CN108689799B - Green synthesis method of chlorocyclohexane - Google Patents
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Abstract
The invention discloses a green synthesis method of chlorocyclohexane, which comprises the following steps: cyclohexane and chlorine are used as raw materials, and cyclohexane, chlorocyclohexane and polychlorinated cyclohexane are separated from chlorination products through distillation; absorbing hydrogen chloride by a falling film absorption method, and recovering the hydrogen chloride as industrial hydrochloric acid; hydrolyzing the byproduct polychlorinated cyclohexane by using alkali liquor to generate a cyclohexene substance, separating the hydrolysate to obtain 2-cyclohexenol, and carrying out catalytic hydrogenation reaction on the residual cyclohexene substance to obtain cyclohexane. The invention has fast reaction rate, adopts light as initiator and has no problem of catalyst recovery. The method has the advantages that the difficultly-treated polychlorinated cyclohexane is converted into the important chemical raw materials 2-cyclohexene alcohol and cyclohexane, so that the production cost is reduced, the cyclic utilization of resources is realized, the requirements of green environmental protection and sustainable development are met, the carcinogen dioxin generated by the incineration of the polychlorinated cyclohexane is avoided, the chemical production is cleaned, and the method has important practical significance.
Description
Technical Field
The invention relates to a synthesis method of chlorocyclohexane, in particular to a green synthesis method of chlorocyclohexane, belonging to the technical field of synthesis of anti-scorching agent CTP raw materials.
Background
In modern chemical production, the most direct method for producing chlorocyclohexane is to chlorinate cyclohexane with chlorine gas, the reaction condition is mild, the reaction speed is high, a blue light source is used as an initiator, the problem of catalyst recovery does not exist, but a plurality of byproducts are generated in the reaction process, and the product yield is reduced. The most important by-products of cyclohexane chlorination are hydrogen chloride and the different isomers of polychlorinated cyclohexane. The direct discharge of hydrogen chloride gas not only causes resource waste, but also pollutes the environment. The use of polychlorinated cyclohexane is very limited, and the polychlorinated cyclohexane is generally treated as waste, and dioxin, a carcinogenic and highly toxic substance, is generated in the combustion process, so that the treatment difficulty is further increased.
Therefore, it is an urgent matter to develop a green synthesis method of chlorocyclohexane with less side reaction, less waste discharge and simple post-treatment.
Disclosure of Invention
Aiming at the defects of the existing chlorocyclohexane synthesis method, the invention provides a green synthesis method of chlorocyclohexane, which fully recycles the byproducts generated by the reaction, realizes the cyclic utilization of resources, reduces the discharge of wastes, reduces the pollution to the environment and meets the requirements of green environmental protection and sustainable development.
The chlorine and cyclohexane chlorination reaction can generate hydrogen chloride gas and polychlorinated cyclohexane by-products, and through research, the hydrogen chloride gas is recycled as industrial hydrochloric acid, and the polychlorinated cyclohexane is hydrolyzed by alkali liquor under the conditions of high temperature and high pressure to be converted into 2-cyclohexenol, cyclohexene and cyclohexadiene with high additional values. Cyclohexene and cyclohexadiene are converted into cyclohexane for production through catalytic hydrogenation reaction. Finally, the invention converts polychlorinated cyclohexane into important chemical raw materials 2-cyclohexene alcohol and cyclohexane, and converts hydrogen chloride into industrial hydrochloric acid, and the route not only reduces the production cost and realizes the cyclic utilization of resources, but also meets the requirements of green environmental protection and sustainable development.
The specific technical scheme of the invention is as follows:
a green synthesis method of chlorocyclohexane comprises the following steps:
(1) chlorine and cyclohexane are subjected to chlorination reaction under photocatalysis, and hydrogen chloride gas generated by the reaction is absorbed by water and used as industrial hydrochloric acid;
(2) distilling the mixture obtained by the chlorination reaction to separate cyclohexane, chlorocyclohexane and polychlorinated cyclohexane, and washing the chlorocyclohexane to obtain a chlorocyclohexane finished product;
(3) hydrolyzing polychlorinated cyclohexane with alkali liquor under protective gas and high temperature environment, separating obtained hydrolysate after hydrolysis to obtain water phase and oil phase, rectifying the oil phase, collecting fractions at 80-95 ℃ and 165-180 ℃, wherein the obtained fraction at 165-180 ℃ is 2-cyclohexenol;
(4) and (3) carrying out catalytic hydrogenation reaction on the fraction with the temperature of 80-95 ℃ in the step (3) to obtain cyclohexane, and reusing the cyclohexane in the step (1).
