CN117886675A - Method for synthesizing chlorophenol by catalytic chlorination - Google Patents
Method for synthesizing chlorophenol by catalytic chlorination Download PDFInfo
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 46
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000460 chlorine Substances 0.000 claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 34
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 31
- 239000007789 gas Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 238000003756 stirring Methods 0.000 description 28
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 21
- 238000005273 aeration Methods 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 16
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 9
- 238000012544 monitoring process Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005574 MCPA Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000234653 Cyperus Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing chlorophenol by catalytic chlorination, which comprises the steps of reacting phenol with a mixed gas of chlorine and air in water in the presence of a catalyst to obtain a chlorination reaction liquid, separating the chlorination reaction liquid, and then distilling and dehydrating to obtain a chlorophenol product. The invention takes phenol as raw material, reacts with the mixed gas of chlorine and air under the action of the catalyst, and obviously improves the reaction rate while obtaining higher reaction selectivity, pure oxygen and concentrated hydrochloric acid are not used after improvement, a large amount of phenol-containing hydrochloric acid is not produced, the product quality and the product yield are greatly improved, and the invention is more suitable for industrial mass production.
Description
Technical Field
The invention relates to a method for synthesizing chlorophenol, in particular to a method for synthesizing chlorophenol by chlorination, which can improve the catalytic selectivity, and belongs to the technical field of organic synthesis.
Background
The phenoxy carboxylic acid herbicide is a first type of hormone-type selective herbicide commercially produced in the world, is also the second highest in global demand, is environment-friendly, has the characteristics of short residual period, low toxicity to human beings and other organisms and the like, rarely generates drug resistance, and is mainly used for preventing and killing dicotyledonous weeds, nutgrass flatsedge and certain malignant weeds in gramineous crop fields such as corn, wheat, rice and the like. The most widely used phenoxy carboxylic acid herbicides are 2,4-D followed by MCPA.
2, 4-Dichlorophenol and 4-chloro-o-cresol are respectively important intermediates for synthesizing 2,4-D, MCPA. The current general synthesis method of 2, 4-dichlorophenol and 4-chloro-o-cresol is that phenol and o-cresol are obtained by chlorination of sulfuryl chloride or chlorine in the presence of a catalyst, and a large amount of byproduct hydrochloric acid is generated by the method, and the hydrochloric acid contains phenol, so that the hydrochloric acid has unpleasant pungent smell, cannot be used by itself or used as a raw material for production of other products, can only be used as hazardous waste for disposal, not only causes waste of byproduct hydrochloric acid, but also increases a large amount of hazardous waste disposal cost, and is neither environment-friendly nor economical.
Yawen Xiong et al, HIGHLY SELECTIVE SYNTHESIS of Chlorophenols under Microwave Irradiation, studied the chlorination of o-cresol. Copper chloride is used as a catalyst, hydrochloric acid is used as a chlorinating agent, oxygen is used as an oxidizing agent, and the selective chlorination of o-cresol into 4-chloro-o-cresol is realized in a microwave environment, wherein the selectivity is 91.7%. The research takes an important step of phenol chlorination process research without by-producing hydrochloric acid, and has great practical significance. But we also note that their research still has many problems: (1) there is still room for the selectivity to rise; (2) Pure oxygen is needed instead of cheaper and easily available air, and the cost is high; (3) The reactant must be activated by microwave, otherwise, the reaction rate is very slow, even if the reaction rate is not very ideal after activation, the industrialization value is low; (4) Concentrated hydrochloric acid is consumed, but a large amount of dilute hydrochloric acid which is difficult to use is produced. These drawbacks, in particular the slow reaction rate, severely limit its industrial application.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for synthesizing chlorophenol by catalytic chlorination on the basis of fully and scientifically analyzing reaction mechanism, which improves the selectivity of chlorination reaction, improves the reaction rate, has low-cost and easily-obtained raw materials, does not generate a large number of difficult-to-process byproducts, and is more suitable for industrial production.
The specific technical scheme of the invention is as follows:
A method for synthesizing chlorophenol by catalytic chlorination includes such steps as reacting phenol with the mixture of chlorine and air in water in the presence of catalyst to obtain the reaction liquid of chlorination.
