CN104045521B - A kind of parachlorometacresol green synthesis process - Google Patents
A kind of parachlorometacresol green synthesis process Download PDFInfo
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Abstract
The present invention provides a kind of parachlorometacresol green synthesis process, employing metacresol is raw material, tetrachloroethylene is solvent and chlorosulfuric acid is that chlorinating agent reacts with prepared parachlorometacresol, the mol ratio of wherein said metacresol and described tetrachloroethylene is 1:0.5-1.5, and the mol ratio of described metacresol and described chlorosulfuric acid is 1:0.9-1.1. Compared with prior art, the present invention process response time is short, solvent recovering rate is high, production process clean environment firendly, automaticity high, and reaction terminates the conversion ratio of rear metacresol up to 98%, has good industrialization prospect.
Description
Technical field
The present invention relates to chloridization process in chemical process, particularly relate to a kind of parachlorometacresol synthesis technique.
Background technology
Parachlorometacresol (C7H7ClO) it is a kind of organic synthesis raw material, colourless liquid, fusing point 66～68 DEG C, boiling point 196 DEG C, water insoluble, it is soluble in benzene, ether, ethanol, acetone, chloroform and petroleum ether. .
Parachlorometacresol is low toxicity efficient germicide, is mainly used in organic synthesis, can film preservative processed, as disinfectant for the field such as poultry. Can also as industrial fungicide for fields such as leather, adhesive, coating, papermaking. In sour environment, the bactericidal activity than in alkaline environment is high. Higher concentration with 0.2% is as disinfection sanitizer. Low concentration with 0.05～0.1% is as bacteriostatic preservative. The concentration of 0.1% is used as the antibacterial of water-soluble multiple dose injection, aseptic to ensure that injection continuous several times is taken out. As intravenous antibacterial, each dosage must not exceed 15ml. It also is used as the antibacterial of the injection of solution or the epidural used in sheath, in brain pond. The concentration of 0.05% is used as the antibacterial of eye drop, nasal drop. Additionally, can be additionally used in the bacteriostatic preservative of the external preparation such as emulsifiable paste, liniment, lotion.
Edit according to " fine Organic Chemicals and intermediate handbook " Xu Kexun, Chemical Industry Press, 1998 editions 3-121 pages, describe " being obtained by m-cresol and this sodium chlorate effect, technological process is: be slowly added into by metacresol in 9.5%～10% sodium chlorate solution, and controlling reaction temperature is 30～40 DEG C; add stirring 1h; placing 48h in the sunlight, then adding hydrochloric acid is neutralized to acidity, separates oil reservoir; Again with 1:1 (φ) water washing; Oil reservoir is carried out decompression distillation and obtains finished product. Except 4-chloro-m-cresol, also has by-product neighbour's chlorine m-cresol ".
Describe according to http://www.ichemistry.cn/chemistry/59-50-7.htm: reacted with dichloro sulfonyl by metacresol. Under agitation, metacresol being slowly added into dichloro sulfonyl, reaction temperature controls at 30-50 DEG C. Being incubated 16h after adding, wash with water, be washed till alkalescence with sodium carbonate liquor, reusable heat is washed to neutrality. Separating oil reservoir anhydrous calcium chloride to dry, after elimination desiccant, decompression distillation, pours into distillate in petroleum ether, and cooling is filtered, and dries to obtain finished product. Quality index appearance white crystalline melt point 64-66 DEG C, content >=99%, moisture content≤0.5%.
There is response time length (16～48h), separation difficulty, feature that neutralization washing waste water amount is big in existing technique, constrains industrialization and produce. It is thus desirable to exploitation has, the response time is short, conversion ratio is high, the sufficient technology of recycled solvent.
Therefore, it is necessary to prior art to be done further improvement.
Summary of the invention
For drawbacks described above, it is an object of the invention to provide a kind of parachlorometacresol synthesis technique, its response time is short, solvent recovering rate is high, production process clean environment firendly, and conversion ratio is high.
For reaching object defined above, the invention provides following technical scheme, a kind of parachlorometacresol synthesis technique, employing metacresol is raw material, tetrachloroethylene is solvent and chlorosulfuric acid is that chlorinating agent reacts with prepared parachlorometacresol, the mol ratio of wherein said metacresol and described tetrachloroethylene is 1:0.5-1.5, and the mol ratio of described metacresol and described chlorosulfuric acid is 1:0.9-1.1.
