CN109970682B - Method for recovering cyclohexene oxide from cyclohexane oxidation light oil - Google Patents
Method for recovering cyclohexene oxide from cyclohexane oxidation light oil Download PDFInfo
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Abstract
The invention relates to a method for recovering cyclohexene oxide from cyclohexane oxidation light oil, which comprises the following steps: performing addition reaction on the cyclohexane oxidation light oil and carbon dioxide under the action of an addition catalyst to obtain a first reaction liquid, and then rectifying to obtain a fraction containing cyclohexene carbonate; and (3) carrying out decarboxylation reaction on the fraction containing the cyclohexene carbonate under the action of a decarboxylation catalyst to obtain a second reaction liquid, and then rectifying to obtain the cyclohexene oxide. According to the method, the carbon dioxide addition and decarboxylation cyclic reaction are combined with rectification to separate the cyclohexene oxide in the light oil, the use of halide is avoided, the product does not contain halogen, acid and alkali treatment is not needed, the carbon dioxide can be recycled, the method is green and environment-friendly, the cost is reduced, and the application range is wider.
Description
Technical Field
The invention relates to the technical field of light oil, in particular to a method for recovering cyclohexene oxide from cyclohexane oxidation light oil.
Background
Cyclohexene oxide, a Cyclohexene oxide, is a colorless or pale yellow liquid with fragrance. The cyclohexene oxide is a main raw material for synthesizing a pesticide acaricide propargite (2- (4-tert-butylphenoxy) cyclohexyl-prop-2-alkynyl sulfite) and can also be used for synthesizing a surfactant, a rubber auxiliary agent and the like. Because the molecular structure of the epoxy group has very active epoxy groups, the epoxy group can react with amine, phenol, alcohol, carboxylic acid and the like to generate a series of compounds with high added values. For example, it can be used as raw material to synthesize high-hardness, high-temp. resistant, acid-and alkali-resistant unsaturated resin, photosensitive paint and photosensitive adhesive, etc. In addition, the epoxy resin reactive diluent is an organic solvent with strong dissolving capacity and can be used as an epoxy resin reactive diluent. There are many factories for preparing cyclohexanone by oxidizing cyclohexane in China, and the light oil as a byproduct contains a large amount of cyclohexene oxide, so that the method has sufficient recycling value. However, the current recovery method usually needs to use halide, and the recovered cyclohexene oxide product also contains certain halogen, so that the application field of the product is limited.
Disclosure of Invention
Based on this, there is a need for a new method for recovering cyclohexene oxide from cyclohexane oxidation light oil without using halides.
A method for recovering cyclohexene oxide from cyclohexane oxidation light oil comprises the following steps:
performing addition reaction on the cyclohexane oxidation light oil and carbon dioxide under the action of an addition catalyst to obtain a first reaction liquid, and then rectifying the first reaction liquid to obtain a fraction containing cyclohexene carbonate;
and carrying out decarboxylation reaction on the fraction containing the cyclohexene carbonate under the action of a decarboxylation catalyst to obtain a second reaction liquid, and rectifying the second reaction liquid to obtain the cyclohexene oxide.
According to the method, carbon dioxide and cyclohexene oxide in cyclohexane oxidation light oil are subjected to addition reaction to obtain cyclohexene carbonate with a higher boiling point, then components such as n-amyl alcohol and n-hexanal with a low boiling point are removed through rectification, and fractions containing the cyclohexene carbonate are collected. Then, the fraction containing the cyclohexene carbonate is subjected to decarboxylation reaction, so that the cyclohexene carbonate is reduced into cyclohexene oxide and carbon dioxide, and then the high-purity cyclohexene oxide product can be obtained through rectification. According to the method, the carbon dioxide addition and decarboxylation cyclic reaction are combined with rectification to separate the cyclohexene oxide in the light oil, the use of halide is avoided, the product does not contain halogen, acid and alkali treatment is not needed, the carbon dioxide can be recycled, the method is green and environment-friendly, the cost is reduced, and the application range is wider.
