Method for refining epoxycyclododecadiene

Abstract

A method for refining epoxycyclododecadiene. The method comprises: performing activated carbon adsorption and solid alkali adsorption on epoxycyclododecadiene to obtain an adsorbed material; and performing a hydrogenation reaction on the adsorbed material to obtain a hydrotreated material, wherein the hydrotreated material is subjected to gas-liquid separation to obtain an epoxycyclododecadiene product having an acidity of less than 0.1 mg KOH / g and a chromaticity of less than 20 Hazen. By means of an activated carbon adsorption operation and a solid alkali adsorption operation, in combination with a hydrogenation reaction, a high-quality epoxycyclododecadiene product is obtained. The present application has a simple process flow, strong operability, and wide application prospects.

Description

Refining method of epoxy cyclododecene TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a refining method of epoxy cyclododecene. BACKGROUND

[0002] Epoxy cyclododecene is an important precursor for the production of cyclododecanone, and cyclododecanone can be used for the production of muscone, dodecanedioic acid, lauramide and other fine chemicals. Therefore, epoxy cyclododecene has a wide application in the fields of essence and perfume, high-grade lubricating oil, long carbon chain nylon, polyurethane and the like.

[0003] Epoxy cyclododecene is generally prepared from cyclododecatriene through oxidation. According to different oxidizing agents, the preparation methods of epoxy cyclododecene include chlorohydrination method, organic peroxy acid oxidation method, hydrogen peroxide method, alkyl peroxide oxidation method and air / oxygen oxidation method. At present, the preparation of epoxy cyclododecene in industry mainly includes alkyl peroxide oxidation method and organic peroxy acid oxidation method. For example, patents CN104650007A, CN106964337A and CN111704633A develop the preparation methods of epoxy cyclododecene, which are to make cyclododecatriene (CDT) as a raw material to react with tert-butyl hydroperoxide (TBHP) under the action of a molybdenum catalyst to generate epoxy cyclododecene, and tert-butyl alcohol (TBA) is generated as a byproduct. The preparation methods of epoxy cyclododecene provided in patents EP0033763B1 and EP0032990A1 are mainly to make cyclododecatriene react with peroxyformic acid, wherein the peroxyformic acid is directly formed by the reaction of formic acid and hydrogen peroxide.

[0004] No matter which preparation method is used, the generated epoxy cyclododecene product always contains various impurities. For example, patent CN117658954A mentions that when the organic peroxide tert-butyl hydroperoxide (TBHP) epoxidation method is used to produce epoxy cyclododecene, the product usually contains some acid and ester impurities, including but not limited to formic acid, acetic acid, isobutyric acid, tert-butyl formate, isobutyl formate and the like. If these impurities are not removed in time, they will accumulate in the system, which not only causes corrosion of the system, but also catalyzes the occurrence of side reactions to affect the product quality. Therefore, the product removed of acid and ester impurities is obtained after the treatment of the tert-butyl alcohol recovery tower and the impurity separation tower. Patent CN116102526A provides a post-treatment method of epoxy cyclododecene reaction liquid to solve the problem that the product produced by the TBHP method contains trace amounts of TBHP (500-5000 ppm). The method uses ferrocene-modified bisphenol A type epoxy resin porous microspheres as an adsorbent, and the microspheres can simultaneously adsorb and catalytically decompose TBHP in the reaction liquid.

[0005] In addition, the preparation of epoxy cyclododecadiene by using organic peroxy acid to oxidize cyclododecatriene is also one of the commonly used preparation methods. However, industrial practice shows that even after strict rectification and purification, the acidity of the product is >1 mgKOH / g, and the colority is >100 Hazen. Such high acidity and colority values seriously affect the subsequent reaction effect and the quality of the final product. Therefore, it is an urgent technical problem to reduce the acidity and colority of epoxy cyclododecadiene product. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application discloses a refining method for epoxy cyclododecadiene, which can effectively reduce the acidity of high-purity epoxy cyclododecadiene to less than 0.1 mgKOH / g and the colority to less than 20 Hazen, thereby improving the quality of epoxy cyclododecadiene and widening its application field.