As one preferred embodiment of the present invention, it specifically includes following steps:
(1) enter after metacresol and tetrachloroethylene being mixed with the flow of 1mol/s:0.5-1.5mol/s in the first tubular reactor, then chlorosulfuric acid is passed into by 0.85mol/s flow and the first tubular reactor carries out first time chlorination reaction under 35 DEG C of-25 DEG C of conditions of temperature;
(2) material that step (1) is obtained by reacting is passed in the second tubular reactor and supplementary 0.1mol/s chlorosulfuric acid reacts under 25 DEG C of-15 DEG C of conditions of temperature;
(3) material that step (2) is obtained by reacting is passed in three-tube type reactor and supplementary 0.05mol/s chlorosulfuric acid reacts under 15 DEG C of-5 DEG C of conditions of temperature, obtain liquid phase material;
(4) the described liquid phase material that step (3) obtains is passed in reception tank, remove sour gas in liquid phase material by nitrogen bubble, obtain reactant liquor;
(5) the described reactant liquor that step (4) is obtained carries out purification and obtains parachlorometacresol finished product.
Mol ratio as one preferred embodiment of the present invention, described metacresol and described tetrachloroethylene is 1:0.8-1.2, and the mol ratio of described metacresol and described chlorosulfuric acid is 1:1-1.05.
As one preferred embodiment of the present invention, described metacresol, tetrachloroethylene and the chlorosulfuric acid mixed solution pressure in described first tubular reactor, the second tubular reactor and three-tube type reactor is 0-0.05Mpa.
As one preferred embodiment of the present invention, in step (4), the purity of described nitrogen is 99%, and described sour gas includes hydrogen chloride and sulfur dioxide.
As one preferred embodiment of the present invention, in step (5), described purification includes crystallization or distillation.
As one preferred embodiment of the present invention, described first tubular reactor, it is respectively arranged with thread mixing device in second tubular reactor and three-tube type reactor, described thread mixing device is the anticorrosion heat pipe of hollow, it removes reaction heat in time for being connected with coolant, described first tubular reactor, second tubular reactor and three-tube type reactor are respectively arranged with temperature detection mouth, pressure detecting mouth, chlorosulfuric acid charging aperture and sample tap, described first tubular reactor, the outer wall respectively jacketed piping of the second tubular reactor and three-tube type reactor.
As one preferred embodiment of the present invention, described first tubular reactor, the second tubular reactor and three-tube type reactor are sequentially connected in series by pipeline and distributor interface.
As one preferred embodiment of the present invention, the tubular reactor being connected with described three-tube type reactors in series is also included after step (3), before step (4), described tubular reactor is several, and these several tubular reactors are sequentially connected in series.
Beneficial effects of the present invention: compared with prior art, the present invention process response time is short, solvent recovering rate is high, production process clean environment firendly, automaticity high, and reaction terminates the conversion ratio of rear metacresol up to 98%, has good industrialization prospect.
Accompanying drawing explanation
Fig. 1 is parachlorometacresol synthesis technique of the present invention process chart in a specific embodiment;
Fig. 2 is the systematic schematic diagram of processing step in Fig. 1.
Detailed description of the invention
Below in conjunction with specific embodiment, new technology of the present invention is described in detail.
" embodiment " or " embodiment " referred to herein refers to the special characteristic, structure or the characteristic that may be included at least one implementation of the present invention. Different local in this manual " in one embodiment " occurred not refer both to same embodiment, neither be independent or selective and that other embodiments are mutually exclusive embodiment.
In the present invention, employing metacresol is raw material, tetrachloroethylene is solvent and chlorosulfuric acid is that chlorinating agent reacts with prepared parachlorometacresol, the mol ratio of wherein said metacresol and described tetrachloroethylene is 1:0.5-1.5, and the mol ratio of described metacresol and described chlorosulfuric acid is 1:0.9-1.1. The reaction equation of the present invention is as follows:
Referring to Fig. 1 and Fig. 2, Fig. 1 is parachlorometacresol synthesis technique of the present invention process chart in a specific embodiment. Fig. 2 is the systematic schematic diagram of processing step in Fig. 1.