In one embodiment, the conditions of the addition reaction are: the reaction is carried out in the atmosphere of carbon dioxide, the air pressure is 0.5MPa to 10MPa, the reaction temperature is 50 ℃ to 230 ℃, and the reaction time is 0.1 hour to 25 hours.
In one embodiment, the decarboxylation reactionThe conditions of (a) are as follows: the air pressure is-0.09 MPa-0.5 MPa, the reaction temperature is 60 ℃ to 400 ℃, and the mass space velocity is 0.1h-1～5h-1。
In one embodiment, the step of rectifying the first reaction liquid comprises: rectifying the first reaction liquid, wherein the theoretical plate number is more than 15, and collecting fraction with the boiling point of 150-260 ℃ under-0.09-0 MPa.
In one embodiment, the step of rectifying the second reaction liquid comprises: and (3) rectifying the second reaction liquid, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points between 128 and 130 ℃ under normal pressure.
In one embodiment, the addition catalyst is one or more of a quaternary ammonium salt catalyst, an alkali metal salt catalyst, and an ionic liquid catalyst.
In one embodiment, the decarboxylation catalyst is one or more of an alkali metal sulfate catalyst, an alkali metal carbonate catalyst, an alkali metal nitrate catalyst, an alkyl imidazolium salt catalyst, an ionic liquid catalyst, an alkali metal catalyst, and an alkali metal oxide catalyst.
In one embodiment, before the addition reaction, the pretreatment step of the cyclohexane oxidation light oil is further included: rectifying the cyclohexane oxidation light oil, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points of 120-137 ℃ under normal pressure.
In one embodiment, the mass ratio of the addition catalyst to the cyclohexane oxidation light oil is (0.05-5): 100.
In one embodiment, the mass ratio of the decarboxylation catalyst to the fraction containing the cyclohexene carbonate is (1-60): 100.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The method for recovering cyclohexene oxide from the cyclohexane oxidation light oil of the embodiment of the invention comprises the following steps of S1-S2:
s1, carrying out addition reaction on the cyclohexane oxidized light oil and carbon dioxide under the action of an addition catalyst to obtain a first reaction liquid, and rectifying the first reaction liquid to obtain fraction containing cyclohexene carbonate.
And S2, carrying out decarboxylation reaction on the fraction containing cyclohexene carbonate under the action of a decarboxylation catalyst to obtain a second reaction liquid, and rectifying the second reaction liquid to obtain the cyclohexene oxide.
According to the method, carbon dioxide and cyclohexene oxide in cyclohexane oxidation light oil are subjected to addition reaction to obtain cyclohexene carbonate with a higher boiling point, then components such as n-amyl alcohol and n-hexanal with a low boiling point are removed through rectification, and fractions containing the cyclohexene carbonate are collected. Then, the fraction containing the cyclohexene carbonate is subjected to decarboxylation reaction, so that the cyclohexene carbonate is reduced into cyclohexene oxide and carbon dioxide, and then the high-purity cyclohexene oxide product can be obtained through rectification. According to the method, the carbon dioxide addition and decarboxylation cyclic reaction are combined with rectification to separate the cyclohexene oxide in the light oil, the use of halide is avoided, the product does not contain halogen, acid and alkali treatment is not needed, the carbon dioxide can be recycled, the method is green and environment-friendly, the cost is reduced, and the application range is wider.
In one specific example, the conditions of the addition reaction are: the reaction is carried out in the atmosphere of carbon dioxide, the air pressure is 0.5MPa to 10MPa, the reaction temperature is 50 ℃ to 230 ℃, and the reaction time is 0.1 hour to 25 hours. Preferably, the air pressure is 1MPa to 5MPa, the reaction temperature is 100 ℃ to 180 ℃, and the addition reaction effect is better.