[0007] In order to achieve the above technical purposes, on the one hand, the present application proposes a refining method for epoxy cyclododecadiene, which comprises:

[0008] The epoxy cyclododecadiene is subjected to activated carbon adsorption and solid alkali adsorption to obtain adsorbed material;

[0009] The adsorbed material is subjected to hydrogenation reaction to obtain hydrogenation treated material;

[0010] The hydrogenation treated material is subjected to gas-liquid separation to obtain epoxy cyclododecadiene product with acidity less than 0.1 mgKOH / g and colority less than 20 Hazen.

[0011] Based on a large amount of production and industrial practice, the research and development team of the present application found that the epoxy cyclododecadiene prepared by using cyclododecatriene as raw material and oxidized by organic peroxy acid has high acidity and colority. Even after rectification and purification to a purity of more than 99.5%, the acidity of the product is still greater than 1 mgKOH / g, and the colority is greater than 100 Hazen. Through exploration experiments and results of the process, the research and development team speculates that the high acidity value of high-purity epoxy cyclododecadiene may be due to the generation of some high-boiling fatty acids from epoxy cyclododecadiene under the action of organic acid, and the possible reaction formula is as follows:

[0012] The high colority value of high-purity epoxy cyclododecadiene may be mainly due to the generation of unsaturated hydrocarbons or unsaturated aldehydes by excessive oxidation, and the possible reaction formula is as follows:

[0013] It is worth noting that during the cyclododecatriene oxidation reaction, polymerization reactions occur between the reaction products to generate some oligomers, such as:

[0014] These macromolecular oligomers may still exist in the high-purity epoxy cyclododecadiene product after rectification purification and affect the acidity and colority, and the presence of these oligomers affects the subsequent reaction, so it is necessary to remove them as much as possible.

[0015] Based on the above speculation, the research and development team of the present application tried to remove macromolecular polymer impurities in the epoxy cyclododecadiene product by activated carbon adsorption, and combined with solid alkali adsorption to neutralize and adsorb acidic impurities, but the exploration results were unexpected: although the acidity value of the epoxy cyclododecadiene product was significantly reduced to a lower value, the colority was still high, and even if the conditions of activated carbon adsorption operation were optimized or the activated carbon adsorption treatment time was increased, the colority of the epoxy cyclododecadiene product remained at a certain level. Based on the experimental results of this exploration, further, the research and development team tried to increase the hydrogenation reaction process on the basis of activated carbon adsorption and solid alkali adsorption to reduce the acidity and colority of the epoxy cyclododecadiene product, which achieved unexpected excellent results: the colority of the refined epoxy cyclododecadiene was less than 20 Hazen, which was speculated to be due to the reduction of trace amounts of unsaturated impurities in the high-purity epoxy cyclododecadiene product after activated carbon adsorption operation by hydrogenation reaction, thereby the colority of the epoxy cyclododecadiene can be further reduced to a lower value; in addition, the synergistic effect of activated carbon adsorption and solid alkali adsorption makes the acidity of the epoxy cyclododecadiene less than 0.1 mgKOH / g. The examples and comparative examples of the present application show the above exploration process. Based on the above findings, the research and development team of the present application proposes the above technical scheme.

[0016] It should be noted that the present application is not limited to the order of activated carbon adsorption operation and solid alkali adsorption operation, and the order of activated carbon adsorption operation and solid alkali adsorption operation can be interchanged, such as the epoxy cyclododecadiene can be adsorbed by activated carbon to obtain a first material, the first material is adsorbed by solid alkali to obtain a second material, the second material is subjected to hydrogenation reaction to obtain a third material, and the third material is subjected to gas-liquid separation to obtain an epoxy cyclododecadiene product with an acidity of less than 0.1 mgKOH / g and a colority of less than 20 Hazen; or the epoxy cyclododecadiene can be adsorbed by solid alkali to obtain a fourth material, the fourth material is adsorbed by activated carbon to obtain a fifth material, and the fifth material is subjected to hydrogenation reaction to obtain the third material, and the third material is subjected to gas-liquid separation to obtain an epoxy cyclododecadiene product with an acidity of less than 0.1 mgKOH / g and a colority of less than 20 Hazen.

