum.The production method of 2,4 dichloro phenol mainly has parachlorophenol
Catalytic chlorination process, o-chlorphenol catalytic chlorination process, phenol direct chlorination method etc..
Zhao Meifa and Li Congbao are reported with parachlorophenol as raw material, by homemade ZMF-1 catalysts chlorination pair
Chlorophenol method successfully prepares the 2,4 dichloro phenol of content more than 99% (referring to " high content 2,4 dichloro phenol synthesizes work
Skill research ", Zhao Meifa, Li Congbao, Anhui chemical industry, 02 phase in 1996, page 33~34), the method is suitable logical by selection
Chlorine pipe, the aspect such as the logical chlorine speed of control, time, logical chlorine dose, stirring efficiency greatly reduces the trichlorine of many chlorinated secondary products 2,4,6-
The generation of phenol, but content used be up to 99% parachlorophenol raw material be in itself by after phenol chlorination through rectifying just can obtain,
Thus result in and the parachlorophenol that content is 99% is used as the relatively costly of raw material preparation 2,4- chlorophenesic acids, carry out industrialized
Economy is not enough.
Sun Changjun etc. reports o-chlorphenol catalytic chlorination process and prepares 2,4 dichloro phenol (referring to " selective chlorination method is closed
Into 2,4- chlorophenesic acids ", Sun Changjun etc., Henan chemical industry, nineteen ninety o. 11th, the 19-21 pages), the method is industrially producing
The content obtained during parachlorophenol is that 96.5% accessory substance o-chlorphenol is raw material, with aluminum trichloride (anhydrous) and diphenyl sulfide
Make catalyst, chlorinating agent is made with chlorosulfuric acid, carry out chlorination reaction at 15 DEG C or so, product 2,4- chlorophenesic acid contents are in 95wt%
More than, remaining is 4wt% or so 2,6- chlorophenesic acids；Because the boiling point (being 220 DEG C under normal pressure) of 2,6- chlorophenesic acids only compares 2,4-
Chlorophenesic acid boiling point (being 210 DEG C under normal pressure) is high 10 DEG C, and more than 95wt% 2 is purified by distillation or rectifying, and 4- chlorophenesic acids are obtained
It is extremely difficult to content 99wt% above 2,4 dichloro phenols.
Phenol direct chlorination method is traditional production technology, the features such as with low cost, process is simple, but phenol and chlorine
The direct chlorination reaction time is more long, and 2,4- chlorophenesic acids content is less than 90% in general gained chlorination crude product, and impurity includes adjacent chlorine
Phenol, parachlorophenol, 2,6- chlorophenesic acids, 2,4,5 trichlorophenol, 2,4,6,-Ts and 2,4,6 trichlorophenol, 2,4,6,-Ts etc., particularly 2,6- chlorophenesic acids
Content is up to 8% or so and is closely difficult to separate with the physical property of 2,4 dichloro phenol.It is public in CN102659530A
Open with phenol as raw material, reaction temperature is controlled at 40~80 DEG C, 2,4- chlorophenesic acids prepared through multistage chlorination tower continuous chlorination,
Yield reaches 94.19-96.03wt%；Being disclosed in CN104529757B carries out the continuous chlorine of phenol using micro passage reaction
Change reaction, reaction temperature is controlled at 50 DEG C or 100 DEG C, and synthesis yield reaches as high as 98.8%, and control condition causes required product
2,4 dichloro phenol content is more than 90wt%.Micro passage reaction is developed recently and a kind of novel chemical equipment applied, and is made
It is to be carried out in micron-sized microchannel that must chemically react in characteristic dimension, because the miniaturization of yardstick causes chemical industry stream in microchannel
The mass transfer of body, heat transfer property have compared with conventional system and largely improve, so that more preferable reaction result is obtained,
Advantage in CN104529757B using the equipment realizes that required product 2,4 dichloro phenol content is more than 90wt% and yield
Up to 98.8% better result is a much progress, but the characteristics of due to MCA, it is applied in industrial production most
Big annual production is 2000 tons, thus this equipment to annual requirement up to more than 80,000 tons of 2,4- chlorophenesic acid products be improper
's；Furthermore, the World Food Programme (FAO) to agricultural chemicals 2, the specification standards of 4-D active compounds be content no less than 96%, and from 2,4- bis-