In one particular example, the decarboxylation reaction conditions are: the air pressure is-0.09 MPa-0.5 MPa, the reaction temperature is 60 ℃ to 400 ℃, and the mass space velocity is 0.1h-1～5h-1. Preferably, the air pressure is-0.05 MPa-0 MPa, the reaction temperature is 150-250 ℃, and the mass space velocity is 0.5h-1～2h-1The decarboxylation reaction can be carried out more preferably.
In one specific example, the step of rectifying the first reaction liquid comprises: rectifying the first reaction liquid, with the theoretical plate number being more than 15, discarding the fraction with the normal pressure boiling point between 100 ℃ and 150 ℃, and then collecting the fraction with the boiling point between 150 ℃ and 260 ℃ under-0.09 MPa to 0MPa, thereby obtaining the fraction containing 70 percent to 99.5 percent (mass percentage) of cyclohexene carbonate, which is beneficial to subsequent recovery to obtain the cyclohexene oxide product with higher purity.
In one specific example, the step of rectifying the second reaction liquid comprises: and (3) rectifying the second reaction liquid, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points between 128 and 130 ℃ under normal pressure, so that an epoxy cyclohexane product with high purity can be obtained.
In one particular example, the addition catalyst is one or more of a quaternary ammonium salt catalyst, an alkali metal salt catalyst, and an ionic liquid catalyst. Specifically, the addition catalyst is 4-dimethylaminopyridine, N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt ionic liquid, N-tetrabutylammonium halide, triethylamine, tri-N-propylamine, tri-N-butylamine, ammonium bromide, ammonium iodide, octadecyltrimethylammonium bromide, sodium bromide, potassium iodide, potassium bromide and the like. It is to be understood that the selection of the addition catalyst is not limited thereto, and may be adjusted as necessary.
In one particular example, the decarboxylation catalyst is one or more of an alkali metal sulfate catalyst, an alkali metal carbonate catalyst, an alkali metal nitrate catalyst, an alkyl imidazolium salt catalyst, an ionic liquid catalyst, an alkali metal catalyst, and an alkali metal oxide catalyst. Specifically, the decarboxylation catalyst is potassium carbonate, magnesium oxide, hexadecyl imidazole ammonium chloride and/or dodecyl pyridine ammonium bromide. It will be appreciated that the choice of decarboxylation catalyst is not limited thereto and may be adjusted as desired.
In one specific example, before the addition reaction, the pretreatment step of oxidizing light oil with cyclohexane is further included: rectifying the cyclohexane oxidized light oil, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points of 120-137 ℃ under normal pressure. Thus, most of impurities can be removed through the primary separation, and impurities such as n-amyl alcohol, n-hexanal and the like are left, so that a fraction containing 75-85% (mass percent) of cyclohexene oxide is obtained, and the subsequent recovery operation is facilitated. It will be appreciated that this step may be omitted, depending on the particular impurity content of the cyclohexane-oxidized light oil.
In a specific example, the mass ratio of the addition catalyst to the cyclohexane oxidation light oil is (0.05-5): 100, preferably (0.1-0.5): 100, and the addition reaction can be preferably performed.
In a specific example, the mass ratio of the decarboxylation catalyst to the cyclohexene carbonate-containing fraction is (1-60): 100, preferably (5-20): 100.
The following are specific examples.