[0017] In further examples of the present application, the control conditions of the activated carbon adsorption operation are explored and optimized. Optionally, the activated carbon adsorption operation is carried out in a first adsorption tower filled with activated carbon, and the operating temperature of the first adsorption tower is 30-100℃, and the pressure is 0-0.2Mpa. The conditions of the activated carbon adsorption operation of the present application are mild, energy consumption is saved, and operability is strong. Optionally, the feed space velocity of the epoxide cyclododecene relative to the activated carbon is 0.5-1.5h -1 , so as to obtain better adsorption effect.

[0018] It should be noted that the present application is not limited to the specific structure of the first adsorption tower, which can be a fixed bed adsorption tower or a moving bed adsorption tower, etc. Those skilled in the art can select a suitable adsorption tower based on the technical scheme of the present application and according to the actual working conditions, and the technical scheme formed thereby is within the protection scope of the present application.

[0019] In further examples of the present application, the specific surface area of the activated carbon is 900-1200m 2 / g, which can optimize the adsorption effect and facilitate the industrial application of the present application; and optionally, the bulk density of the activated carbon is 0.3-0.6g / ml, thereby improving the mass transfer effect and increasing the production efficiency.

[0020] In further examples of the present application, the type of solid base used in the solid base adsorption is explored and optimized, which can be a weak base adsorbent, and further can be one or more of calcium oxide, magnesium oxide, calcium hydroxide, sodium carbonate, sodium bicarbonate or basic ion exchange resin. By using a weak base catalyst, the present application ensures the stability and high yield of the process.

[0021] In further examples of the present application, the control conditions of the solid base adsorption operation are explored and optimized. Optionally, the solid base adsorption operation is carried out in a second adsorption tower filled with solid base, and the operating temperature of the second adsorption tower is 30-80℃, and the pressure is 0-0.1Mpa. The relatively mild operating conditions of the present application can obtain better deacidification effect, which is suitable for industrial application. Optionally, in the solid base adsorption operation, the feed space velocity of the material input into the second adsorption tower relative to the solid base is 0.5-1h -1 , the adjustment of the first material feed space velocity optimizes the deacidification effect.

[0022] The kind of catalyst for the hydrogenation reaction is not limited in the present application, and in further examples of the present application, the kind of catalyst for the hydrogenation reaction is explored and optimized. Optionally, the catalyst for the hydrogenation reaction is a supported catalyst, and the active component of the supported catalyst is one of Pd, Ru and Pb. In the process of the present application, the use of a noble metal catalyst for the hydrogenation of trace amounts of unsaturated impurities has better effect, and can significantly reduce the colority of the product of epoxy cyclododecadiene. Optionally, the loading amount of the active component is 0.1-3wt%, and a better hydrogenation effect of the catalyst can be obtained.

[0023] It should be noted that the specific preparation process of the catalyst used in the present application can be selected: the nitrate or chloride salt of the noble metal is first loaded onto the carrier, and then dried and calcined to form the catalyst product, at this time the noble metal exists in the form of oxidation state; the catalyst product is loaded into the reactor, and before use, hydrogen is used for pre-reduction operation to reduce the oxidation state to the metal state.

[0024] In further examples of the present application, the carrier of the supported catalyst is one or more of active alumina, silica, titanium oxide and zirconium oxide, and the catalyst carrier is selected in various ways, which embodies the flexibility and applicability of the process of the present application.

[0025] In further examples of the present application, the specific surface area of the carrier is 200-400m 2 / g. Optionally, the pore volume of the carrier is 0.3-0.8ml / g. Optionally, the bulk density of the carrier is 0.5-1g / ml. The exploration and optimization of the related parameters of the catalyst carrier improve the activity and selectivity of the supported catalyst, and enhance the catalytic effect of the hydrogenation catalyst.