Chlorophenol sets out and prepares 2,4-D active compounds and typically will also be subjected to following three-step reaction：1) 2,4 dichloro phenol and NaOH
Reaction prepares 2,4- chlorophenesic acid sodium salts, 2) condensation of 2,4- chlorophenesic acids sodium salt and sodium chloroacetate prepares 2,4- Dichlorophenoxies
Acetic acid sodium salt；3) 2,4 dichlorophenoxyacetic acid sodium salt obtains 2,4-D and (can be found in CN104529757B explanations in detail with hydrochloric acid reaction
[0010] and [0011] section of book), this three-step reaction is all difficult to yield and reaches 100wt%, will all have new impurity to produce or draw
In entering 2,4-D active compounds, therefore 2,4-D active compound of the content no less than 96% is obtained, 2,4- chlorophenesic acids content used is necessarily
Higher than 96wt%；2, the 4-D active compound contents for otherwise obtaining do not reach the standard of FAO, to realize sale, it is necessary to will be less than
The 2,4-D active compounds crude product of 96wt% contents by the purifying of the conventional purification methods such as recrystallization be allowed to content reach 96wt% and with
On, and this will increase equipment investment, production cost, three wastes generation etc..Thus according to FAO to the specification mark of agricultural chemicals 2,4-D active compounds
Standard, according to 2,4- chlorophenesic acids prepared by the method disclosed in CN102659530A, content not necessarily disclosure satisfy that preparation 2,4-D
The requirement of active compound；According to the preparation 2 disclosed in CN104529757B, the method for 4- chlorophenesic acids, control 2,4- chlorophenesic acids contain
Amount is inadequate more than 90%, and this chlorination is selectively not high enough, and 2, the 4- chlorophenesic acid contents obtained by reaction are likely to not
It is too high, it is necessary to just can be used for the preparation of 2,4-D active compounds after purification by distillation or rectifying etc., or be directly used in preparation 2,4-D
Active compound crude product, then also needs by the agricultural chemicals 2 that can just obtain meeting FAO standards after purification process such as recrystallizing, 4-D active compounds, this
The economy of a little production technologies is all also improved space.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide one kind 2,4- chlorophenesic acids preparation method and its
Using.By the way that using phosphorus pentachloride as catalyst, the heat produced in itself using chlorination reaction is passed through speed by controlling chlorine
Whole chlorination process temperature control is carried out in suitable scope with the circulation rate of ordinary cycle water, has not only saved energy
Source, and 2,4- chlorophenesic acid of the content more than 98% has been prepared, its impurity content is low, can directly be used as preparation content
The raw material of 96wt% and above 2,4-D active compounds.
It is up to this purpose, present invention employs following technical scheme：
In a first aspect, the invention provides the preparation method of one kind 2,4- chlorophenesic acids, methods described includes：
With phenol and chlorine as raw material, under the catalytic action of phosphorus pentachloride, 2,4- dichloro-benzenes is obtained by chlorination reaction
Phenol.
Present invention employs using phosphorus pentachloride as catalyst, by the effect of the catalyst, chlorination reaction can be realized
High selectivity carry out, 2, the 4- chlorophenesic acids high income for preparing, content are high, and chlorinated impurities content is low.
Preferably, the consumption of the phosphorus pentachloride accounts for the 0.005~0.10% of raw material phenol molar fraction, for example
0.005%th, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% or
0.10%, preferably 0.01~0.07%, further preferred 0.03~0.05%.
Preferably, the consumption of the chlorine for raw material phenol molal quantity 2.00~2.12 equivalents, such as 2.00 equivalents,
2.01 equivalents, 2.02 equivalents, 2.03 equivalents, 2.04 equivalents, 2.05 equivalents, 2.06 equivalents, 2.07 equivalents, 2.08 equivalents, 2.09
Equivalent, 2.10 equivalents, 2.11 equivalents or 2.12 equivalents, preferably 2.01~2.09 equivalents, further preferred 2.05 equivalent.
Preferably, the temperature of the reaction be 42~55 DEG C, such as 42 DEG C, 43 DEG C, 44 DEG C, 45 DEG C, 46 DEG C, 47 DEG C, 48
DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C or 55 DEG C, preferably 42~47 DEG C, further preferred 42~45 DEG C.