Example 1
Roughly separating the cyclohexane oxidation light oil in a rectifying tower with the theoretical plate number of 30, and collecting the fraction with the boiling point of 120-137 ℃ under normal pressure to obtain a fraction containing 80% (w/w) of cyclohexene oxide. 1200g of the fraction containing 80% (w/w) of cyclohexene oxide and 2.5g of 4-Dimethylaminopyridine (DMAP) are put into a 2L high-pressure reaction kettle, carbon dioxide is used for replacing for 2-4 times, carbon dioxide is continuously filled to the pressure of 4Mpa, the reaction temperature is controlled to be 160-170 ℃, carbon dioxide is intermittently supplemented in the reaction process, the reaction is carried out for 20 hours, the conversion rate of sampling analysis reaction is 99%, the reaction selectivity is 80%, and the main impurity is cyclohexanediol. Intermittently rectifying the obtained reaction liquid, wherein the theoretical plate number of a rectifying tower is 15, light components containing n-amyl alcohol, n-hexanal and the like are obtained at the temperature of 100-150 ℃ under normal pressure, and the boiling point of the light components is collected under the negative pressure of-0.09 Mpa150-260 ℃ to obtain a fraction containing 90% (w/w) of cyclohexene carbonate. Performing decarboxylation reaction on the obtained fraction containing 90% (w/w) of cyclohexene carbonate, adopting potassium carbonate as a catalyst, wherein the mass ratio of the catalyst to the fraction containing the cyclohexene carbonate is 10:100, the reaction temperature is 240 ℃, the reaction pressure is-0.02 Mpa, and the mass space velocity is 0.5h-1The reaction conversion rate was 99.5%, the reaction selectivity was 65%, and the main impurity was cyclohexanone. Recovering the obtained carbon dioxide, intermittently rectifying the obtained reaction liquid, collecting fractions with the boiling point of 128-130 ℃ by normal pressure rectification, wherein the theoretical plate number of the rectification tower is 30, and the content of the epoxycyclohexane product is 99.9% (mass ratio).
Example 2
Roughly separating the cyclohexane oxidation light oil in a rectifying tower with the theoretical plate number of 30, and collecting the fraction with the boiling point of 120-137 ℃ under normal pressure to obtain a fraction containing 80% (w/w) of cyclohexene oxide. 1200g of the fraction containing 80% (w/w) of cyclohexene oxide and 2.5g N-butylpyridinium bis (trifluoromethanesulfonyl) imide ionic liquid catalyst are put into a 2L high-pressure reaction kettle, carbon dioxide is used for replacing for 2-4 times, carbon dioxide is continuously filled until the pressure is 5Mpa, the reaction temperature is controlled to be 140-150 ℃, carbon dioxide is intermittently supplemented in the reaction process, the reaction lasts for 22 hours, the conversion rate of sampling analysis reaction is 99%, the reaction selectivity is 90%, and the main impurity is cyclohexanediol. Intermittently rectifying the obtained reaction liquid, wherein the theoretical plate number of a rectifying tower is 15, light components containing n-amyl alcohol, n-hexanal and the like are obtained at the temperature of 100-150 ℃ under normal pressure, and components with the boiling point of 150-260 ℃ are collected under the negative pressure of-0.09 Mpa to obtain fraction containing 92% (w/w) of cyclohexene carbonate. Performing decarboxylation reaction on the obtained fraction containing 92% (w/w) of cyclohexene carbonate, wherein hexadecyl imidazole ammonium chloride is used as a catalyst, the mass ratio of the catalyst to the fraction containing the cyclohexene carbonate is 5:100, the reaction temperature is 220 ℃, the reaction pressure is-0.02 Mpa, and the mass space velocity is 1h-1The reaction conversion was 99.5%, the reaction selectivity was 92%, and the main impurity was cyclohexanone. Recovering the obtained carbon dioxide, intermittently rectifying the obtained reaction solution, collecting the reaction solution with the boiling point of the reaction solution at normal pressure, wherein the number of theoretical plates of a rectifying tower is 30, and the reaction solution is rectified at normal pressureThe epoxy cyclohexane product can be obtained by distillation at 128-130 ℃, and the content is 99.9% (mass ratio).
Example 3
The recovery process of this example is essentially the same as example 1, except that the conditions of the addition reaction are: the air pressure is 0.5MPa, the reaction temperature is 50 ℃, the reaction time is 12 hours, the sampling analysis reaction conversion rate is 94.55 percent, and the reaction selectivity is 81.3 percent. The content of the obtained epoxycyclohexane product was 99.45% (mass ratio).