Further, the hydrogen chloride gas is preferably recovered by a falling film absorption method. The falling film absorption is realized by adopting corresponding equipment disclosed in the prior art. Preferably, the absorption time of the hydrogen chloride gas is controlled within the range of 6-9 h.
Furthermore, the chlorination reaction is carried out in the chlorination tower, and the light source of the chlorination reaction is preferably a blue light source, namely light with the wavelength of 450-475 nm. The steps of the chlorination reaction are prior art and can be accomplished by one skilled in the art. For example, chlorine and cyclohexane are continuously fed into the chlorination tower according to a certain flow rate, and the flow rate ratio of the chlorine to the cyclohexane is preferably 1: 25-50. For example, the temperature of the chlorination reaction is 40.0 to 75.0 ℃. The products obtained by the reaction are mixtures comprising chlorocyclohexane, cyclohexane and polychlorinated cyclohexane, and can be separated through the procedures of rough steaming and fine steaming. Wherein, cyclohexane is used as a reaction raw material and is recycled; chlorocyclohexane was collected as the product after washing. The washing is carried out by using alkali liquor or sodium chloride aqueous solution, wherein the alkali liquor is an aqueous solution of an alkaline substance and can be sodium carbonate aqueous solution, sodium bicarbonate aqueous solution and the like. The concentration of the alkali liquor and the concentration of the sodium chloride aqueous solution can be selected at will, and in order to reduce the discharge of waste water, alkali liquor or sodium chloride aqueous solution with higher concentration is preferred. In washing, the chlorocyclohexane is preferably added into the alkali liquor or the sodium chloride water solution and stirred for a period of time, such as 20-45 minutes, and the washing can be carried out once or for multiple times.
Further, in the step (3), the byproduct polychlorinated cyclohexane is hydrolyzed by alkali liquor, so that chlorine atoms are removed, and a cyclohexene substance is generated. The alkaline solution is aqueous solution of alkaline substance such as sodium hydroxide, potassium hydroxide, sodium sulfide, etc., and various alkalis have equivalent hydrolysis effect on polychlorinated cyclohexane. The concentration and the dosage of the alkali liquor can be randomly selected, and the polychlorinated cyclohexane can be fully hydrolyzed and can be added in excess. Preferably, the molar ratio of the polychlorinated cyclohexane to the alkali in the alkali liquor is 1: 1.5-3.0, and preferably, the mass fraction of the alkali liquor is 10-25%, so that the hydrolysis speed can be ensured, and the generation of waste liquor can be reduced. The alkaline hydrolysis is carried out at high temperature under the protection of gas. The protective gas may be nitrogen, an inert gas, or the like. The alkaline hydrolysis temperature is 165-185 ℃. Preferably, the reaction solution is continuously stirred during the alkaline hydrolysis, and the stirring speed can be controlled within 650-850 r/min, generally within 100-150min, to complete the alkaline hydrolysis.
Further, after the alkaline hydrolysis is completed, the polychlorinated cyclohexane is converted into cyclohexene substances such as 2-cyclohexenol, cyclohexene, cyclohexadiene and the like, the substances exist in an oil phase, a water phase and the oil phase are separated by a separation method such as a centrifugal separation method, a natural sedimentation method, a coarse granulation method and the like, then the oil phase is rectified, and the cyclohexene substances are obtained by controlling the rectification temperature. Wherein, the 2-cyclohexenol has high boiling point and high added value, and the fraction of 165-180 ℃ is selected as the 2-cyclohexenol during rectification. During rectification, the product is distilled out separately and can be directly sold or used in other processes. In addition, the fractions with the temperature of 80-95 ℃ are selected, the fractions are residual cyclohexene substances such as cyclohexene and cyclohexadiene, and the substances further enter the step (4) and are converted into cyclohexane after catalytic hydrogenation treatment, so that the cyclohexane can be recycled as a raw material.