[0026] It should be noted that the specific equipment for the hydrogenation reaction is not limited in the present application, and can be a fixed bed reactor, and further can be a fixed bed reactor with tubes. Those skilled in the art can select appropriate hydrogenation reaction equipment and facilities based on the technical scheme of the present application and according to the actual working conditions, and the technical scheme formed thereby is within the protection scope of the present application.

[0027] In further examples of the present application, the control conditions of the hydrogenation reaction are explored and optimized. Optionally, the molar ratio of hydrogen to the adsorbed material in the hydrogenation reaction is (1-4):1. Optionally, the temperature of the hydrogenation reaction is 40-100℃, and the reaction pressure is 0-0.5Mpa. The operating conditions are relatively mild, and the operability is better. Optionally, the feed space velocity of the adsorbed material relative to the catalyst for the hydrogenation reaction is 0.5-1h -1 The control of the hydrogenation reaction material feed facilitates the adjustment and control to improve the hydrogenation reaction effect.

[0028] In addition, it is worth noting that, considering the interference of impurities such as acid and oligomer in the refined epoxy cyclododecadiene product on the catalytic activity of the hydrogenation catalyst, and in order to improve the industrial operability and save process cost, the research and development team optimizes the hydrogenation reaction after completing the activated carbon adsorption and solid alkali adsorption.

[0029] Compared with the prior art, the beneficial effects of the present application are: the present application obtains high-quality epoxy cyclododecadiene product through activated carbon adsorption operation, solid alkali adsorption operation and hydrogenation reaction, the product has an acidity of less than 0.1 mgKOH / g and a colority of less than 20 Hazen, and has wide application value. The process flow of the method of the present application is simple and has strong operability, and is suitable for industrial popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0030] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the present application, and the illustrative embodiments of the present application and their description serve the purpose of explaining the present application. The present application is not limited by the accompanying drawings.

[0031] Figure 1 shows a comparison chart of the refined epoxy cyclododecadiene product obtained after refining the epoxy cyclododecadiene to be refined in Example 1 of the present application. DETAILED DESCRIPTION

[0032] In order to facilitate the understanding of the present application, the present application will be described more fully below, and the preferred embodiments of the present application are given. However, it should be understood that these embodiments are only used for more detailed description, and should not be understood as limiting the present application in any form, i.e. not intended to limit the protection scope of the present application.

[0033] Unless otherwise defined, the technical terms used in the following examples have the same meaning as generally understood by those skilled in the art to which the present application belongs. The test reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the experimental methods, unless otherwise specified, are conventional methods.

[0034] It should be noted that in the description of the preferred embodiments, unless otherwise explicitly specified and limited, the terms "first", "second", "third", "fourth", "fifth" and the like are only used for description purposes, and the above terms in the present application can be understood by those skilled in the art according to the specific circumstances, therefore it should not be understood as limiting the present application.

[0035] It should be noted that the method for measuring the acidity in the embodiments of the present application refers to GB / T264-83; the method for measuring the colority is that: a proper amount of sample solution is subjected to colority measurement at a wavelength of 390 nm by using a spectrophotometer, and is compared with a platinum-cobalt standard solution to calculate the colority of the sample; wherein the Hazen units are: the colority of a platinum-cobalt solution containing 1 mg of platinum in the form of potassium chloroplatinate (H2PtCl6) and 2 mg of cobalt chloride hexahydrate (CoCl2·6H2O) per liter.

[0036] Example 1

[0037] A refining method of epoxy cyclododecene, specifically, 100 kg / h of epoxy cyclododecene raw material is subjected to post-treatment, the epoxy cyclododecene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, the purity is >99.5%, the acidity is 1.54 mgKOH / g, and the colority is 167.69 Hazen:

[0038] The epoxy cyclododecene raw material to be refined is input into a first adsorption tower for activated carbon adsorption, the first adsorption tower is a fixed bed adsorption tower, the activated carbon loading amount in the tower is 100 kg, the bulk density is 0.35 g / ml, the specific surface area is 900 m 2 / g, the tower operating temperature is 30 ℃, the pressure is 0.1 Mpa, and the bed pressure drop is 40 kpa; a first material is obtained from the bottom of the first adsorption tower. The first material is input into a second adsorption tower, the second adsorption tower is filled with 100 kg of shaped calcium hydroxide pellets, the tower operating temperature is 50 ℃, the pressure is 0.1 Mpa, and the bed pressure drop is 10 kpa; a second material is obtained from the bottom of the second adsorption tower. The second material and hydrogen are input into a hydrogenation refining tower, the refining tower is filled with 100 kg of catalyst, the catalyst is activated alumina loaded with noble metal Pb, the loading amount of Pb is 1.5%, the specific surface area of the carrier alumina is 350 m 2 / g, the pore volume is 0.78 ml / g, and the bulk density is 0.85 g / ml; the reaction temperature of the refining tower is 50 ℃, the pressure is 0.3 Mpa, and the molar ratio of hydrogen to the second material is 1.1; a third material flows out from the bottom of the refining tower, is subjected to gas-liquid separation after being input into a gas-liquid separator, unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecene product is collected from the bottom of the gas-liquid separator.

[0039] The yield of the present embodiment is 99.93%, the acidity of the obtained epoxy cyclododecene product is 0.06 mgKOH / g, and the colority is 13.57 Hazen; FIG. 1 shows the colority comparison of the epoxy cyclododecene to be refined and the refined epoxy cyclododecene product in the present embodiment.

[0040] Example 2

[0041] A method for refining epoxy cyclododecadiene, specifically, involves post-processing a 100 kg / h epoxy cyclododecadiene raw material. This raw material is prepared by an oxidation reaction of cyclododecanetriene and peroxyformic acid, with a purity >99.5%, an acidity of 1.54 mg KOH / g, and a color of 167.69 Hazen.

[0042] The refined epoxy cyclododecadiene feedstock is fed into the first adsorption tower, which contains 70 kg of activated carbon with a bulk density of 0.35 g / ml and a specific surface area of ​​900 m² / g. The tower operates at 100°C, 0.01 MPa, and a bed pressure drop of 30 kPa. The first material is obtained from the bottom of the first adsorption tower. This first material then enters the second adsorption tower, which contains 200 kg of shaped calcium oxide spheres. The tower operates at 80°C, 0.01 MPa, and a bed pressure drop of 25 kPa. The second material is obtained from the bottom of the second adsorption tower. This second material and hydrogen then enter the hydrogenation refining tower, which contains 100 kg of catalyst. The catalyst is activated alumina supported on precious metal Pd, with a Pd loading of 1%. The specific surface area of ​​the alumina support is 350 m² / g. 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 40℃, the pressure is 0.01MPa, and the molar ratio of hydrogen to the second material is 1.1. The third material flows out from the bottom outlet of the refining tower and enters the gas-liquid separator for gas-liquid separation. Unreacted hydrogen is discharged from the top of the separator and can be recycled. The refined epoxy cyclododecadiene product is collected from the bottom of the gas-liquid separator.

[0043] The yield of this embodiment is 99.93%, and the acidity of the obtained epoxy cyclododecadiene product is 0.09 mg KOH / g, and the color is 12.17 Hazen.

[0044] Example 3

[0045] A method for refining epoxy cyclododecadiene, specifically, involves post-processing a 100 kg / h epoxy cyclododecadiene raw material. This raw material is prepared by an oxidation reaction of cyclododecanetriene and peroxyformic acid, with a purity >99.5%, an acidity of 1.99 mg KOH / g, and a color of 145.06 Hazen.

[0046] The purified epoxy cyclododecadiene feedstock is fed into the first adsorption tower, which contains 200 kg of activated carbon with a bulk density of 0.6 g / ml and a specific surface area of ​​1200 m². 2 / g, the bed pressure drop is 80 kPa; the first material is obtained from the bottom of the first adsorption tower. The first material is input into the second adsorption tower, which is filled with 200 kg of shaped magnesium oxide pellets, the tower operating temperature is 30°C, the pressure is 0.05 MPa, and the bed pressure drop is 30 kPa; the second material is obtained from the bottom of the second adsorption tower.