Embodiment 1
As it is shown in figure 1, described technical process comprises the following steps:
S1: by metacresol and tetrachloroethylene with the flow of 1mol/s:0.5mol/s by after mixing in static mixer (not shown), subsequently in the first tubular reactor 101, chlorosulfuric acid is passed in band distributor interface (not shown) the first tubular reactor 101 by 0.85mol/s flow, control reaction temperature 35 DEG C-25 DEG C, carry out first time chlorination reaction (first order reaction). The tetrachloroethylene solvent that the present invention the adds reaction system that can make in course of reaction is in liquid phase state all the time, product is also had diluting effect simultaneously, can delayed response speed, improve selectivity, enable reaction more steady by the dispersion effect of solvent, reduce response speed, and then make reaction more abundant, substantially increase the conversion ratio of metacresol. This step is pressed 0.85mol/s flow and adds chlorosulfuric acid, it is possible to chlorosulfuric acid and metacresol are reacted in time under tetrachloroethylene solvent effect, to reach best reaction effect, improve the conversion ratio of metacresol.
S2: the material being obtained by reacting by step S1 passes in the second tubular reactor 102 and supplementary 0.1mol/s chlorosulfuric acid carries out secondary response under 25 DEG C of-15 DEG C of conditions of temperature.
S3: the material being obtained by reacting by step S2 passes in three-tube type reactor 103 and supplementary 0.05mol/s chlorosulfuric acid carries out third-order reaction under 15 DEG C of-5 DEG C of conditions of temperature, obtains liquid phase material.
The flow pressing 0.1mol/s and 0.05mol/s in step S2 and S3 adds chlorosulfuric acid, and then ensures that reaction in time occurs under tetrachloroethylene solvent effect for chlorosulfuric acid and unreacted metacresol, to reach best reaction effect, improves the conversion ratio of metacresol.
S4: the liquid phase material being obtained by reacting by step S3 passes in reception tank 104, removes sour gas in liquid phase material by nitrogen bubble, obtains reactant liquor. The purity of described nitrogen is 99%, described sour gas includes hydrogen chloride and sulfur dioxide, liquid phase material of the present invention passes in reception tank, hydrogen chloride and sulfur dioxide gas that reaction generates enter exhaust gas processing device (not shown), then pass into highly purified nitrogen and carry out bubbling and can effectively remove a small amount of hydrogen chloride and the sulfur dioxide gas of residual toward receiving in tank 104 again, neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment.Reactant liquor after deacidification then carries out next process and goes to purify.
S5: the reactant liquor obtained in docking closed cans 104 carries out purification and obtains parachlorometacresol finished product. In this embodiment, described purification includes but not limited to crystallization or distillation mode.
Embodiment 2
As it is shown in figure 1, described technical process comprises the following steps:
S1: by metacresol and tetrachloroethylene with the flow of 1mol/s:1mol/s by after mixing in static mixer, subsequently in the first tubular reactor 101, chlorosulfuric acid is passed in band distributor interface the first tubular reactor 101 by 0.85mol/s flow, control reaction temperature 35 DEG C-25 DEG C, carry out first time chlorination reaction (first order reaction). The tetrachloroethylene solvent that the present invention the adds reaction system that can make in course of reaction is in liquid phase state all the time, product is also had diluting effect simultaneously, can delayed response speed, improve selectivity, enable reaction more steady by the dispersion effect of solvent, reduce response speed, and then make reaction more abundant, substantially increase the conversion ratio of metacresol. This step is pressed 0.85mol/s flow and adds chlorosulfuric acid, it is possible to ensure that chlorosulfuric acid and metacresol react in time under tetrachloroethylene solvent effect, to reach best reaction effect, improve the conversion ratio of metacresol.
S2: the material being obtained by reacting by step S1 passes in the second tubular reactor 102 and supplementary 0.15mol/s chlorosulfuric acid carries out secondary response under 25 DEG C of-15 DEG C of conditions of temperature.
S3: the material being obtained by reacting by step S2 passes in three-tube type reactor 103 and supplementary 0.05mol/s chlorosulfuric acid carries out third-order reaction under 15 DEG C of-5 DEG C of conditions of temperature, obtains liquid phase material.
The flow pressing 0.15mol/s and 0.05mol/s in step S2 and S3 adds chlorosulfuric acid, and then chlorosulfuric acid and unreacted metacresol are reacted in time under tetrachloroethylene solvent effect, to reach best reaction effect, improves the conversion ratio of metacresol.
