CN113548949B - Production method of 1,1,3-trichloroacetone - Google Patents
Production method of 1,1,3-trichloroacetone Download PDFInfo
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- CN113548949B CN113548949B CN202110995307.XA CN202110995307A CN113548949B CN 113548949 B CN113548949 B CN 113548949B CN 202110995307 A CN202110995307 A CN 202110995307A CN 113548949 B CN113548949 B CN 113548949B
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Abstract
The invention discloses a method for producing 1,1,3-trichloroacetone, and belongs to the technical field of chemical product preparation. The method comprises the steps of taking acetone as a raw material, carrying out photocatalytic chlorination in an inert solvent to synthesize 1,1,3-trichloroacetone, rectifying chlorinated liquid to recover light components such as the solvent, acetone, monochloroacetone and 1,1-dichloroacetone, separating intermediate components such as 1,3-dichloroacetone and 1,1,3-trichloroacetone in a simulated moving bed filled with an adsorbent to obtain 1,1,3-trichloroacetone, eluting by using a desorption agent to obtain desorption liquid containing 1,3-dichloroacetone and 1,1,3-trichloroacetone, and distilling the desorption liquid to remove the solvent and then returning the desorption liquid to a chlorination kettle for reuse. The method has the characteristics of mild reaction conditions, high reaction rate, high selectivity of 1,1,3-trichloroacetone, less wastewater discharge, green and environment-friendly process and the like.
Description
Technical Field
The invention relates to a production method of 1,1,3-trichloroacetone, belonging to the technical field of chemical product preparation.
Background
1,1,3-trichloroacetone is a colorless transparent liquid with strong pungent smell, is mainly used as an important intermediate for synthesizing folic acid, and has wide application in the aspects of medicines, insecticides, perfumes, dyes and the like. The main methods for preparing 1,1,3-trichloroacetone at present are acetone direct chlorination method, acetone indirect chlorination method and acetone catalytic chlorination method.
For example, CN106542979A reacts acetone with 2-alkylaniline to form imine, and then the imine is chlorinated to obtain 1,1,3-trichloroacetone, the yield is 80%, but the reaction process needs a large amount of sodium hydroxide to adjust the pH value, and the salt-containing wastewater is more. CN105461529A chloridizes acetone in methanol to generate 1,3-dichloroacetone dimethyl acetal, then deprotects, and chloridizes to obtain 1,1,3-trichloroacetone with yield of 73.9%, but the process is complex. CN1047853A uses triethylamine and diethylamine to catalyze the reaction of acetone and chlorine to prepare 1,1,3-trichloroacetone, but the reaction takes 10-20 hours and the reaction rate is slow. CN101768066A discloses a method for refining 1,1,3-trichloroacetone, wherein trichloroacetone with the purity of about 50% is refined by a two-step method using two different solvents to obtain 1,1,3-trichloroacetone with high purity, but the solvent amount is large and the yield is low. CN105130780A discloses a method for refining 1,1,3-trichloroacetone by recrystallization with water and petroleum ether as solvents, but 1,1,3-trichloroacetone content is required to be more than 42%.
1,1,3-trichloroacetone is used as an important raw material for synthesizing folic acid, and the stable quality of the raw material is the guarantee of the quality of the folic acid. But the prior method mostly adopts organic amine as a catalyst for catalytic chlorination synthesis, has slower reaction speed, and the direct acetone chlorination method has long reaction time, poor selectivity of 1,1,3-trichloroacetone, difficult separation and low product purity. In the actual production, 1,1,3-trichloroacetone is extracted and purified by water and an organic solvent, more wastewater is generated in the process, and the organic solvent is used for recrystallization, so that the process is complex and the cost is high. These factors all cause the problems of high production cost of folic acid, difficult improvement of purity and the like in China.
In view of the above-mentioned drawbacks, the present invention is to provide a production method of 1,1,3-trichloroacetone, which has industrial application value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for producing 1,1,3-trichloroacetone, which has the advantages of mild reaction conditions, high reaction rate, high 1,1,3-trichloroacetone selectivity, low wastewater discharge and green and environment-friendly process.