[0047] The second material and hydrogen are input into a hydrogenation refining tower, which is filled with 100 kg of catalyst, which is active alumina supported noble metal Pd, wherein the loading amount of Pd is 0.3%, the specific surface area of the support alumina is 400 m 2 / g, the pore volume is 0.56 ml / g, and the bulk density is 0.62 g / ml; the reaction temperature of the hydrogenation refining tower is 100°C, the pressure is 0.5 MPa, and the molar ratio of hydrogen to the second material is 4. The third material flows out from the bottom of the refining tower, is input into a gas-liquid separator for gas-liquid separation, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is collected from the bottom of the gas-liquid separator.

[0048] The yield of the present embodiment is 99.97%, and the acidity of the obtained epoxy cyclododecadiene product is 0.09 mgKOH / g, and the colority is 12.73 Hazen.

[0049] Example 4

[0050] A refining method of epoxy cyclododecadiene, specifically, 100 kg / h of epoxy cyclododecadiene raw material is post-treated, the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, the purity is >99.5%, the acidity is 1.99 mgKOH / g, and the colority is 145.06 Hazen:

[0051] The epoxy cyclododecadiene raw material to be refined is input into the second adsorption tower, which is filled with 200 kg of shaped magnesium oxide pellets, the tower operating temperature is 30°C, the pressure is 0.05 MPa, and the bed pressure drop is 30 kPa; the fourth material is obtained from the bottom of the second adsorption tower. The fourth material is input into the first adsorption tower, which is filled with 200 kg of active carbon, the bulk density is 0.6 g / ml, and the specific surface area is 1200 m 2 / g, the bed pressure drop is 80 kPa; the fifth material is obtained from the bottom of the first adsorption tower. The fifth material and hydrogen are input into a hydrogenation refining tower, which is filled with 100 kg of refining catalyst, which is active alumina supported noble metal Pd, wherein the loading amount of Pd is 0.3%, the specific surface area of the support alumina is 400 m 2 / g, the bulk density is 0.62 g / ml; the reaction temperature of the refining column is 100°C, the pressure is 0.5 MPa, and the molar ratio of hydrogen to the fifth material is 4. The third material flows out from the bottom of the refining column, enters a gas-liquid separator for gas-liquid separation, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is collected from the bottom of the gas-liquid separator.

[0052] The yield of this example is 99.97%, the acidity of the obtained epoxy cyclododecadiene product is 0.085 mgKOH / g, and the colority is 13.56 Hazen.

[0053] Example 5

[0054] A refining method of epoxy cyclododecadiene, in particular, for the post-treatment of 100 kg / h of epoxy cyclododecadiene raw material prepared by the oxidation reaction of cyclododecatriene with peroxyformic acid, the purity of which is >99.5%, the acidity is 1.12 mgKOH / g, and the colority is 145.92 Hazen:

[0055] The epoxy cyclododecadiene raw material to be refined is input into a first adsorption column, the activated carbon in the first adsorption column is filled in an amount of 150 kg, the bulk density is 0.55 g / ml, and the specific surface area is 1140 m 2 / g. The operation temperature of the column is 100°C, the pressure is 0.05 MPa, and the bed pressure drop is 50 kPa. The first material is obtained from the bottom of the first adsorption column. The first material enters a second adsorption column, the second adsorption column is filled with 200 kg of shaped magnesium oxide pellets, the operation temperature of the column is 80°C, the pressure is 0.01 MPa, and the bed pressure drop is 30 kPa. The second material is obtained from the bottom of the second adsorption column. The second material and hydrogen enter a hydrogenation refining column, the column is filled with 200 kg of refining catalyst, the catalyst is activated alumina loaded with noble metal Ru, the loading amount of Ru is 0.1%, the specific surface area of the carrier alumina is 220 m 2 / g, the pore volume is 0.38 ml / g, and the bulk density is 0.53 g / ml. The reaction temperature of the hydrogenation refining column is 100°C, the pressure is 0.3 MPa, and the molar ratio of hydrogen to the second material is 3.4. The third material flows out from the bottom of the refining column, enters a gas-liquid separator for gas-liquid separation, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is collected from the bottom of the gas-liquid separator.