Preferably, the time of the reaction be 16~22h, such as 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h,
19.5h, 20h, 21h or 22h, preferably 16.5~22h, further preferred 17~19.5h.
In the present invention, chlorination reaction process need not be heated additionally, but the heat produced in itself using chlorination reaction, lead to
That crosses control chlorine is passed through the circulation rate of speed and ordinary cycle water by whole chlorination process temperature control within the specific limits,
So as to save energy resource consumption.
For the speed that is passed through of chlorine, preferably controlled in 390~410m3In the range of/h, such as 391m3/h、393m3/
h、394m3/h、395m3/h、396m3/h、399m3/h、400m3/h、401m3/ h or 403m3/h；For the circulation speed of recirculated water
Degree, is preferably controlled in 0.50~0.70m3/ h, such as 0.52m3/h、0.54m3/h、0.55m3/h、0.56m3/h、0.58m3/
h、0.60m3/h、0.62m3/ h or 0.65m3/h.It should be understood by those skilled in the art that chlorine is passed through speed and recirculated water
The realization of circulation rate is carried out using technology and equipment well known in the art, and particular determination is not done herein.
Preferably, the preparation method of 2, the 4- chlorophenesic acids is carried out under the following conditions：
The consumption of the catalyst phosphorus pentachloride accounts for the 0.01~0.07% of raw material phenol molar fraction；
Total intake of the chlorine is 2.01~2.09 equivalents of raw material phenol molal quantity；
The temperature of reaction is 42~47 DEG C；
The time for being passed through chlorine reaction is 16.5~22h.
Under the above-described reaction conditions, 2, the 4- chlorophenesic acids of content up to more than 98wt% can be obtained, main chlorination is miscellaneous
Matter 2,6- chlorophenesic acids content is less than 0.90wt%, and 2,4,6- trichlorophenol, 2,4,6 ,-T contents are less than 1.30wt%, o-chlorphenol, to chlorobenzene
The content of impurities such as phenol and 2,4,5- trichlorophenol, 2,4,6,-Ts is less than 0.25wt%；Using the 2,4- dichloros prepared under the reaction condition
Phenol can be directly used for preparing 2,4-D active compounds (content 96wt%) for meeting FAO standards.
It is further preferred that the preparation method of 2, the 4- chlorophenesic acids is carried out under the following conditions：
The consumption of the catalyst phosphorus pentachloride accounts for the 0.03~0.05% of raw material phenol molar fraction；
Total intake of the chlorine is 2.05 equivalents of raw material phenol molal quantity；
The temperature of reaction is 42~47 DEG C；
The time for being passed through chlorine reaction is 17~19.5h.
Under the above-described reaction conditions, 2, the 4- chlorophenesic acids of content up to more than 99wt% can be obtained, main chlorination is miscellaneous
Matter 2,6- chlorophenesic acids content is less than 0.40wt%, 2, and 4,6- trichlorophenol, 2,4,6 ,-T contents are less than 0.40wt%, o-chlorphenol, to chlorobenzene
The content of impurities such as phenol and 2,4,5- trichlorophenol, 2,4,6,-Ts is less than 0.25wt%；Using the 2,4- dichloros prepared under the reaction condition
Phenol can be directly used for preparing 2, the 4-D active compounds (higher than FAO standards) of content 98wt%, and the specification active compound impurity is few, to environment
Negatively affected with crop low.
It is further preferred that the preparation method of 2, the 4- chlorophenesic acids is carried out under the following conditions：
The consumption of the catalyst phosphorus pentachloride accounts for the 0.05% of raw material phenol molar fraction；
Total intake of the chlorine is 2.05 equivalents of raw material phenol molal quantity；
The temperature of reaction is 42~47 DEG C；
The time for being passed through chlorine reaction is 17h.
Under the above-described reaction conditions, 2, the 4- chlorophenesic acids of content up to 99.410wt% can be obtained, main chlorination is miscellaneous
Matter 2,6- chlorophenesic acids content is less than 0.35wt%, and 2,4,6- trichlorophenol, 2,4,6 ,-T contents are less than 0.32wt%, o-chlorphenol, to chlorobenzene
The content of impurities such as phenol and 2,4,5- trichlorophenol, 2,4,6,-Ts is less than 0.25wt%；Using the 2,4- dichloros prepared under the reaction condition
Phenol equally can be directly used for preparing 2, the 4-D active compounds (higher than FAO standards) of content 98wt%, and the specification active compound impurity is less,
It is lower to environment and crop negative effect.