Further, in the step (4), the catalytic hydrogenation reaction is a technique which is widely reported in the prior art, and can be easily realized by those skilled in the art according to the report of the prior art, for example, the reaction temperature, the catalyst, the amount of the hydrogen, and the like can be adjusted and selected according to the prior art. In the preferred embodiment of the invention, the reaction is carried out in a high temperature and high pressure resistant reaction kettle, and the catalyst used is preferably Raney nickel.
Preferably, the temperature of catalytic hydrogenation is 110-135 ℃. Generally, the process can be completed within 100-150 min.
The invention improves the synthesis process of chlorocyclohexane, fully recovers and treats reaction products and byproducts, and avoids resource waste. Finally, chlorocyclohexane, industrial hydrochloric acid, cyclohexane and 2-cyclohexenol can be obtained through reaction, the purity and the yield of the chlorocyclohexane, the industrial hydrochloric acid, the cyclohexane and the 2-cyclohexenol are high, the chlorocyclohexane, the industrial hydrochloric acid, the cyclohexane and the 2-cyclohexenol are important chemical raw materials, and the additional value of a chlorocyclohexane synthesis process is greatly improved. The invention has the following advantages:
1. the invention uses chlorine gas to directly chlorinate cyclohexane, the reaction condition is mild, the reaction speed is high, and the problem of catalyst recovery does not exist by using a light source as an initiator.
2. The invention uses the falling film absorption method to absorb the hydrogen chloride to prepare the industrial hydrochloric acid, thereby not only avoiding the waste of resources, but also protecting the ecological environment.
3. According to the invention, polychlorinated cyclohexane which is a byproduct difficult to treat in chlorination reaction is converted into important chemical raw materials 2-cyclohexenol and cyclohexane, so that the production cost is reduced, the cyclic utilization of resources is realized, the requirements of green environmental protection and sustainable development are met, carcinogenic substance dioxin generated by incineration of polychlorinated cyclohexane is avoided, the chemical production is cleaned, and the method has important practical significance.
Detailed Description
The invention is further illustrated by the following specific examples. The following description is intended only to explain the present invention and not to limit the contents thereof. In the following examples, the purity of the produced chlorocyclohexane reaches over 99.0%, the purity of hydrochloric acid reaches over 29.0%, and the purity of cyclohexane reaches over 99.5%.
Example 1
1. Chlorine and cyclohexane are used as raw materials to carry out chlorination reaction, and the method comprises the following steps: the flow rate of cyclohexane into the chlorination tower is set to be 320m through a flowmeter3H, turning on the blue fluorescent lamp, starting to introduce chlorine, and setting the flow rate of the chlorine to be 8m through the flowmeter3H, simultaneously heating the chlorination tower to about 40 ℃. After normal reaction, the reaction liquid at the upper part of the chlorination tower overflows to an inlet at the lower half part of the crude distillation kettle tower, when the liquid overflowing from the crude distillation tower is about three fifths of the crude chlorocyclohexane storage tank, a rectification vacuum system is started, and then a vacuum valve and a discharge valve of a middle distillate tank are opened to absorb the crude chlorocyclohexane into the rectification kettle. And opening a steam valve and a steam return valve on the rectifying still, starting to heat the rectifying still, and respectively recovering cyclohexane, chlorocyclohexane and polychlorinated cyclohexane into different recovery tanks. And opening a discharging valve of the chlorocyclohexane receiving tank, and pumping the finished product into an alkaline washing tank. And simultaneously adding 10-25 wt% of sodium carbonate solution, starting a pump, circulating for 20 minutes, and stopping. Then, a chlorocyclohexane sampling valve is opened, and sampling analysis is carried out, so that the content of chlorocyclohexane is 99.5 percent, and the yield of chlorocyclohexane is 90.1 percent based on the theoretical yield of chlorocyclohexane.
2. The method is characterized in that the generated hydrogen chloride gas is subjected to falling film absorption, and the steps are as follows: and opening a primary water valve, adding 3000 liters of water into the hydrogen chloride gas absorption storage tanks of the 1 and 2 levels respectively, and adding 1500 liters of water into the vacuum box. And opening a glass condenser valve and an absorption circulating pump valve above the absorption circulation, and starting the circulating pump to start circulation. And opening a valve on a pipeline between the vacuum condenser and the absorption condenser and a valve of a vacuum circulating pump, and starting the vacuum pump to perform vacuum absorption on the hydrogen chloride gas. The absorption time was controlled at 6h, and the hydrochloric acid solution obtained was sampled and analyzed to have a hydrochloric acid content of 29.2%.