S4: the liquid phase material being obtained by reacting by step S3 passes in reception tank 104, removes sour gas in liquid phase material by nitrogen bubble, obtains reactant liquor. The purity of described nitrogen is 99%, described sour gas includes hydrogen chloride and sulfur dioxide, liquid phase material of the present invention passes in reception tank 104, hydrogen chloride and sulfur dioxide gas that reaction generates enter exhaust gas processing device, then pass into highly purified nitrogen and carry out bubbling and can effectively remove a small amount of hydrogen chloride and the sulfur dioxide gas of residual toward receiving in tank 104 again, neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment. Reactant liquor after deacidification then carries out next process and goes to purify.
S5: the reactant liquor obtained in docking closed cans 104 carries out purification and obtains parachlorometacresol finished product. In this embodiment, described purification includes but not limited to crystallization or distillation mode.
Embodiment 3
As it is shown in figure 1, described technical process comprises the following steps:
S1: by metacresol and tetrachloroethylene with the flow of 1mol/s:1.5mol/s by after mixing in static mixer, subsequently in the first tubular reactor 101, chlorosulfuric acid is passed in band distributor interface the first tubular reactor 101 by 0.85mol/s flow, control reaction temperature 35 DEG C-25 DEG C, carry out first time chlorination reaction (first order reaction). The tetrachloroethylene solvent that the present invention the adds reaction system that can make in course of reaction is in liquid phase state all the time, product is also had diluting effect simultaneously, can delayed response speed, improve selectivity, enable reaction more steady by the dispersion effect of solvent, reduce response speed, and then make reaction more abundant, substantially increase the conversion ratio of metacresol.This step is pressed 0.85mol/s flow and adds chlorosulfuric acid, it is possible to chlorosulfuric acid and metacresol are reacted in time under tetrachloroethylene solvent effect, to reach best reaction effect, improve the conversion ratio of metacresol.
S2: the material being obtained by reacting by step S1 passes in the second tubular reactor 102 and supplementary 0.15mol/s chlorosulfuric acid carries out secondary response under 25 DEG C of-15 DEG C of conditions of temperature.
S3: the material being obtained by reacting by step S2 passes in three-tube type reactor 103 and supplementary 0.1mol/s chlorosulfuric acid carries out third-order reaction under 15 DEG C of-5 DEG C of conditions of temperature, obtains liquid phase material.
The flow pressing 0.15mol/s and 0.1mol/s in step S2 and S3 adds chlorosulfuric acid, and then chlorosulfuric acid and unreacted metacresol are reacted under tetrachloroethylene solvent effect, to reach best reaction effect, improves the conversion ratio of metacresol.
S4: the liquid phase material being obtained by reacting by step S3 passes in reception tank 104, removes sour gas in liquid phase material by nitrogen bubble, obtains reactant liquor. The purity of described nitrogen is 99%, described sour gas includes hydrogen chloride and sulfur dioxide, liquid phase material of the present invention passes in reception tank, hydrogen chloride and sulfur dioxide gas that reaction generates enter exhaust gas processing device, then pass into highly purified nitrogen and carry out bubbling and can effectively remove a small amount of hydrogen chloride and the sulfur dioxide gas of residual toward receiving in tank 104 again, neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment. Reactant liquor after deacidification then carries out next process and goes to purify.
S5: the reactant liquor obtained in docking closed cans carries out purification and obtains parachlorometacresol finished product. In this embodiment, described purification includes but not limited to crystallization or distillation mode.
Embodiment 4
As it is shown in figure 1, described technical process comprises the following steps:
S1: by metacresol and tetrachloroethylene with the flow of 1mol/s:1.2mol/s by after mixing in static mixer, subsequently in the first tubular reactor 101, chlorosulfuric acid is passed in band distributor interface the first tubular reactor 101 by 0.85mol/s flow, control reaction temperature 35 DEG C-25 DEG C, carry out first time chlorination reaction (first order reaction). The tetrachloroethylene solvent that the present invention the adds reaction system that can make in course of reaction is in liquid phase state all the time, product is also had diluting effect simultaneously, can delayed response speed, improve selectivity, enable reaction more steady by the dispersion effect of solvent, reduce response speed, and then make reaction more abundant, substantially increase the conversion ratio of metacresol. This step is pressed 0.85mol/s flow and adds chlorosulfuric acid, it is possible to chlorosulfuric acid and metacresol are reacted under tetrachloroethylene solvent effect, to reach best reaction effect, improve the conversion ratio of metacresol.