The preparation method of 2,4- chlorophenesic acids of the present invention, specifically may comprise steps of：
With phosphorus pentachloride as catalyst, add it in the phenol solution melted, be then passed through chlorine, it is anti-using chlorination
The heat that itself should be produced, the circulation rate of speed and ordinary cycle water is passed through by whole chlorination process temperature by controlling chlorine
Control is reacted in the range of 42~55 DEG C, obtains 2, the 4- chlorophenesic acids.
Second aspect, present invention also offers 2, the 4- chlorophenesic acids that method as described in relation to the first aspect is prepared.
2,4- chlorophenesic acids obtained by the present invention, its content can reach more than 98%, and main chlorinated impurities 2,6-
Chlorophenesic acid content be less than 0.90wt%, 2,4,6- trichlorophenol, 2,4,6 ,-T contents be less than 1.30wt%, o-chlorphenol, parachlorophenol and 2,
The content of impurities such as 4,5- trichlorophenol, 2,4,6,-Ts are less than 0.25wt%, so that 2, the 4- chlorophenesic acids are without distillation or rectifying purifying
Preparation can be directly used as and meet FAO standards (content 96wt%) and above agricultural chemicals 2, the raw material of 4-D active compounds, so as to substantially reduce
Prepare the energy consumption of high content 2,4 dichloro phenol.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention is by using phosphorus pentachloride as catalyst, the heat produced in itself using chlorination reaction, by control
Chlorine is passed through speed and the circulation rate of ordinary cycle water and whole chlorination process temperature control is carried out in suitable scope, no
The energy is only saved, and has prepared 2,4- chlorophenesic acid of the content more than 98%, its impurity content is low, wherein 2,6-
Chlorophenesic acid content be less than 0.90wt%, 2,4,6- trichlorophenol, 2,4,6 ,-T contents be less than 1.30wt%, o-chlorphenol, parachlorophenol and 2,
The content of impurities such as 4,5- trichlorophenol, 2,4,6,-Ts are less than 0.25wt%, can directly be used as 2, the 4-D originals for preparing content 96wt% and the above
The raw material of medicine；
(2) heat that the present invention is produced using chlorination reaction in itself, speed and ordinary cycle are passed through by control chlorine
Whole chlorination process temperature control within the specific limits, so as to save energy resource consumption, and is realized 2 by the circulation rate of water,
4- chlorophenesic acids are in high yield.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as to concrete restriction of the invention.
Embodiment 1
Phenol (content 99.9wt%) is heated to 42 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol) rises to reactor to 20,000, add content for 99wt% 3.1 kilograms of phosphorus pentachloride (14.8mol,
0.01mol% equivalents), stir, the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is connected by measuring pump
It is continuous to be passed through at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, external heat source insulation is not provided in course of reaction or is added
Heat, using chlorination reaction itself liberated heat, is caused by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water
Chlorination reaction is reacted between 50~55 DEG C, and tail gas exports to one-level tail gas absorption kettle preparation 30% by the conduit at the top of reactor
Hydrochloric acid is personal as by-product or sells；First order absorption kettle overflows gas and enters two grades of absorption kettles equipped with 20% sodium hydroxide solution
Absorbed.As logical chlorine 22h, chlorine is passed through up to 6709.4m3(equivalent chlorine 298.9kmol, 2.01mol equivalent), reaction solution
Temperature is 44.5 DEG C, and sampling carries out HPLC analyses, and phenol area normalization content 0.011%, 2,4- chlorophenesic acid area normalizations contain
Amount 98.505%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorine dissolved in reactant mixture
Change hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24547 kilograms, sampling carries out HPLC
Outer marking quantitative is analyzed, and 2,4- chlorophenesic acid contents are 98.015wt%, and phenol content is 0.093wt%, 2,4,6- trichlorophenol, 2,4,6,-Ts
Content is 0.889wt%, and 2,6- chlorophenesic acid contents are 0.817wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts
It is 0.186wt% Deng content of impurities, does not quantitative determine respectively；Thus calculate 2,4 dichloro phenol yield and reach 99.2wt%；Institute
The micro phosphorus pentachloride contained in 2,4 dichloro phenol or derivatives thereof (partly or entirely hydrolysis gained POCl3, phosphoric acid
Deng) when 2,4- chlorophenesic acids are prepared into 2,4- chlorophenesic acid sodium salts, sodium chloride and sodium ascorbyl phosphate being eventually converted into, this two
The coupling reaction that salt cannot participate in sodium chloroacetate is planted, negative effect will not be also played to coupling reaction, the present embodiment gained height contains
Amount 2,4 dichloro phenol can be directly used for preparing the 2,4-D active compounds of content 96wt%.