The invention relates to a method for producing 1,1,3-trichloroacetone, which mainly comprises the following steps:
(1) Adding acetone and a solvent into a photochlorination circulation reaction kettle in proportion, and preheating the materials to a certain temperature while stirring;
(2) Turning on a light source, turning on chlorine, gradually adjusting the flow of introduced chlorine to produce a reaction solution, and simultaneously controlling the chlorination reaction temperature by adjusting the flow of cooling water;
(3) Taking part of the reaction liquid every 15min to remove the solvent trichloromethane and then taking the part of the reaction liquid as a detection liquid for detection, stopping introducing chlorine when the content of 1,1,3-trichloroacetone in the detection liquid reaches a certain concentration, continuing to react for a period of time under illumination, and then carrying out desolventizing treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorinated solution into a light component removal rectifying tower, obtaining solvents of trichloromethane, acetone and monochloroacetone at the tower top, recycling 1,1-dichloroacetone light components, introducing the tower bottom material of the light component removal rectifying tower into a high boiling removal tower, and obtaining mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone at the tower top;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone to a certain temperature, adding the mixed solution into a simulated moving bed filled with an adsorbent by using a pump, obtaining 1,1,3-trichloroacetone products, performing reverse feeding elution regeneration on the adsorbent adsorbed with 1,3-dichloroacetone in the simulated moving bed by using a desorbent, and obtaining desorption solution containing 1,3-dichloroacetone and 1,1,3-trichloroacetone;
(6) Distilling the desorption solution obtained by elution to obtain a desorption agent and mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone, returning the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained by distillation to a chlorination kettle for reuse, returning the desorption agent obtained by distillation to a simulated moving bed for reuse, and thus obtaining 1,1,3-trichloroacetone by reciprocating circulation.
Further, the solvent in the step (1) is trichloromethane, the mass ratio of the trichloromethane to the acetone is 1:1-3, and the preheating temperature is 44.5-45.0 ℃.
Further, the wavelength of the light source in the step (2) is 350-460 nm, and the chlorination reaction temperature is-10-45 ℃.
Further, after the solvent is removed in the step (3), the chlorine introduction is stopped when the 1,1,3-trichloroacetone content in the material is close to 35%, and the reaction is stopped after the light irradiation reaction is continued for 5-30 min.
Further, the preheating temperature of the mixed solution in the step (5) is 45-65 ℃, and the used desorption agent is one of methanol, ethanol and trichloromethane.
Further, the adsorbent in the step (5) is a zeolite adsorbent having a pore diameter of 0.5 to 20 angstroms.
The principle of the invention is as follows:
acetone and chlorine are used as raw materials, the raw materials are subjected to photocatalytic chlorination in trichloromethane to synthesize 1,1,3-trichloroacetone, the obtained chlorinated solution is added into a light component removal rectifying tower, trichloromethane, acetone, monochloroacetone, 1,1-dichloroacetone and other light components are separated by rectification and reused, the tower bottom of the rectifying tower is removed to a high boiling tower, 1,3-dichloroacetone and 1,1,3-trichloroacetone mixed solution is obtained at the top of the high boiling tower, the mixed solution is added into a simulated moving bed filled with an adsorbent, the 1,3-dichloroacetone is selectively adsorbed by utilizing the pore diameter and surface polarity principle of the adsorbent, and the unadsorbed 1,1,3-trichloroacetone flows out, so that a 1,1,3-trichloroacetone product is obtained. After the desorption agent is used for eluting 1,3-dichloroacetone and 1,1,3-trichloroacetone adsorbed on the pore channels and the surfaces of the adsorbent, the bed pressure is reduced to vacuum so as to evaporate and desorb the desorption agent adsorbed on the surface of the adsorbent, thereby regenerating the adsorption separation capacity of the adsorbent. The 1,3-dichloroacetone and 1,1,3-trichloroacetone mixed solution containing the desorption agent obtained by elution of the desorption agent is recovered by distillation, the obtained 1,3-dichloroacetone and 1,1,3-trichloroacetone mixed solution returns to the chlorination kettle, and the obtained desorption agent returns to the simulated moving bed for use.