Further, in actual operation, phenol, water and a catalyst are mixed first, then the reaction temperature is raised, and a mixed gas of chlorine and air is continuously introduced into the mixed liquid under vigorous stirring until the conversion rate of the phenol reaches an expected value, the introduction of the mixed gas is stopped, and the reaction is stopped.
Further, when the conversion rate of phenol reaches more than 99%, the phenol is considered to be completely converted to reach the expected value. The conversion of phenol can be measured by monitoring the progress of the reaction by Gas Chromatography (GC).
Further, the phenol is one of phenol, 2-chlorophenol, 4-chlorophenol and o-cresol. When the phenol is phenol, the main product of chlorination is 2, 4-dichlorophenol (the reaction progress can also be controlled so that the main product is 4-chlorophenol); when the phenol is 2-chlorophenol, the main chlorination product is 2, 4-dichlorophenol; when the phenol is 4-chlorophenol, the main chlorination product is 2, 4-dichlorophenol; when the phenol is o-cresol, the main chlorinated product is 4-chloro-o-cresol.
Further, the catalyst is a mixture of two different types of first catalyst and second catalyst. Wherein the first catalyst is one or two of cupric chloride and cuprous chloride; the second catalyst is one or two of 2,2 '-bipyridine and 4,4' -bipyridine.
Further, the first catalyst is used in an amount of 1% to 5%, for example 1%, 2%, 3%, 4%, 5% by weight of phenol, preferably in an amount of 1% to 3%.
Further, the second catalyst is used in an amount of 0.5% to 2.5%, for example 0.5%, 1.0%, 1.5%, 2.0%, 2.5% by weight of phenol, preferably in an amount of 0.5% to 1.5%.
Further, in the mixed gas, the volume ratio of air to chlorine is 1.25-1.5: 1, for example 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.5:1. Wherein, air is used as an oxidant, chlorine is used as a chlorinating agent, the air amount is not too much, the utilization rate of the chlorine is reduced due to too much air, and the air amount is not too little, otherwise, more hydrochloric acid is generated.
Further, the mixed gas is introduced into the mixed solution of phenol, water and the catalyst at a certain rate, and in order to increase the reaction rate and shorten the reaction time, the introduction rate of the mixed gas can be increased. In addition, in order to make the mixed gas fully contact and react with phenol in the liquid environment more fully, the mixed gas can be introduced in a manner disclosed in the prior art, for example, from the bottom of the mixed liquid, through a gas distributor, through a suction stirrer, through a venturi device, under turbine stirring, etc., and the type of the reactor can be a kettle type, a micro-channel reactor suitable for gas-liquid reaction, a packed tower, a plate type tower, a bubbling tower, a supergravity device, etc.
The mixture is added under intense stirring to increase the contact efficiency with phenol and to increase the reaction efficiency, and the stirring speed is preferably 600r/min or more, for example, 600r/min、700r/min、800r/min、900r/min、1000r/min、1200r/min、1500r/min、1800r/min、2000r/min、2500r/min、3000r/min or the like, or a range between any two. The lower stirring speed can obviously reduce the gas-liquid reaction rate.
Further, the reaction temperature is 50 to 80 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, and the higher the reaction temperature, the lower the reaction selectivity, preferably 50 to 60 ℃. At the preferred temperature, the reaction selectivity is higher.
Further, the reaction time is generally 0.25 to 1.0h.
Further, the amount of water to be used is usually 1 to 5 times, for example 1, 2,3,4, 5 times the mass of phenol. Too much water will result in a reduced single pass yield of the product, preferably 1 to 3 times the mass of phenol, and particularly preferably 1 to 1.5 times the mass of phenol.
Further, after the reaction is carried out to obtain a chlorination reaction liquid, the method further comprises the steps of separating the chlorination reaction liquid to obtain crude chlorophenol and dehydrating the crude chlorophenol to obtain a chlorophenol finished product. Standing the chlorination reaction liquid at a certain temperature for separating liquid, wherein the lower oil phase is a crude chlorophenol product, and the upper oil phase is a water phase; and (3) dehydrating the obtained crude chlorophenol product in a distillation mode to obtain a chlorophenol finished product.
Further, the liquid separation temperature is 50-60 ℃, the delamination is not favored due to the too high temperature, and phenol in the material with the too low temperature can be crystallized.