Embodiment 2
Phenol (content 99.9wt%) is heated to 43 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol) rises to reactor to 20,000, add content for 99wt% 9.3 kilograms of phosphorus pentachloride (44.6mol,
0.03mol% equivalents), stir, the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is connected by measuring pump
It is continuous to be passed through at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, external heat source insulation is not provided in course of reaction or is added
Heat, using chlorination reaction itself liberated heat, is caused by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water
Chlorination reaction is reacted between 42~45 DEG C, and tail gas exports to one-level tail gas absorption kettle preparation 30% by the conduit at the top of reactor
Hydrochloric acid is personal as by-product or sells；First order absorption kettle overflows gas and enters two grades of absorption kettles equipped with 20% sodium hydroxide solution
Absorbed.As logical chlorine 19.5h, chlorine is passed through up to 6846.3m3(equivalent chlorine 305.0kmol, 2.05mol equivalent), reaction
Liquid temperature degree is 45 DEG C, and sampling carries out HPLC analyses, and phenol area normalization content 0.009%, 2,4- chlorophenesic acid area normalizations contain
Amount 99.513%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorine dissolved in reactant mixture
Change hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24251 kilograms, sampling carries out HPLC
Outer marking quantitative is analyzed, and 2,4- chlorophenesic acid contents are 99.114wt%, and phenol content is 0.007wt%, 2,4,6- trichlorophenol, 2,4,6,-Ts
Content is 0.317wt%, and 2,6- chlorophenesic acid contents are 0.340wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts
It is 0.222wt% Deng content of impurities, does not quantitative determine respectively；Thus 2,4- chlorophenesic acids yield up to 99.1wt% is calculated, this
Embodiment gained high content 2,4 dichloro phenol can be directly used for preparing the 2,4-D active compounds of content 98wt%.
Embodiment 3
Phenol (content 99.9wt%) is heated to 44 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol, 0.05mol% equivalent) rises to reactor to 20,000, it is 15.5 kilograms of the phosphorus pentachloride of 99wt% to add content
(74.4mol), is stirred, and the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is continuously passed through by measuring pump
External heat source insulation is not provided at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, in course of reaction or is heated, utilize
Chlorination reaction itself liberated heat, the circulation rate of speed and ordinary cycle water is passed through so that chlorination reaction by controlling chlorine
React between 42~47 DEG C, tail gas exports to one-level tail gas absorption kettle 30% hydrochloric acid of preparation and is used as by the conduit at the top of reactor
By-product is personal or sells；First order absorption kettle overflows gas to be inhaled into two grades of absorption kettles equipped with 20% sodium hydroxide solution
Receive.As logical chlorine 17h, chlorine is passed through up to 6846.3m3(equivalent chlorine 305.0kmol, 2.05mol equivalent), reacting liquid temperature is
46 DEG C, sampling carries out HPLC analyses, phenol area normalization content 0.007%, 2,4- chlorophenesic acid area normalization contents
99.691%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorination dissolved in reactant mixture
Hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24251 kilograms, sampling is carried out outside HPLC
Scalar quantity is analyzed, and 2,4- chlorophenesic acid contents are 99.410wt%, and phenol content is 0.005wt%, and 2,4,6- trichlorophenol, 2,4,6,-Ts contain
It is 0.152wt% to measure, and 2,6- chlorophenesic acid contents are 0.193wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts etc.
Content of impurities is 0.240wt%, is not quantitative determined respectively；Thus 2,4- chlorophenesic acids yield up to 99.4wt%, this reality are calculated
Apply the 2,4-D active compounds that example gained high content 2,4 dichloro phenol can be directly used for preparing content 98wt%.