By the scheme, the invention at least has the following advantages:
1. the production method of 1,1,3-trichloroacetone adopts trichloromethane as a solvent, can play a role in diluting and dispersing acetone, can reduce deep chlorination products by controlling the content of 1,1,3-trichloroacetone in a reaction solution to be lower than 35%, and further improves the selectivity of a target product 1,1,3-trichloroacetone;
2. the production method of 1,1,3-trichloroacetone adopts a photocatalysis method to replace an organic amine catalyst, avoids the separation operation of the catalyst after reaction, and can greatly improve the reaction speed and shorten the reaction time;
3. the production method of 1,1,3-trichloroacetone adopts a simulated moving bed method to separate and purify 1,1,3-trichloroacetone, avoids the use of water and has less discharge amount of process wastewater;
4. the production method of 1,1,3-trichloroacetone adopts the modified molecular sieve adsorption-desorption method to purify 1,1,3-trichloroacetone, the obtained purity is higher, and the product competitiveness is improved;
5. the intermediate produced in the process and the distilled and recovered organic solvent can be used indiscriminately, so that the discharge of three wastes is further reduced, and the process is more green and environment-friendly;
the foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate a certain embodiment of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of the process flow for producing 1,1,3-trichloroacetone according to the present invention.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
(1) Adding trichloromethane and acetone as solvent in 1:1-3 weight proportion into photochlorination circular reactor, controlling the liquid level in the reactor at 65-80%, and preheating the material to 44.5-45.0 deg.c while stirring;
(2) Starting a light source, wherein the wavelength of the light source is 350-460 nm, starting chlorine gas introducing equipment, gradually adjusting the flow of introduced chlorine gas to generate a reaction solution, and simultaneously controlling the chlorination reaction temperature to be-10-45 ℃ by adjusting the flow of cooling water;
(3) Taking the reaction liquid obtained in the step (2) as a detection liquid for detection after removing the solvent trichloromethane, stopping introducing chlorine when the content of 1,1,3-trichloroacetone in the detection liquid is close to 35%, continuing to react for 5-30 min under illumination, and then carrying out desolvation treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorination liquid obtained in the step (3) into a light component removal rectifying tower, obtaining solvents of trichloromethane, acetone and monochloroacetone at the tower top, recycling 1,1-dichloroacetone light components, introducing the tower bottom material of the light component removal rectifying tower into a high boiling removal tower, and obtaining mixed liquid of 1,3-dichloroacetone and 1,1,3-trichloroacetone at the tower top;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone in the step (4) to 45-65 ℃, adding the mixed solution into a simulated moving bed filled with an adsorbent by using a pump, adsorbing 1,3-dichloroacetone to obtain 1,1,3-trichloroacetone product, performing reverse feeding, elution and regeneration on the adsorbent which adsorbs 1,3-dichloroacetone in the simulated moving bed by using a desorption agent, and obtaining desorption solution containing 1,3-dichloroacetone and 1,1,3-trichloroacetone, wherein the desorption agent is one of methanol, ethanol and trichloromethane, and the adsorbent is zeolite with the pore diameter of 0.5-20 angstrom;
(6) Distilling the desorption solution obtained in the step (5) to obtain a desorption agent and mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone, returning the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained by distillation to a chlorination kettle for reuse, returning the desorption agent obtained by distillation to a simulated moving bed for reuse, and thus obtaining 1,1,3-trichloroacetone by reciprocating circulation.