3. The polychlorinated cyclohexane of the product is processed, and the steps are as follows: the discharge valve of the polychlorinated cyclohexane storage tank is opened, 368kg of polychlorinated cyclohexane is injected into the high-pressure kettle, 1400kg of sodium hydroxide aqueous solution (the mass fraction is 10 percent) is added, and the kettle is sealed. After nitrogen is used for replacement and deoxygenation, stirring is started (the rotating speed is 650 r/min), steam is used for heating to 165 ℃, then heat preservation is carried out for 100 minutes, circulating water is started for cooling to room temperature, a valve is started for liquid separation, the water phase is separated into a brine tank for subsequent treatment, the oil phase is subjected to rectification operation, and the first fraction (80-95 ℃) and the later fraction (165-180 ℃) are respectively separated into different storage tanks. And after alkali washing, the after-fraction is directly sold as a finished product of 2-cyclohexenol. The first fraction is then fed into a high-pressure autoclave, and Raney nickel catalyst (the catalyst amount is 1% of the first fraction) is added, and after oxygen removal by nitrogen replacement, nitrogen is replaced by hydrogen. Introducing hydrogen (1.0-1.2 MPa), carrying out hydrogenation reaction at 110 ℃ for 100 minutes, cooling to room temperature after the reaction is finished, opening the kettle, discharging, and analyzing the purity to be 99.7% by HPLC.
Example 2
1. Chlorine and cyclohexane are used as raw materials to carry out chlorination reaction, and the method comprises the following steps: the flow rate of cyclohexane introduced into the chlorination tower is set to be 200m through a flowmeter3H, turning on the blue fluorescent lamp, starting to introduce chlorine, and setting the flow rate of the chlorine to be 8m through the flowmeter3H, simultaneously heating the chlorination tower to about 60 ℃. After normal reaction, the reaction liquid at the upper part of the chlorination tower overflows to an inlet at the lower half part of the crude distillation kettle tower, when the liquid overflowing from the crude distillation tower is about three fifths of the crude chlorocyclohexane storage tank, a rectification vacuum system is started, and then a vacuum valve and a discharge valve of a middle distillate tank are opened to absorb the crude chlorocyclohexane into the rectification kettle. And opening a steam valve and a steam return valve on the rectifying still, starting to heat the rectifying still, and respectively recovering cyclohexane, chlorocyclohexane and polychlorinated cyclohexane into different recovery tanks. And opening a discharging valve of the chlorocyclohexane receiving tank, and pumping the finished product into an alkaline washing tank. And simultaneously adding 10-25 wt% of sodium carbonate solution, starting a pump, circulating for 30 minutes, and stopping. Then, a chlorocyclohexane sampling valve was opened, and sampling analysis was performed, whereby the content of chlorocyclohexane was 99.4%, and the yield of chlorocyclohexane was 89.6% based on the theoretical yield of chlorocyclohexane.
2. The method is characterized in that the generated hydrogen chloride gas is subjected to falling film absorption, and the steps are as follows: and opening a primary water valve, adding 3000 liters of water into the hydrogen chloride gas absorption storage tanks of the 1 and 2 levels respectively, and adding 1500 liters of water into the vacuum box. And opening a glass condenser valve and an absorption circulating pump valve above the absorption circulation, and starting the circulating pump to start circulation. And opening a valve on a pipeline between the vacuum condenser and the absorption condenser and a valve of a vacuum circulating pump, and starting the vacuum pump to perform vacuum absorption on the hydrogen chloride gas. The absorption time was controlled to 7.5h, and the hydrochloric acid content of the obtained hydrochloric acid solution was 29.1% by sampling analysis.