Embodiment 4
Phenol (content 99.9wt%) is heated to 42 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol) rises to reactor to 20,000, add content for 99wt% 21.7 kilograms of phosphorus pentachloride (103.6mol,
0.07mol% equivalents), stir, the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is connected by measuring pump
It is continuous to be passed through at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, external heat source insulation is not provided in course of reaction or is added
Heat, using chlorination reaction itself liberated heat, is caused by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water
Chlorination reaction is reacted between 42~47 DEG C, and tail gas exports to one-level tail gas absorption kettle preparation 30% by the conduit at the top of reactor
Hydrochloric acid is personal as by-product or sells；First order absorption kettle overflows gas and enters two grades of absorption kettles equipped with 20% sodium hydroxide solution
Absorbed.As logical chlorine 16.5h, chlorine is passed through up to 6846.3m3(equivalent chlorine 305.0kmol, 2.05mol equivalent), reaction
Liquid temperature degree is 46 DEG C, and sampling carries out HPLC analyses, and phenol area normalization content 0.000%, 2,4- chlorophenesic acid area normalizations contain
Amount 98.545%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorine dissolved in reactant mixture
Change hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24641 kilograms, sampling carries out HPLC
Outer marking quantitative is analyzed, and 2,4- chlorophenesic acid contents are 98.036wt%, and phenol content is 0.000wt%, 2,4,6- trichlorophenol, 2,4,6,-Ts
Content is 1.134wt%, and 2,6- chlorophenesic acid contents are 0.643wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts
It is 0.187wt% Deng content of impurities, does not quantitative determine respectively；Thus 2,4- chlorophenesic acids yield up to 99.6wt% is calculated, this
Embodiment gained high content 2,4 dichloro phenol can be directly used for preparing the 2,4-D active compounds of content 96wt%.
Embodiment 5
Phenol (content 99.9wt%) is heated to 42 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol) rises to reactor to 20,000, add content for 99wt% 15.5 kilograms of phosphorus pentachloride (74.4mol,
0.05mol% equivalents), stir, the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is connected by measuring pump
It is continuous to be passed through at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, external heat source insulation is not provided in course of reaction or is added
Heat, using chlorination reaction itself liberated heat, is caused by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water
Chlorination reaction is reacted between 42~47 DEG C, and tail gas exports to one-level tail gas absorption kettle preparation 30% by the conduit at the top of reactor
Hydrochloric acid is personal as by-product or sells；First order absorption kettle overflows gas and enters two grades of absorption kettles equipped with 20% sodium hydroxide solution
Absorbed.As logical chlorine 17.8h, chlorine is passed through up to 6979.8m3(equivalent chlorine 310.9kmol, 2.09mol equivalent), reaction
Liquid temperature degree is 46 DEG C, and sampling carries out HPLC analyses, and phenol area normalization content 0.000%, 2,4- chlorophenesic acid area normalizations contain
Amount 98.219%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorine dissolved in reactant mixture
Change hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24219 kilograms, sampling carries out HPLC
Outer marking quantitative is analyzed, and 2,4- chlorophenesic acid contents are 98.042wt%, and phenol content is 0.000wt%, 2,4,6- trichlorophenol, 2,4,6,-Ts
Content is 1.236wt%, and 2,6- chlorophenesic acid contents are 0.550wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts
It is 0.172wt% Deng content of impurities, does not quantitative determine respectively；Thus 2,4- chlorophenesic acids yield up to 97.9wt% is calculated, this
Embodiment gained high content 2,4 dichloro phenol can be directly used for preparing the 2,4-D active compounds of content 96wt%.