Examples
Example 1
(1) Adding solvents trichloromethane and acetone into a 5L photochlorination circulation reaction kettle according to the mass ratio of 1.02, controlling the liquid level in the reaction kettle to be 65%, and preheating the materials to 44.8 ℃ under stirring;
(2) Starting a 457nm blue-green light source (rated power is 50W), starting chlorine gas introducing equipment, gradually adjusting the flow of introduced chlorine gas to be 0-60L/h to generate reaction liquid, and simultaneously controlling the chlorination reaction temperature to be-10 ℃ by adjusting the flow of cooling water;
(3) Taking the reaction liquid obtained in the step (2) every 15min in the reaction process as a detection liquid after removing the trichloromethane solvent, analyzing the composition of the detection liquid by adopting a gas chromatography area normalization method, stopping introducing chlorine when the 1,1,3-trichloroacetone content in a chromatogram obtained by deducting a solvent peak from the chromatogram of the detection liquid reaches 34.5%, and after continuing to react for 30min under illumination, performing desolvation treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorination liquid obtained in the step (3) into a light component removal rectifying tower with the pressure of-0.089 Mpa, wherein the size of the light component removal rectifying tower is phi 50X 3500mm, the size of a spring glass filler in the light component removal rectifying tower is phi 3X 6mm, the temperature of the tower bottom is 108.7 ℃, the light component obtained at the tower top consists of trichloromethane 62.5%, acetone 0.3%, monochloroacetone 7.9%, 1,1-dichloroacetone 21.7%, 1,1,1-trichloroacetone 7.1% and other 0.5%, the light component is returned to the chlorination kettle for reuse, and the tower kettle material is removed to a high boiling tower, wherein the size of the high boiling tower is phi 50X 4500mm, the size of the spring glass filler in the high boiling tower is phi 3X 6mm, the pressure in the high boiling tower is-0.095 Mpa, the temperature of the tower bottom is 103.5 ℃, and the mixed liquid obtained at the top of the high boiling tower is 1,3-dichloroacetone 18.7% and 1,1,3-trichloroacetone 81.3%;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained from the top of the high-boiling tower in the step (4) to 45.6 ℃, and pumping for 0.5h -1 The mass airspeed is added into a simulated moving bed filled with zeolite with a pore size of 0.5 angstrom, wherein the size of an adsorption column in the simulated moving bed is phi 2.5 multiplied by 1000mm, 6 columns are totally filled, the mass of the adsorbent is 30.2g per column, and after adsorption, 1,1,3-trichloroacetone finished products are collected at an outlet; after the adsorption is finished, the trichloromethane is added for 1.0h -1 Adding the mass space velocity reversely into a simulated moving bed, eluting the adsorbent adsorbing 1,3-dichloroacetone to obtain desorption solution containing 1,3-dichloroacetone and 1,1,3-trichloroacetone, reducing the pressure of a bed layer eluted by the desorbent to-0.090 Mpa to remove trichloromethane with low boiling point adsorbed on the surface of the adsorbent, and adding 1,3-dichloropropan obtained in the step (4) into the bed layer after desorption elution-vacuum desorption regeneration treatmentThe mixed solution of the ketone and 1,1,3-trichloroacetone is subjected to the periodic operation of adsorption, elution and vacuum desorption, and the finally obtained 1,1,3-trichloroacetone product has the purity of 98.3% and the yield of 90.2%.
(6) Distilling the desorption solution obtained in the step (5) under normal pressure, recovering part of the chloroform desorbent to return to the simulated moving bed for use, and returning the mixed solution of 3.5% of chloroform, 68.6% of 1,3-dichloroacetone and 27.9% of 1,1,3-trichloroacetone in the tower bottom of the distillation tower to the chlorination kettle for use.
Example 2
(1) Adding solvents trichloromethane and acetone into a 5L photochlorination circulation reaction kettle according to the mass ratio of 1.98, controlling the liquid level in the reaction kettle to be 70%, and preheating the materials to 44.9 ℃ under stirring;
(2) Starting a 403nm violet light source (rated power is 50W), starting chlorine gas introducing equipment, gradually adjusting the flow rate of introduced chlorine gas to be 0-80L/h to generate reaction liquid, and simultaneously controlling chlorination reaction to be 15.5 ℃ by adjusting the flow rate of cooling water;