[0056] The yield of this example is 99.98%, the acidity of the obtained epoxy cyclododecadiene product is 0.089 mgKOH / g, and the colority is 11.59 Hazen.

[0057] Comparative Example 1

[0058] The 100 kg / h epoxy cyclododecadiene raw material, which was prepared by the oxidation reaction of cyclododecatriene with peroxyformic acid, had a purity of >99.5%, an acidity of 1.54 mgKOH / g, and a colority of 167.69 Hazen, was subjected to post-treatment refining:

[0059] The epoxy cyclododecadiene raw material to be refined was first subjected to activated carbon adsorption in an activated carbon fixed bed adsorption tower, which had an activated carbon loading of 100 kg, a bulk density of 0.35 g / ml, and a specific surface area of 900 m 2 / g. The tower was operated at a temperature of 30°C and a pressure of 0.1 Mpa, and had a bed pressure drop of 40 kpa. A first material was obtained from the bottom of the activated carbon fixed bed adsorption tower. The first material was introduced into a base tower filled with 100 kg of shaped calcium hydroxide pellets, which was operated at a temperature of 50°C and a pressure of 0.1 Mpa, and had a bed pressure drop of 10 kpa. A refined epoxy cyclododecadiene product was obtained from the bottom of the base tower.

[0060] The product yield of this comparative example was 99.93%, and the refined epoxy cyclododecadiene product had an acidity of 0.06 mgKOH / g and a colority of 148.71 Hazen.

[0061] Comparative Example 2

[0062] The 100 kg / h epoxy cyclododecadiene raw material, which was prepared by the oxidation reaction of cyclododecatriene with peroxyformic acid, had a purity of >99.5%, an acidity of 1.54 mgKOH / g, and a colority of 167.69 Hazen, was subjected to post-treatment refining:

[0063] The epoxy cyclododecadiene raw material to be refined was first subjected to activated carbon adsorption in an activated carbon fixed bed adsorption tower, which had an activated carbon loading of 200 kg, a bulk density of 0.35 g / ml, and a specific surface area of 900 m 2 / g. The tower was operated at a temperature of 30°C and a pressure of 0.1 Mpa, and had a bed pressure drop of 70 kpa. A first material was obtained from the bottom of the activated carbon fixed bed adsorption tower. The first material was introduced into a base tower filled with 100 kg of shaped calcium hydroxide pellets, which was operated at a temperature of 50°C and a pressure of 0.1 Mpa, and had a bed pressure drop of 10 kpa. A refined epoxy cyclododecadiene product was obtained from the bottom of the base tower.

[0064] The product yield of this comparative example was 99.93%, and the refined epoxy cyclododecadiene product had an acidity of 0.06 mgKOH / g and a colority of 148.71 Hazen.

[0065] Comparative Example 3

[0066] A 100 kg / h epoxy cyclododecadiene feedstock was post-processed and refined. This epoxy cyclododecadiene feedstock was prepared by the oxidation reaction of cyclododecanetriene and peroxyformic acid, with a purity >99.5%, an acidity of 1.54 mg KOH / g, and a color of 167.69 Hazen.

[0067] The epoxy cyclododecadiene feedstock to be refined first enters the alkali tower, which is packed with 100 kg of molded calcium hydroxide pellets. The tower operates at a temperature of 50°C, a pressure of 0.1 MPa, and a bed pressure drop of 10 kPa. The material obtained from the bottom of this tower, along with a certain amount of hydrogen, enters the hydrogenation refining tower, which is packed with 100 kg of refining catalyst. This catalyst is activated alumina supported on the noble metal Pb, with a Pb loading of 1.5%. The specific surface area of ​​the alumina support is 350 μm. 2 The pore volume is 0.78 ml / g, and the bulk density is 0.85 g / ml. The reaction temperature of the hydrogenation refining tower is 50℃, the pressure is 0.3 MPa, and the molar ratio of hydrogen to epoxide dodecadiene in the feed is 1.1. After the material from the bottom of the hydrogenation refining tower enters the gas-liquid separator, the unreacted hydrogen is discharged from the top of the separator for recycling, and the refined epoxide dodecadiene product is discharged from the bottom of the gas-liquid separator.