S2: the material being obtained by reacting by step S1 passes in the second tubular reactor 102 and supplementary 0.15mol/s chlorosulfuric acid carries out secondary response under 25 DEG C of-15 DEG C of conditions of temperature.
S3: the material being obtained by reacting by step S2 passes in three-tube type reactor 103 and supplementary 0.1mol/s chlorosulfuric acid carries out third-order reaction under 15 DEG C of-5 DEG C of conditions of temperature, obtains liquid phase material.
The flow pressing 0.15mol/s and 0.1mol/s in step S2 and S3 adds chlorosulfuric acid, and then ensures that chlorosulfuric acid and unreacted metacresol react under tetrachloroethylene solvent effect, to reach best reaction effect, improves the conversion ratio of metacresol.
S4: the liquid phase material being obtained by reacting by step S3 passes in reception tank 104, removes sour gas in liquid phase material by nitrogen bubble, obtains reactant liquor.The purity of described nitrogen is 99%, described sour gas includes hydrogen chloride and sulfur dioxide, liquid phase material of the present invention passes in reception tank, hydrogen chloride and sulfur dioxide gas that reaction generates enter exhaust gas processing device, then pass into highly purified nitrogen and carry out bubbling and can effectively remove a small amount of hydrogen chloride and the sulfur dioxide gas of residual toward receiving in tank 104 again, neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment. Reactant liquor after deacidification then carries out next process and goes to purify.
S5: the reactant liquor obtained in docking closed cans 104 carries out purification and obtains parachlorometacresol finished product. In this embodiment, described purification includes but not limited to crystallization or distillation mode.
Embodiment 5
As it is shown in figure 1, described technical process comprises the following steps:
S1: by metacresol and tetrachloroethylene with the flow of 1mol/s:0.8mol/s by after mixing in static mixer, subsequently in the first tubular reactor 101, chlorosulfuric acid is passed in band distributor interface the first tubular reactor 101 by 0.8mol/s flow, control reaction temperature 35 DEG C-25 DEG C, carry out first time chlorination reaction (first order reaction). The tetrachloroethylene solvent that the present invention the adds reaction system that can make in course of reaction is in liquid phase state all the time, product is also had diluting effect simultaneously, can delayed response speed, improve selectivity, enable reaction more steady by the dispersion effect of solvent, reduce response speed, and then make reaction more abundant, substantially increase the conversion ratio of metacresol. This step is pressed 0.8mol/s flow and adds chlorosulfuric acid, it is possible to chlorosulfuric acid and metacresol are reacted under tetrachloroethylene solvent effect, to reach best reaction effect, improve the conversion ratio of metacresol.
S2: the material being obtained by reacting by step S1 passes in the second tubular reactor 102 and supplementary 0.15mol/s chlorosulfuric acid carries out secondary response under 25 DEG C of-15 DEG C of conditions of temperature.
S3: the material being obtained by reacting by step S2 passes in three-tube type reactor 103 and supplementary 0.05mol/s chlorosulfuric acid carries out third-order reaction under 15 DEG C of-5 DEG C of conditions of temperature, obtains liquid phase material.
The flow pressing 0.15mol/s and 0.05mol/s in step S2 and S1 adds chlorosulfuric acid, and then chlorosulfuric acid and unreacted metacresol are reacted under tetrachloroethylene solvent effect, to reach best reaction effect, improves the conversion ratio of metacresol.
S4: the liquid phase material being obtained by reacting by step S3 passes in reception tank 104, removes sour gas in liquid phase material by nitrogen bubble, obtains reactant liquor. The purity of described nitrogen is 99%, described sour gas includes hydrogen chloride and sulfur dioxide, liquid phase material of the present invention passes in reception tank, hydrogen chloride and sulfur dioxide gas that reaction generates enter exhaust gas processing device, then pass into highly purified nitrogen and carry out bubbling and can effectively remove a small amount of hydrogen chloride and the sulfur dioxide gas of residual toward receiving in tank 104 again, neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment. Reactant liquor after deacidification then carries out next process and goes to purify.
S5: the reactant liquor obtained in docking closed cans 104 carries out purification and obtains parachlorometacresol finished product. In this embodiment, described purification includes but not limited to crystallization or distillation mode.