(3) Taking the reaction liquid obtained in the step (2) every 15min in the reaction process as a detection liquid after removing the trichloromethane solvent, analyzing the composition of the detection liquid by adopting a gas chromatography area normalization method, stopping introducing chlorine when the 1,1,3-trichloroacetone content in a chromatogram obtained by deducting a solvent peak from the chromatogram of the detection liquid reaches 33.9%, and after continuing to react for 30min under illumination, performing desolvation treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorination liquid obtained in the step (3) into a light component removal rectifying tower with the pressure of-0.089 Mpa, wherein the light component removal rectifying tower is phi 50X 3500mm, the size of an internal spring glass filler is phi 3X 6mm, the bottom temperature of the tower is 108.6 ℃, the light component obtained at the top of the tower consists of 45.8% of trichloromethane, 0.5% of acetone, 11.2% of monochloroacetone, 11.54% of 1,1-dichloroacetone, 31.7% of 1,1,1-trichloroacetone and 0.5% of the others, returning the light component to the chlorination kettle for reuse, and removing high-boiling tower materials from a tower kettle, wherein the size of the high-boiling tower is phi 50X 4500mm, the size of the internal spring glass filler is phi 3X 6mm, the internal pressure of the high-boiling tower is-0.095 Mpa, the bottom temperature of the tower is 103.5 ℃, and the mixed liquid obtained at the top of the high-boiling tower consists of 1,3-dichloroacetone, 19.4% of 3425-trichloroacetone;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained from the top of the high-boiling tower in the step (4) to 54.8 ℃, and pumping for 0.5h -1 The mass airspeed is added into a simulated moving bed filled with a zeolite adsorbent with the pore diameter of 10 angstrom in a pulse mode, wherein the size of an adsorption column in the simulated moving bed is phi 2.5 multiplied by 1000mm, 6 columns are totally filled, the mass of the adsorbent is 30.2g per column, and 1,1,3-trichloroacetone finished products are collected at an outlet after adsorption; after the adsorption is finished, the trichloromethane is added for 1.0h -1 Adding the mass space velocity reversely into a simulated moving bed, eluting the adsorbent adsorbing 1,3-dichloroacetone to obtain desorption solution containing 1,3-dichloroacetone and 1,1,3-trichloroacetone, reducing the pressure of a bed layer eluted by the desorbent to-0.090 Mpa to remove trichloromethane adsorbed on the surface of the adsorbent, adding the bed layer subjected to desorption-vacuum desorption regeneration treatment to 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained in the step (4) again, and performing adsorption-elution-vacuum desorption periodic operation to obtain 1,1,3-trichloroacetone product with purity of 98.9% and yield of 91.9%.
(6) Distilling the desorption solution obtained in the step (5) under normal pressure, recovering part of the chloroform desorbent to return to the simulated moving bed for use, and returning the mixed solution of 3.4% of chloroform, 71.3% of 1,3-dichloroacetone and 25.3% of 1,1,3-trichloroacetone in the tower bottom of the distillation tower to the chlorination kettle for use.
Example 3
(1) Adding solvents trichloromethane and acetone into a 5L photochlorination circulation reaction kettle according to the mass ratio of 1.99, controlling the liquid level in the reaction kettle to be 80%, and preheating the materials to 44.7 ℃ under stirring;
(2) Starting a 354nm violet light source (rated power of 50W), starting chlorine gas introducing equipment, gradually adjusting the flow rate of introduced chlorine gas to be 0-90L/h to generate reaction liquid, and simultaneously controlling chlorination reaction to be 43.6 ℃ by adjusting the flow rate of cooling water;
(3) Taking the reaction liquid obtained in the step (2) every 15min in the reaction process as a detection liquid after removing the trichloromethane as a gas chromatography area normalization method to analyze the composition of the detection liquid, stopping introducing chlorine when the 1,1,3-trichloroacetone content in a chromatogram of the detection liquid after deducting a solvent peak reaches 33.5%, and after continuing to react for 30min under illumination, performing desolvation treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorination liquid obtained in the step (3) into a light component removal rectifying tower with the pressure of-0.089 Mpa, wherein the size of the light component removal rectifying tower is phi 50 x 3500mm, the size of an internal spring glass filler is phi 3 x 6mm, the bottom temperature of the tower is 108.7 ℃, the light component obtained at the top of the tower consists of trichloromethane 36.3%, acetone 0.6%, monochloroacetone 13.6%, 1,1-dichloroacetone 37.4%, 1,1,1-trichloroacetone 11.7% and other 0.4%, the light component returns to the chlorination kettle for reuse, and the tower kettle material is removed to a high boiling tower, wherein the size of the high boiling tower is phi 50 x 4500mm, the size of the internal spring glass filler is phi 3 x 6mm, the internal pressure of the high boiling tower is-0.095 Mpa, the bottom temperature of the tower is about 103.6 ℃, and the mixed liquid obtained at the top of the high boiling tower consists of 1,3-dichloroacetone 20.1% and 3425-trichloroacetone 9.79%;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained from the top of the high-boiling tower in the step (4) to 64.7 ℃, and pumping for 0.5h -1 The mass airspeed is added into a simulated moving bed filled with a zeolite adsorbent with the pore diameter of 20 angstrom in a pulse mode, wherein the size of an adsorption column in the simulated moving bed is phi 2.5 multiplied by 1000mm, 6 columns are used in total, the mass of the adsorbent is 30.2g in each column, and 1,1,3-trichloroacetone finished products are collected at an outlet after adsorption; after the adsorption is finished, the trichloromethane is added for 1.0h -1 And (3) adding the mass space velocity reversely into the simulated moving bed, eluting the adsorbent adsorbing 1,3-dichloroacetone to obtain desorption liquid containing 1,3-dichloroacetone and 1,1,3-trichloroacetone, reducing the pressure of a bed layer after the desorption agent is eluted to-0.091 Mpa to remove trichloromethane with low boiling point adsorbed on the surface of the adsorbent, adding the 1,3-dichloroacetone and 1,1,3-trichloroacetone mixed liquid obtained in the step (4) into the bed layer after desorption agent elution-vacuum desorption regeneration treatment again, and performing adsorption-elution-vacuum desorption periodic operation. The purity of the 1,1,3-trichloroacetone product is 98.4% and the yield is 92.3%.
(6) Distilling the desorption solution obtained by elution in the step (5) under normal pressure, recovering part of the chloroform desorbent to return to the simulated moving bed for reuse, and returning the mixed solution containing 3.6% of chloroform, 73.9% of 1,3-dichloroacetone and 22.5% of 1,1,3-trichloroacetone in the tower bottom of the distillation tower to the chlorination kettle for reuse.
Example 4
This example differs from example 2 in that the desorbent used in step 5) was ethanol, and the resulting 1,1,3-trichloroacetone had a purity of 98.9% and a yield of 87.7%. And (4) delivering the desorption solution obtained by elution in the step 5) to the step 6), distilling at-0.05 to-0.09 Mpa, recovering all the ethanol desorbent, returning the ethanol desorbent to the simulated moving bed for reuse, and returning a mixed solution containing 1,3-dichloroacetone 67.7 percent and 1,1,3-trichloroacetone 32.3 percent in a tower kettle of the distillation tower to the chlorination kettle for reuse.
Example 5
This example differs from example 2 in that the desorbent used in step 5) was methanol, and the resulting 1,1,3-trichloroacetone had a purity of 98.9% and a yield of 89.1%. And (3) delivering desorption liquid obtained by elution in the step 5) to the step 6), distilling at-0.025 to-0.09 Mpa, recovering all methanol desorbent, and returning the methanol desorbent to the simulated moving bed for use, wherein a mixed liquid of 1,3-dichloroacetone 70.2% and 1,1,3-trichloroacetone 29.8% in a tower kettle of the distillation tower is returned to the chlorination kettle for use.
Comparative example
Comparative example 1
This example differs from example 2 in that no chloroform solvent is added in step 1); stopping introducing chlorine when the content of 1,1,3-trichloroacetone in the step 3) is 34.3 percent; the other conditions were unchanged, and the purity of the obtained 1,1,3-trichloroacetone was 97.6%, and the yield was 67%.
Comparative example 2
The difference between this example and example 2 is that the chlorination catalysis in step 1) and step 2) is performed by using triethylenediamine catalyst instead of photocatalysis, and the final purity of 1,1,3-trichloroacetone is 96.6% and the yield is 60% without changing other conditions.
Comparative example 3
This example differs from example 2 in that in step 5) the adsorbent of the invention was replaced by the most common zeolite with a pore size of 0.76nm, and the conditions were otherwise unchanged, resulting in a 1,1,3-trichloroacetone purity of 93.6% and a yield of 52%.