Further, the dehydration is preferably carried out under vacuum or reduced pressure, the temperature is 80 to 100 ℃, too low a temperature may cause difficulty in removing moisture, and too high a temperature may cause deterioration of a small amount of chlorophenols. The absolute pressure of the system during dehydration is generally 3-5 kPa.
The preparation method provided by the invention has the following advantages:
1) The method provided by the invention has the advantages that the selectivity of the reaction is greatly improved by using the synergistic catalyst, the reaction rate is greatly accelerated, the reaction can be ended within one hour, and the industrialization is easier.
2) The method provided by the invention does not need to use oxygen, but uses the mixed gas of chlorine and air, wherein the chlorine and the air are all widely-sourced materials, and the cost is low.
3) The method provided by the invention does not use hydrochloric acid as a chlorine source, and does not produce hydrochloric acid as a byproduct, so that the problem that a large amount of phenol-containing hydrochloric acid is produced in the conventional chlorophenol synthesis method is solved.
4) The method provided by the invention takes phenol as a raw material, and reacts with the mixed gas of chlorine and air under the action of the catalyst, so that the reaction rate is obviously improved while the higher reaction selectivity is obtained, pure oxygen and concentrated hydrochloric acid are not used any more, a large amount of phenol-containing hydrochloric acid is not byproduct any more, and the product quality and the product yield are greatly improved.
5) The method provided by the invention has simple and easy flow, the selectivity can reach more than 97.0%, and the purity of the chlorophenol can reach more than 97.0%.
Detailed Description
In order to further illustrate the present invention, the method for preparing chlorophenols provided by the present invention will be described in detail with reference to specific examples.
In the following examples, the concentrations are mass percent concentrations unless otherwise specified.
Example 1
108.4G of 98.64% o-cresol, 109.9g of water, 1.1g of copper chloride and 0.5g of 4,4' -bipyridine are added into a 500mL four-neck flask with suction stirring, the temperature is raised to 50 ℃ under stirring, the suction stirring rotating speed is regulated to 800r/min, and the volume ratio of air to chlorine is 1.3:1, uniformly mixing air and chlorine through a mixer with a filler at an aeration rate of 0.9L/min, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature at 50-55 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the o-cresol conversion rate is more than or equal to 99%, accumulating aeration for 59min, and continuing to perform heat preservation reaction for 15min to obtain a chlorination reaction liquid. The chlorination reaction liquid was sampled and detected by GC, and the selectivity of 4-chloro-o-cresol was calculated to be 98.3%.
Reducing the stirring rotation speed to 150r/min, heating the chlorination reaction liquid to about 55 ℃, stopping stirring, standing for 15min under the heat preservation, transferring into a separating funnel, standing for 15min, separating liquid, and obtaining the lower-layer oil phase as the crude chlorophenol product.
Transferring the obtained chlorophenol crude product into a clean 250mL four-mouth bottle, connecting a distillation device, heating to 80 ℃ under stirring at 3-5 kPa absolute pressure, distilling and dehydrating, distilling a small amount of fractions (water and trace phenol) at the gas phase temperature of about 32 ℃, slowly rising the material temperature from 80 ℃ along with the distillation of water, and weighing the rest material in the flask, namely 4-chloro-o-cresol, to obtain 139.1g of 4-chloro-o-cresol, quantitatively analyzing by using HPLC, wherein the content is 98.4%, and calculating the product yield to be 97.1% of o-cresol.
Example 2
To a 500mL four-necked flask with suction stirring, 98.7g of 98.23% phenol, 191.7g of water, 4.7g of cuprous chloride and 0.9g of 2,2' -bipyridine were added, and the temperature was raised to 80℃with stirring, the suction stirring rotation speed was adjusted to 1000r/min, and the volume ratio of air to chlorine was 1.3:1, uniformly mixing air and chlorine at an aeration rate of 6.7L/min by a mixer with a filler, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature at 75-80 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the phenol conversion rate is more than or equal to 99%, accumulating aeration for 16min, and continuing to perform heat preservation reaction for about 15min to obtain a chlorination reaction liquid. The chlorination reaction liquid was sampled and detected by GC to calculate the selectivity of 2, 4-dichlorophenol to 97.1%.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain 164.5g of a 2, 4-dichlorophenol product, and the product was quantitatively analyzed by HPLC to obtain 97.6% of the product, and the yield was calculated to be 95.6% based on phenol.