Please continue to refer to Fig. 2. In this embodiment, tubular reactor is three (i.e. the first tubular reactor, the second tubular reactor and three-tube type reactors), described first tubular reactor the 101, second tubular reactor 102 and three-tube type reactor 103 are for being connected in series, it is capable of the serialization operating of technique, compare gap reaction, the in-line tubular reactor of the present invention has technique and is easier to control, it is easy to the advantage of operation.First tubular reactor 101 of the present invention, it is respectively arranged with thread mixing device (not shown) in second tubular reactor 102 and three-tube type reactor 103, described thread mixing device is that the heat pipe of hollow is through preservative treatment, can be connected with coolant and remove reaction heat in time, described first tubular reactor 101, second tubular reactor 102 and three-tube type reactor 103 are respectively arranged with temperature detection mouth (not shown), pressure detecting mouth (not shown), chlorosulfuric acid charging aperture (not shown) and sample tap (not shown), described first tubular reactor 101, second tubular reactor 102 and three-tube type reactor 103 outer wall respectively jacketed piping (not shown), can the temperature of assist control reactor. in other embodiments, the present invention can also adopt three and above tubular reactor is connected in series, in order to reaction sufficiently conducted.
Described metacresol, tetrachloroethylene and the chlorosulfuric acid mixed solution pressure in described first tubular reactor, the second tubular reactor and three-tube type reactor is 0-0.05Mpa, and this pressure is pressure-fired system.
The present invention is by adopting tetrachloroethylene solvent, and when first order reaction, the conversion ratio of metacresol reaches 85%, and by the conversion ratio of secondary response metacresol up to 92%, the conversion ratio through third-order reaction metacresol can reach 98%. Further, the present invention first order reaction control reaction temperature be 35 DEG C-25 DEG C, secondary response control reaction temperature be 25 DEG C-15 DEG C and third-order reaction to control reaction temperature be 15 DEG C-5 DEG C, adopt this temperature trend declined successively to be more beneficial for the carrying out of reaction.
Owing to the reaction of the present invention is favourable to selectivity under cryogenic, but the fusing point of parachlorometacresol is 66～68 DEG C of (MSDS (MaterialSafetyDataSheet, material safety technology/data description, it is called for short MSDS) data), if temperature is too low, can cause that the parachlorometacresol that reaction generates precipitates out on the reactor wall, it is unfavorable for that reaction carries out further, and the present invention makes reaction carry out under liquid phase by adding tetrachloroethylene solvent, then in course of reaction, temperature is gradually lowered, it is possible not only to significantly improve reaction yield, and the problem that the parachlorometacresol avoiding reaction generation precipitates out on the reactor wall. furthermore, the present invention is possible not only to carry out reaction serialization in the first tubular reactor, the second tubular reactor and three-tube type reactor under tetrachloroethylene solvent effect, and substantially increases production efficiency, reduces labor intensity.
Response speed is reduced owing to the present invention adds tetrachloroethylene solvent, when the liquid phase material of reaction enters the reception tank in step S4, receive the chlorosulfuric acid (chlorinating agent) still having trace in tank and do not participate in reaction completely, under the inert nitrogen gas bubbling effect that the present invention adds, not only act as deacidification effect, and Determination of Trace Sulfur acyl chlorides can be continued reaction with metacresol, improve conversion ratio. The method of this deacidification of the present invention does not pollute the environment, environmental protection, and neutralization reaction compared to existing technology can avoid secondary pollution to greatest extent, reduces the harm to environment.
The present invention is by ensureing enough consumptions of chlorosulfuric acid, it is possible to the effective conversion ratio improving parachlorometacresol, by reasonably distributing the input amount of chlorosulfuric acid in step S1 to S3, it can be ensured that reduce the generation of side reaction, and then improve economic benefit.
After present invention reaction, the content of each composition refers to following table:
| Embodiment | Metacresol | Parachlorometacresol | Adjacent chloro-m-cresol | Other |
| 1 | 1.7% | 89.34% | 6.76% | 2.2% |
| 2 | 1.45% | 91.05% | 5.82% | 1.68% |
| 3 | 0.48% | 94.54% | 4.66% | 0.32% |
| 4 | 1.36% | 93.38% | 4.82% | 0.44% |
| 5 | 1.58% | 89.95% | 6.55% | 1.92% |
In sum, the technique of the present invention, selectivity reaches 94%, by-product neighbour's chloro-m-cresol that reaction generates is few, the present invention response time is short, solvent recovering rate is high, production process clean environment firendly, automaticity high, reaction terminates the conversion ratio of rear metacresol up to 98%, has good industrialization prospect.