3. The polychlorinated cyclohexane of the product is processed, and the steps are as follows: the discharge valve of the polychlorocyclohexane storage tank is opened, 368kg of polychlorocyclohexane is put into the autoclave, 1344kg of sodium hydroxide aqueous solution (mass fraction is 15%) is added, and the autoclave is sealed. After nitrogen is used for replacement and deoxygenation, stirring is started (the rotating speed is 800 r/min), steam is used for heating to 180 ℃, then heat preservation is carried out for 120 minutes, circulating water is started for cooling to room temperature, a valve is started for liquid separation, the water phase is separated into a brine tank for subsequent treatment, the oil phase is subjected to rectification operation, and the first fraction (80-95 ℃) and the later fraction (165-180 ℃) are respectively separated into different storage tanks. And after alkali washing, the after-fraction is directly sold as a finished product of 2-cyclohexenol. The first fraction was charged into an autoclave and Raney nickel catalyst (the amount of catalyst was 1.2% by mass of the first fraction) was added, and after oxygen removal by displacement with nitrogen, nitrogen was displaced with hydrogen. Introducing hydrogen (0.8-1.0 MPa), carrying out hydrogenation reaction at 120 ℃ for 120 minutes, cooling to room temperature after the reaction is finished, opening the kettle, discharging, and analyzing the purity to be 99.6% by HPLC.
Example 3
1. Chlorine and cyclohexane are used as raw materials to carry out chlorination reaction, and the method comprises the following steps: the flow rate of cyclohexane to the chlorination tower is set to be 400m through a flowmeter3H, turning on the blue fluorescent lamp, starting to introduce chlorine, and setting the flow rate of the chlorine to be 8m through the flowmeter3H, simultaneously heating the chlorination tower to about 75 ℃. After normal reaction, the reaction liquid at the upper part of the chlorination tower overflows to an inlet at the lower half part of the crude distillation kettle tower, when the liquid overflowing from the crude distillation tower is about three fifths of the crude chlorocyclohexane storage tank, a rectification vacuum system is started, and then a vacuum valve and a discharge valve of a middle distillate tank are opened to absorb the crude chlorocyclohexane into the rectification kettle. Opening a steam valve and a steam return valve on the rectifying still, starting to heat the rectifying still, and adding cyclohexane and chlororingThe hexane and the polychlorinated cyclohexane were separately recovered in different recovery tanks. And opening a discharging valve of the chlorocyclohexane receiving tank, and pumping the finished product into an alkaline washing tank. And simultaneously adding 10-25 wt% of sodium carbonate solution, starting a pump, circulating for 45 minutes, and stopping. Then, a chlorocyclohexane sampling valve was opened, and sampling analysis was performed, whereby the content of chlorocyclohexane was 99.5%, and the yield of chlorocyclohexane was 89.1% based on the theoretical yield of chlorocyclohexane.
2. The method is characterized in that the generated hydrogen chloride gas is subjected to falling film absorption, and the steps are as follows: and opening a primary water valve, adding 3000 liters of water into the hydrogen chloride gas absorption storage tanks of the 1 and 2 levels respectively, and adding 1500 liters of water into the vacuum box. And opening a glass condenser valve and an absorption circulating pump valve above the absorption circulation, and starting the circulating pump to start circulation. And opening a valve on a pipeline between the vacuum condenser and the absorption condenser and a valve of a vacuum circulating pump, and starting the vacuum pump to perform vacuum absorption on the hydrogen chloride gas. The absorption time was controlled to 9 hours, and the hydrochloric acid solution obtained was sampled and analyzed to have a hydrochloric acid content of 29.0%.