Embodiment 6
Phenol (content 99.9wt%) is heated to 42 DEG C in still preheater, 14000 kilograms are conveyed by pipe insulation
During (148.8kmol) rises to reactor to 20,000, add content for 99wt% 12.4 kilograms of phosphorus pentachloride (59.5mol,
0.04mol% equivalents), stir, the content of room temperature will be preheated under stirring for the chlorine of 99.8wt% is connected by measuring pump
It is continuous to be passed through at 2/3rds under the liquid level of phenol and phosphorus pentachloride mixed liquor, external heat source insulation is not provided in course of reaction or is added
Heat, using chlorination reaction itself liberated heat, is caused by the circulation rate for controlling chlorine to be passed through speed and ordinary cycle water
Chlorination reaction is reacted between 42~45 DEG C, and tail gas exports to one-level tail gas absorption kettle preparation 30% by the conduit at the top of reactor
Hydrochloric acid is personal as by-product or sells；First order absorption kettle overflows gas and enters two grades of absorption kettles equipped with 20% sodium hydroxide solution
Absorbed.As logical chlorine 19.5h, chlorine is passed through up to 6846.3m3(equivalent chlorine 305.0kmol, 2.05mol equivalent), reaction
Liquid temperature degree is 45 DEG C, and sampling carries out HPLC analyses, and phenol area normalization content 0.008%, 2,4- chlorophenesic acid area normalizations contain
Amount 99.605%, chlorination terminates, and stops logical chlorine；Change logical nitrogen (content 99.5%) 1h and remove the chlorine dissolved in reactant mixture
Change hydrogen and a small amount of chlorine, it is common enter nitrogen 210m3；Product is put into metering tank and is weighed as 24229 kilograms, sampling carries out HPLC
Outer marking quantitative is analyzed, and 2,4- chlorophenesic acid contents are 99.302wt%, and phenol content is 0.006wt%, 2,4,6- trichlorophenol, 2,4,6,-Ts
Content is 0.235wt%, and 2,6- chlorophenesic acid contents are 0.278wt%；O-chlorphenol, parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts
It is 0.185wt% Deng content of impurities, does not quantitative determine respectively；Thus 2,4- chlorophenesic acids yield up to 99.2wt% is calculated, this
Embodiment gained high content 2,4 dichloro phenol can be directly used for preparing the 2,4-D active compounds of content 98wt%.
Comparative example 1
Compared with Example 1, except phosphorus pentachloride is replaced with into alchlor (14.8mol, 0.01mol% equivalent) outward, its
It is same as Example 1.
After measured and calculate, the content of 2, the 4- chlorophenesic acids for preparing is 92.564wt%, and phenol content is
0.000wt%, 2,4,6- trichlorophenol, 2,4,6 ,-T contents are 3.494wt%, and 2,6- chlorophenesic acid contents are 1.763wt%；O-chlorphenol,
The content of impurities such as parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts are 2.032wt%.
Comparative example 2 (with reference to CN103435453A)
Compared with Example 1, except phosphorus pentachloride is replaced with into iron powder (14.8mol, 0.01mol% equivalent) and dibenzo
Outward, other are same as Example 1 for [b, f] [Isosorbide-5-Nitrae] sulphur azatropylidene -11- ketone-phosphoryl chloride phosphorus oxychloride (829g).
After measured and calculate, the content of 2, the 4- chlorophenesic acids for preparing is 96.495wt%, and phenol content is
0.014wt%, 2,4,6- trichlorophenol, 2,4,6 ,-T contents are 0.282wt%, and 2,6- chlorophenesic acid contents are 3.053wt%；O-chlorphenol,
The content of impurities such as parachlorophenol, 2,4,5- trichlorophenol, 2,4,6,-Ts are 0.123wt%.
Comparative example 3
Using CN102659530A embodiment 3 disclosed in method carry out the preparation of 2,4 dichloro phenol.
After measured and calculate, the content of 2, the 4- chlorophenesic acids for preparing is 94.512wt%, its impurity 2,4,6- tri-
Chlorophenol content is 0.889wt%, and 2,6- chlorophenesic acid contents are 3.654wt%；O-chlorphenol, parachlorophenol, 2,4,5- tri-
The content of impurities such as chlorophenol are 0.872wt%.
Comparative example 4
Using CN104529757B example IV disclosed in method carry out the preparation of 2,4 dichloro phenol.
After measured and calculate, the content of 2, the 4- chlorophenesic acids for preparing is 95.121wt%, its impurity 2,4,6- tri-
Chlorophenol content is 1.673wt%, and 2,6- chlorophenesic acid contents are 2.415wt%；O-chlorphenol, parachlorophenol, 2,4,5- tri-
The content of impurities such as chlorophenol are 0.740wt%.