Example 3
127.9G of 98.45% 2-chlorophenol, 391.9g of water, 5.2g of copper chloride and 2.2g of 2,2' -bipyridine are added into a 500mL four-necked flask with suction stirring, the temperature is raised to 70 ℃ under stirring, the suction stirring rotating speed is regulated to 600r/min, and the volume ratio of air to chlorine is 1.3:1, uniformly mixing air and chlorine at an aeration rate of 2.2L/min by a mixer with a filler, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature at 65-70 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the 2-chlorophenol conversion rate is more than or equal to 99%, accumulating aeration for 24min, and continuing to perform heat preservation reaction for about 15min to obtain a chlorination reaction liquid. The chlorination reaction liquid was sampled and detected by GC, and the selectivity of 2, 4-dichlorophenol was calculated to be 97.8%.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain 155.8g of a 2, 4-dichlorophenol product, and the product was quantitatively analyzed by HPLC to obtain a content of 98.3%, and the product yield was calculated to be 95.9% based on phenol.
Example 4
To a 500mL four-necked flask with suction stirring, 133.3g of 98.17% 4-chlorophenol, 523.6g of water, 3.9g of cuprous chloride and 1.4g of 4,4' -bipyridine were added, and the temperature was raised to 60℃under stirring, the suction stirring rotation speed was adjusted to 800r/min, and the volume ratio of air to chlorine was 1.3:1, uniformly mixing air and chlorine at an aeration rate of 2.5L/min by a mixer with a filler, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature to be 55-60 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the 4-chlorophenol conversion rate is more than or equal to 99%, accumulating aeration for 22min, and continuing to perform heat preservation reaction for about 15min to obtain a chlorination reaction liquid. The chlorination reaction liquid was sampled and detected by GC, and the selectivity of 2, 4-dichlorophenol was calculated to be 98.3%.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain 161.5g of a 2, 4-dichlorophenol product, and the product was quantitatively analyzed by HPLC to obtain 98.7% of the product, and the product yield was calculated to be 96.1% based on phenol.
Example 5
To a 500mL four-necked flask with suction stirring, 93.6g of 98.23% phenol, 459.7g of water, 1.9g of copper chloride and 1.8g of 4,4' -bipyridine were added, and the temperature was raised to 50℃with stirring, the suction stirring speed was adjusted to 800r/min, and the volume ratio of air to chlorine was 1.3:1, uniformly mixing air and chlorine through a mixer with a filler at an aeration rate of 1.9L/min, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature at 50-55 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the phenol conversion rate is more than or equal to 99%, accumulating aeration for 55min, and continuing to perform heat preservation reaction for about 15min to obtain a chlorination reaction liquid. The chlorination reaction liquid was sampled and detected by GC, and the selectivity of 2, 4-dichlorophenol was calculated to be 98.6%.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain 154.6g of a 2, 4-dichlorophenol product, and the product was quantitatively analyzed by HPLC to obtain a content of 99.2%, and the product yield was calculated to be 96.3% based on phenol.
Examples 6 to 11
To 500mL four-necked flask with suction stirring, 98.64% of o-cresol, water, copper chloride and 4,4' -bipyridine are added, the mixture is stirred and heated to the reaction temperature, the suction stirring speed is regulated to 800r/min, and the volume ratio of air to chlorine is 1.4:1, uniformly mixing air and chlorine through a mixer with a filler at an aeration rate of 2.1L/min, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the o-cresol conversion rate is more than or equal to 99%, accumulating aeration for 26min, and continuing to perform heat preservation reaction for 15min to obtain a chlorination reaction liquid. Sampling the chlorination reaction liquid, detecting by GC, and calculating to obtain the selectivity of the 4-chloro-o-cresol.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain a 4-chloro-o-cresol product, and quantitative analysis was performed by HPLC to obtain the content and yield.
4-Chloro-o-cresol was prepared under the conditions of Table 1, and the results are shown in Table 2.