Example 4
The recovery process of this example is essentially the same as example 1, except that the decarboxylation reaction conditions are: the air pressure is 1Mpa, the reaction temperature is 200 ℃, and the mass space velocity is 5h-1The reaction conversion was 76.1%, and the reaction selectivity was 79.6%. The content of the obtained epoxycyclohexane product was 99.10% (mass ratio).
Example 5
The recovery method of this example is basically the same as that of example 1, except that when the reaction solution of the addition reaction is rectified, the theoretical plate number is 12, and a fraction having a boiling point of 150 to 260 ℃ at normal pressure is collected. The epoxycyclohexane product was prepared in an amount of 99.03% (by mass).
Example 6
The recovery method in this example was substantially the same as in example 1, except that when the reaction liquid of decarboxylation was subjected to rectification, the theoretical plate number was 25, and the content of the produced epoxycyclohexane product was 99.54% (mass ratio).
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for recovering cyclohexene oxide from cyclohexane oxidation light oil is characterized by comprising the following steps:
performing addition reaction on the cyclohexane oxidation light oil and carbon dioxide under the action of an addition catalyst to obtain a first reaction liquid, and then rectifying the first reaction liquid to obtain a fraction containing cyclohexene carbonate;
and carrying out decarboxylation reaction on the fraction containing the cyclohexene carbonate under the action of a decarboxylation catalyst to obtain a second reaction liquid, and rectifying the second reaction liquid to obtain the cyclohexene oxide.
2. The method for recovering cyclohexene oxide from cyclohexane oxide light oil according to claim 1, wherein the conditions of the addition reaction are as follows: the reaction is carried out in the atmosphere of carbon dioxide, the air pressure is 0.5MPa to 10MPa, the reaction temperature is 50 ℃ to 230 ℃, and the reaction time is 0.1 hour to 25 hours.
3. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to claim 1, characterized in that the decarboxylation reaction conditions are as follows: the air pressure is-0.09 MPa-0.5 MPa, the reaction temperature is 60 ℃ to 400 ℃, and the mass space velocity is 0.1h-1～5h-1。
4. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to claim 1, wherein the step of rectifying the first reaction liquid comprises: rectifying the first reaction liquid, wherein the theoretical plate number is more than 15, and collecting fraction with the boiling point of 150-260 ℃ under-0.09-0 MPa.
5. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to claim 1, wherein the step of rectifying the second reaction liquid comprises: and (3) rectifying the second reaction liquid, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points between 128 and 130 ℃ under normal pressure.
6. The method for recovering cyclohexene oxide from cyclohexane light oil according to any of claims 1 to 5, wherein the addition catalyst is one or more of 4-dimethylaminopyridine, N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt ionic liquid, N-tetrabutylammonium halide, triethylamine, tri-N-propylamine, tri-N-butylamine, ammonium bromide, ammonium iodide, octadecyl trimethyl ammonium bromide, sodium bromide, potassium iodide and potassium bromide.
7. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to any of claims 1 to 5, characterized in that the decarboxylation catalyst is one or more of potassium carbonate, magnesium oxide, hexadecyl imidazole ammonium chloride and dodecyl pyridine ammonium bromide.
8. The method for recovering cyclohexene oxide from cyclohexane oxide light oil according to any of claims 1 to 5, characterized by further comprising a pretreatment step of the cyclohexane oxide light oil before the addition reaction: rectifying the cyclohexane oxidation light oil, wherein the number of theoretical plates is more than 30, and collecting fractions with boiling points of 120-137 ℃ under normal pressure.
9. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to any one of claims 1 to 5, characterized in that the mass ratio of the addition catalyst to the cyclohexane oxidation light oil is (0.05-5): 100.
10. The method for recovering cyclohexene oxide from cyclohexane oxidation light oil according to any of claims 1 to 5, characterized in that the mass ratio of the decarboxylation catalyst to the cyclohexene carbonate-containing fraction is (1-60): 100.
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