Above-described embodiment 1~6 and comparative example 1~2 are compared as can be seen that embodiment 1~6 is made using phosphorus pentachloride
During for catalyst, other catalyst, 2, the 4- chlorophenesic acids that it is prepared are used to contain with higher compared to comparative example 1~2
Amount, and chlorinated impurities content is lower, illustrate that the present invention is used as catalyst and is more conducive to results height by use phosphorus pentachloride and contains
The 2,4 dichloro phenol of amount and low impurity content；Above-described embodiment 1~6 and comparative example 3~4 are compared as can be seen that phase
Than comparative example 3~4,2, the 4- chlorophenesic acids that embodiment 1~6 is prepared equally have content higher, and chlorinated impurities
Content is lower, illustrates that the present invention can obtain 2, the 4- chlorophenesic acids of higher amount, its impurity content by modified technique method
It is low, preparation content 96wt% and above agricultural chemicals 2 can be directly used as, the raw material of 4-D active compounds saves technique, reduces energy consumption, has
There is important application value.
Applicant states that the present invention illustrates detailed process equipment of the invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within of the invention
Within the scope of protection domain and disclosure.
Claims (9)
1. one kind 2, the preparation method of 4- chlorophenesic acids, it is characterised in that methods described includes：
With phenol and chlorine as raw material, under the catalytic action of phosphorus pentachloride, 2,4- chlorophenesic acids are obtained by chlorination reaction.
2. the method for claim 1, it is characterised in that the consumption of the phosphorus pentachloride accounts for raw material phenol molar fraction
0.005~0.10%, preferably 0.01~0.07%, further preferred 0.03~0.05%.
3. method as claimed in claim 1 or 2, it is characterised in that the consumption of the chlorine is raw material phenol molal quantity
2.00~2.12 equivalents, preferably 2.01~2.09 equivalents, further preferred 2.05 equivalent.
4. the method as described in one of claim 1-3, it is characterised in that the temperature of the reaction is 42~55 DEG C, preferably 42
~47 DEG C, further preferred 42~45 DEG C.
5. the method as described in one of claim 1-4, it is characterised in that the time of the reaction is 16~22h, preferably 16.5
~22h, further preferred 17~19.5h.
6. the method as described in one of claim 1-5, it is characterised in that methods described includes：
With phosphorus pentachloride as catalyst, add it in the phenol solution melted, chlorine is then passed through, using chlorination reaction sheet
The heat that body is produced, the circulation rate of speed and ordinary cycle water is passed through by whole chlorination process temperature control by controlling chlorine
Reacted in the range of 42~55 DEG C, obtained 2, the 4- chlorophenesic acids.
7. the 2,4 dichloro phenol that the method as described in one of claim 1-6 is prepared.
8. 2,4- chlorophenesic acids as claimed in claim 7, it is characterised in that the chlorination contained in 2, the 4- chlorophenesic acids is miscellaneous
Matter 2,6- chlorophenesic acids content is less than 0.90wt%, and 2,4,6- trichlorophenol, 2,4,6 ,-T contents are less than 1.30wt%, o-chlorphenol, to chlorobenzene
The content of impurities such as phenol and 2,4,5- trichlorophenol, 2,4,6,-Ts is less than 0.25wt%.
9. purposes of the 2,4 dichloro phenol as claimed in claim 7 or 8 in 2,4-D active compounds are prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452094A (en) * | 2019-06-12 | 2019-11-15 | 东南大学 | Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol |
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085722A (en) * | 2007-01-10 | 2007-12-12 | 胡汉忠 | Industrial preparation method for p-chloroalkylphenols |
| CN102659530A (en) * | 2012-04-27 | 2012-09-12 | 沙隆达集团公司 | Continuous preparation method of herbicide intermediate of 2, 4-dichlorophenol |
| CN106349025A (en) * | 2016-07-28 | 2017-01-25 | 连云港致诚化工有限公司 | Preparation process of 2,4-dichlorophenol |
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2017
- 2017-04-25 CN CN201710277943.2A patent/CN106883103B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085722A (en) * | 2007-01-10 | 2007-12-12 | 胡汉忠 | Industrial preparation method for p-chloroalkylphenols |
| CN102659530A (en) * | 2012-04-27 | 2012-09-12 | 沙隆达集团公司 | Continuous preparation method of herbicide intermediate of 2, 4-dichlorophenol |
| CN106349025A (en) * | 2016-07-28 | 2017-01-25 | 连云港致诚化工有限公司 | Preparation process of 2,4-dichlorophenol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452094A (en) * | 2019-06-12 | 2019-11-15 | 东南大学 | Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol |
| CN110452094B (en) * | 2019-06-12 | 2022-05-13 | 东南大学 | Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol |
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
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