Examples 12 to 14
Adding 98.64% of o-cresol, water, cuprous chloride and 4,4' -bipyridine into a 500mL four-neck flask with suction stirring, heating to 50 ℃ under stirring, adjusting the suction stirring rotating speed to 800r/min, and adjusting the volume ratio of air to chlorine to be 1.4:1, uniformly mixing air and chlorine through a mixer with a filler at an aeration rate of 2.1L/min, introducing the mixture into a flask at a uniform speed, aerating for about 1min, then obviously raising the temperature of materials in the flask, cooling by using an ice water bath, maintaining the reaction temperature to be 50 ℃, periodically sampling and monitoring by using GC in the reaction process, stopping aeration when the o-cresol conversion rate is more than or equal to 99%, accumulating aeration for 27min, and continuing to perform heat preservation reaction for 15min to obtain a chlorination reaction liquid. Sampling the chlorination reaction liquid, detecting by GC, and calculating to obtain the selectivity of the 4-chloro-o-cresol.
The chlorination reaction liquid was post-treated in the same manner as in example 1 to obtain a 4-chloro-o-cresol product, and quantitative analysis was performed by HPLC to obtain the content and yield.
4-Chloro-o-cresol was prepared under the conditions of Table 3, and the results are shown in Table 4.
Comparative example 1
4-Chloro-o-cresol was prepared as in example 1, except that: instead of 4,4' -bipyridine, 1.1g of copper chloride was replaced with 1.6g of copper chloride. The result showed that the content of 4-chloro-o-cresol as a product was 91.4% and the yield was 89.8% based on o-cresol.
Comparative example 2
4-Chloro-o-cresol was prepared as in example 1, except that: copper chloride was not added and 0.5g of 4,4 '-bipyridine was replaced with 1.6g of 4,4' -bipyridine. The result showed that the content of 4-chloro-o-cresol as a product was 78.7% and the yield was 76.5% based on o-cresol.
Comparative example 3
4-Chloro-o-cresol was prepared as in example 1, except that: 1.1g of copper chloride was replaced by 1.1g of copper sulfate. The result showed that the content of 4-chloro-o-cresol as a product was 84.1% and the yield was 82.1% based on o-cresol.
Comparative example 4
4-Chloro-o-cresol was prepared as in example 1, except that: 0.5g of 4,4' -bipyridine was replaced with 0.5g of pyridine. The result showed that the content of 4-chloro-o-cresol of the product was 92.2% and the yield was 90.3% based on o-cresol.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it is possible for those skilled in the art to make several improvements and modifications to the present invention without departing from the principle of the present invention, for example, the chlorophenols in the chlorination reaction liquid may also be separated by extraction, rectification, extraction, stripping, etc., and these improvements and modifications fall within the protection scope of the claims of the present invention.
Claims (10)
1. A method for synthesizing chlorophenol by catalytic chlorination is characterized by comprising the following steps: comprises the step of reacting phenol with a mixed gas of chlorine and air in water in the presence of a catalyst to obtain a chlorination reaction liquid.
2. The method according to claim 1, characterized in that: the catalyst is a mixture of a first catalyst and a second catalyst, wherein the first catalyst is one or two of cupric chloride and cuprous chloride, and the second catalyst is one or two of 2,2 '-bipyridine and 4,4' -bipyridine.
3. The preparation method according to claim 2, characterized in that: the first catalyst is used in an amount of 1-5% by weight of phenol, and the second catalyst is used in an amount of 0.5-2.5% by weight of phenol.
4. The preparation method according to claim 1, characterized in that: the phenol is one of phenol, 2-chlorophenol, 4-chlorophenol and o-cresol.
5. The preparation method according to claim 1, characterized in that: the volume ratio of air to chlorine is 1.25-1.5: 1.
6. The preparation method according to claim 1, characterized in that: the reaction temperature is 50-80 ℃.
7. The preparation method according to claim 1, characterized in that: the water is 1-5 times of the phenol mass.
8. The preparation method according to claim 1, characterized in that: the method also comprises the steps of separating the chlorination reaction liquid, and dehydrating the crude chlorophenol obtained by separating the chlorination reaction liquid to obtain a chlorophenol finished product.
9. The method for preparing the composite material according to claim 8, wherein: the liquid separation temperature is 50-60 ℃.
10. The method for preparing the composite material according to claim 8, wherein: the dehydration is carried out by distillation, and the dehydration temperature is 80-100 ℃.
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