It should be noted that, above example is only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail with reference to preferred embodiment, it will be understood by those within the art that, technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of scope of the presently claimed invention.
Claims (3)
1. a parachlorometacresol green synthesis process, it is characterised in that:
Employing metacresol is raw material, tetrachloroethylene is solvent and chlorosulfuric acid is that chlorinating agent reacts with prepared parachlorometacresol,
It specifically includes following steps:
(1) enter after metacresol and tetrachloroethylene being mixed with the flow of 1mol/s:0.5-1.5mol/s in the first tubular reactor, then chlorosulfuric acid is passed into by 0.85mol/s flow and the first tubular reactor carries out first time chlorination reaction under 35 DEG C of-25 DEG C of conditions of temperature;
(2) material that step (1) is obtained by reacting is passed in the second tubular reactor and supplementary 0.1mol/s chlorosulfuric acid reacts under 25 DEG C of-15 DEG C of conditions of temperature;
(3) material that step (2) is obtained by reacting is passed in three-tube type reactor and supplementary 0.05mol/s chlorosulfuric acid reacts under 15 DEG C of-5 DEG C of conditions of temperature, obtain liquid phase material;
(4) the described liquid phase material that step (3) obtains is passed in reception tank, remove sour gas in liquid phase material by nitrogen bubble, obtain reactant liquor;
(5) the described reactant liquor that step (4) is obtained carries out purification and obtains parachlorometacresol finished product,
The mol ratio of described metacresol and described tetrachloroethylene is 1:0.8-1.2, and the mol ratio of described metacresol and described chlorosulfuric acid is 1:1-1.05,
Described metacresol, tetrachloroethylene and the chlorosulfuric acid mixed solution pressure in described first tubular reactor, the second tubular reactor and three-tube type reactor is 0-0.05Mpa,
It is respectively arranged with thread mixing device in described first tubular reactor, the second tubular reactor and three-tube type reactor, described thread mixing device is the anticorrosion heat pipe of hollow, it removes reaction heat in time for being connected with coolant, described first tubular reactor, the second tubular reactor and three-tube type reactor are respectively arranged with temperature detection mouth, pressure detecting mouth, chlorosulfuric acid charging aperture and sample tap, the outer wall respectively jacketed piping of described first tubular reactor, the second tubular reactor and three-tube type reactor
Described first tubular reactor, the second tubular reactor and three-tube type reactor are sequentially connected in series by pipeline and distributor interface,
Also including the tubular reactor being connected with described three-tube type reactors in series after step (3), before step (4), described tubular reactor is several, and these several tubular reactors are sequentially connected in series.
2. parachlorometacresol green synthesis process according to claim 1, it is characterised in that: in step (4), the purity of described nitrogen is 99%, and described sour gas includes hydrogen chloride and sulfur dioxide.
3. parachlorometacresol green synthesis process according to claim 1, it is characterised in that: in step (5), described purification includes crystallization or distillation.
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| CN201410302920.9A CN104045521B (en) | 2014-06-27 | 2014-06-27 | A kind of parachlorometacresol green synthesis process |
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| CN104045521B true CN104045521B (en) | 2016-06-15 |
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| CN113185561A (en) * | 2021-04-24 | 2021-07-30 | 无锡济煜山禾药业股份有限公司 | Method for obtaining 1-N-ethyl gentamicin C1a by pipeline reaction hydrolysis |
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| CN102659528A (en) * | 2012-04-01 | 2012-09-12 | 江苏焕鑫高新材料科技有限公司 | Continuous kettle type chlorination technology |
| CN103772153A (en) * | 2014-01-02 | 2014-05-07 | 湖南利洁生物化工有限公司 | Synthesis method of 4-chloro-3-cresol and system thereof |
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| CN102659528A (en) * | 2012-04-01 | 2012-09-12 | 江苏焕鑫高新材料科技有限公司 | Continuous kettle type chlorination technology |
| CN103772153A (en) * | 2014-01-02 | 2014-05-07 | 湖南利洁生物化工有限公司 | Synthesis method of 4-chloro-3-cresol and system thereof |
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