Firstly, the purity and the yield of the final product in examples 1-3 of the invention are compared, wherein the main difference is the wavelength difference of photocatalysis, and the purity and the yield of the product in example 2 are the highest, so that the 403nm violet light source is taken as the photocatalysis light source, the production efficiency is higher, and the technical scheme of the invention can be implemented;
comparing the purity and yield of the final product in example 2 and examples 4 and 5 of the invention, wherein in examples 4 and 5, ethanol and methanol are respectively used to replace trichloromethane in example 2 as a desorption agent, the purity and yield of the final product are reduced, and therefore, the effect of trichloromethane as the desorption agent is best;
comparing the purity and yield of the final product in the embodiment 2 and the comparative example 1, wherein the chloroform solvent is not added in the comparative example 1, the purity and yield of the final product are obviously reduced, and the method can be seen from the side, the production method of 1,1,3-trichloroacetone adopts chloroform as the solvent, can play the roles of diluting and dispersing acetone, and can reduce deep chlorination products and further improve the selectivity of the target product 1,1,3-trichloroacetone by controlling the content of 1,1,3-trichloroacetone in the reaction liquid to be lower than 35%;
comparing the purity and yield of the final product in the example 2 and the comparative example 2, wherein the chlorination catalysis mode in the comparative example 2 is to use triethylene diamine catalyst to replace photocatalysis for chlorination reaction, and the purity and yield of the final product are also obviously reduced, so that the 1,1,3-trichloroacetone production method adopts a photocatalysis method to replace an organic amine catalyst, the separation operation of the catalyst after reaction is avoided, the reaction speed can be greatly improved, and the reaction time is shortened;
comparing the purity and yield of the final product in example 2 and comparative example 3, wherein the adsorbent of the present invention is replaced by the most common zeolite with a pore size of 0.76nm in comparative example 3, the yield of the final product is significantly reduced, thus it can be seen that the adsorbent zeolite of the present invention performs a special treatment on the pores, can better adsorb the target product, and can improve the yield of the product.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (3)
1. The method for producing 1,1,3-trichloroacetone is characterized by mainly comprising the following steps:
(1) Adding acetone and a solvent trichloromethane into a photochlorination circulation reaction kettle in proportion, and preheating the materials to a certain temperature while stirring;
(2) Starting a light source, turning on chlorine, gradually adjusting the flow of introduced chlorine to produce a reaction solution, and simultaneously controlling the chlorination reaction temperature by adjusting the flow of cooling water;
(3) Taking part of the reaction liquid every 15min to remove the solvent trichloromethane and then taking the part of the reaction liquid as a detection liquid for detection, stopping introducing chlorine when the content of 1,1,3-trichloroacetone in the detection liquid reaches 35%, continuing to react for 5-30 min under illumination, and then carrying out desolventizing treatment on the reaction liquid to remove the trichloromethane to obtain a chlorinated liquid;
(4) Adding the chlorinated solution into a light component removal rectifying tower, obtaining solvents of trichloromethane, acetone and monochloroacetone at the tower top, recycling 1,1-dichloroacetone light components, introducing the tower bottom material of the light component removal rectifying tower into a high boiling removal tower, and obtaining mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone at the tower top;
(5) Preheating the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone to 45-65 ℃, adding the mixed solution into a simulated moving bed filled with an adsorbent by using a pump, obtaining 1,1,3-trichloroacetone products, performing reverse feeding elution regeneration on the adsorbent adsorbed with 1,3-dichloroacetone in the simulated moving bed by using a desorption agent, and obtaining desorption solution containing 1,3-dichloroacetone and 1,1,3-trichloroacetone;
the desorption agent is one of methanol, ethanol and chloroform;
the adsorbent is zeolite adsorbent with pore diameter of 0.5-20 angstrom;
(6) Distilling the desorption solution obtained by elution to obtain a desorption agent and mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone, returning the mixed solution of 1,3-dichloroacetone and 1,1,3-trichloroacetone obtained by distillation to a chlorination kettle for reuse, returning the desorption agent obtained by distillation to a simulated moving bed for reuse, and thus obtaining 1,1,3-trichloroacetone by reciprocating circulation.
2. The method for producing 1,1,3-trichloroacetone as claimed in claim 1, wherein the solvent in step (1) is trichloromethane, the mass ratio of trichloromethane to acetone is 1:1-3, and the preheating temperature is 44.5-45.0 ℃.
3. The method for producing 1,1,3-trichloroacetone as claimed in claim 1, wherein the wavelength of the light source in step (2) is 350-460 nm and the chlorination reaction temperature is-10-45 ℃.
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