3. The polychlorinated cyclohexane of the product is processed, and the steps are as follows: the discharge valve of the polychlorinated cyclohexane storage tank is opened, 368kg of polychlorinated cyclohexane is injected into the high-pressure kettle, 1152kg of sodium hydroxide aqueous solution (the mass fraction is 25%) is added, and the kettle is sealed. After nitrogen is used for replacement and deoxygenation, stirring is started (the rotating speed is 850 r/min), steam is used for heating to 185 ℃, then heat preservation is carried out for 150 minutes, circulating water is started for cooling to room temperature, a valve is started for liquid separation, the water phase is separated into a brine pool for subsequent treatment, the oil phase is subjected to rectification operation, and the first fraction (80-95 ℃) and the later fraction (165-180 ℃) are respectively separated into different storage tanks. And after alkali washing, the after-fraction is directly sold as a finished product of 2-cyclohexenol. The first fraction was charged into an autoclave and Raney nickel catalyst (the amount of catalyst was 1.2% by mass of the first fraction) was added, and after oxygen removal by displacement with nitrogen, nitrogen was displaced with hydrogen. Introducing hydrogen (0.8-1.0 MPa), carrying out hydrogenation reaction at 135 ℃ for 150 minutes, cooling to room temperature after the reaction is finished, opening the kettle, discharging, and analyzing the purity to be 99.5% by HPLC.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention, such as changing the type of the alkali solution, changing the concentration of the alkali solution, changing the type and amount of the catalyst, and the like. Any modification, equivalent replacement, improvement, simulation and the like made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (1)
1. A green synthesis method of chlorocyclohexane is characterized by comprising the following steps:
(1) chlorine and cyclohexane are used as raw materials to carry out chlorination reaction, and the method comprises the following steps: the flow rate of cyclohexane into the chlorination tower is set to be 320m through a flowmeter3H, turning on the blue fluorescent lamp, starting to introduce chlorine, and setting the flow rate of the chlorine to be 8m through the flowmeter3H, simultaneously heating the chlorination tower to about 40 ℃; after normal reaction, the reaction liquid at the upper part of the chlorination tower overflows to an inlet at the lower half part of the crude distillation kettle tower, when the liquid overflowing from the crude distillation tower is about three fifths of that of a crude chlorocyclohexane storage tank, a rectification vacuum system is started, and then a vacuum valve and a discharge valve of a middle distillate tank are opened to absorb the crude chlorocyclohexane into a rectification kettle; opening a steam valve and a steam return valve on the rectifying still, starting to heat the rectifying still, and respectively recovering cyclohexane, chlorocyclohexane and polychlorinated cyclohexane into different recovery tanks; opening a discharging valve of a chlorocyclohexane receiving tank, and pumping a finished product into an alkaline washing tank; simultaneously adding 10-25 wt% of sodium carbonate solution, starting a pump, circulating for 20 minutes, and stopping; then, a chlorocyclohexane sampling valve is opened, sampling analysis is carried out, the content of chlorocyclohexane is 99.5 percent, and the yield of chlorocyclohexane is 90.1 percent based on the theoretical yield of chlorocyclohexane;
(2) the method is characterized in that the generated hydrogen chloride gas is subjected to falling film absorption, and the steps are as follows: opening a primary water valve, adding 3000 liters of water into the hydrogen chloride gas absorption storage tanks of the 1 and 2 levels respectively, and adding 1500 liters of water into the vacuum box;
opening a glass condenser valve and an absorption circulating pump valve above the absorption circulation, and starting a circulating pump to start circulation; opening a valve on a pipeline between the vacuum condenser and the absorption condenser and a valve of a vacuum circulating pump, and starting a vacuum pump to perform vacuum absorption on hydrogen chloride gas; controlling the absorption time to be 6h, and sampling and analyzing the obtained hydrochloric acid solution to obtain 29.2 percent of hydrochloric acid;
(3) the polychlorinated cyclohexane of the product is processed, and the steps are as follows: opening a discharge valve of a polychlorinated cyclohexane storage tank, feeding 368kg of polychlorinated cyclohexane into a high-pressure kettle, adding 1400kg of sodium hydroxide aqueous solution with the mass fraction of 10%, and sealing the kettle; after nitrogen is used for replacement and deoxygenation, stirring is started, the rotating speed is 650r/min, steam is used for heating to 165 ℃, then heat preservation is carried out for 100 minutes, circulating water is started for cooling to room temperature, a valve is started for liquid separation, a water phase is separated into a brine pool for subsequent treatment, the oil phase is subjected to rectification operation, a first fraction at 80-95 ℃ and a later fraction at 165-180 ℃ are respectively separated into different storage tanks, the later fraction is directly sold as a 2-cyclohexenol finished product after alkali washing, the first fraction is then injected into a high-pressure kettle, a Raney nickel catalyst is added, the catalyst dosage is 1% of the mass of the first fraction, after nitrogen replacement and deoxygenation, nitrogen is replaced by hydrogen, hydrogen is introduced at 1.0-1.2MPa, hydrogenation reaction is carried out for 100 minutes at 110 ℃, after the reaction is finished, the temperature is reduced to room temperature, the kettle is opened for discharging, and the purity is 99.7% through HPLC analysis.
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