[0068] The product yield of this comparative example was 99.93%, with an acidity of 0.55 mg KOH / g and a color of 13.57 Hazen.

[0069] Comparative Example 4

[0070] A 100 kg / h epoxy cyclododecadiene feedstock was post-processed and refined. This epoxy cyclododecadiene feedstock was prepared by the oxidation reaction of cyclododecanetriene and peroxyformic acid, with a purity >99.5%, an acidity of 1.54 mg KOH / g, and a color of 167.69 Hazen.

[0071] The epoxy cyclododecadiene raw material to be refined is first adsorbed in an activated carbon fixed-bed adsorption tower. The tower contains 100 kg of activated carbon with a bulk density of 0.35 g / ml and a specific surface area of ​​900 m². 2 The activated carbon fixed-bed adsorption tower operates at a temperature of 130℃, a pressure of 0.1 MPa, and a bed pressure drop of 40 kPa. The bottom product of the activated carbon fixed-bed adsorption tower enters an alkali tower filled with 100 kg of shaped calcium hydroxide pellets. The alkali tower operates at a temperature of 50℃, a pressure of 0.1 MPa, and a bed pressure drop of 10 kPa. The bottom product of the alkali tower, along with a certain amount of hydrogen, enters a hydrogenation refining tower. The hydrogenation refining tower is filled with 100 kg of refining catalyst, which is activated alumina supported on precious metal Pb, with a Pb loading of 1.5%. The specific surface area of ​​the alumina support is 350 μm. 2 / g, the bulk density is 0.85 g / ml; the reaction temperature of the hydrogenation refining tower is 50°C, the pressure is 0.3 MPa, and the molar ratio of hydrogen to the epoxy cyclododecene in the feed is 1.1; the unreacted hydrogen is discharged from the top of the gas-liquid separator after the material taken out from the tower kettle of the hydrogenation refining tower enters the gas-liquid separator, and can be recycled; and the refined epoxy cyclododecene product is taken out from the bottom of the gas-liquid separator.

[0072] The product yield of the present comparative example is 99.8%, the acidity is 0.14 mgKOH / g, and the colority is 25.1 Hazen.

[0073] Comparative Example 5

[0074] The 100 kg / h epoxy cyclododecene raw material is refined by post-treatment, the epoxy cyclododecene raw material is prepared by oxidation reaction of cyclododecatriene with peroxyformic acid, the purity is >99.5%, the acidity is 1.54 mgKOH / g, and the colority is 167.69 Hazen:

[0075] The epoxy cyclododecene raw material to be refined is first subjected to adsorption by the activated carbon fixed bed adsorption tower, the activated carbon loading amount in the tower is 100 kg, the bulk density is 0.35 g / ml, and the specific surface area is 900 m 2 / g; the tower operating temperature is 30°C, the pressure is 0.1 MPa, and the bed pressure drop is 40 kPa; the material taken out from the tower kettle of the activated carbon fixed bed adsorption tower enters the alkali tower filled with 100 kg of shaped calcium hydroxide pellets, the alkali tower operating temperature is 130°C, the pressure is 0.1 MPa, and the bed pressure drop is 10 kPa; the material taken out from the tower kettle of the alkali tower and a certain amount of hydrogen enter the hydrogenation refining tower, the hydrogenation refining tower is filled with 100 kg of the refining catalyst, the catalyst is active alumina loaded with noble metal Pb, and the loading amount of Pb is 1.5%; the specific surface area of the carrier alumina is 350 m 2 / g, the pore volume is 0.78 ml / g, and the bulk density is 0.85 g / ml; the reaction temperature of the hydrogenation refining tower is 50°C, the pressure is 0.3 MPa, and the molar ratio of hydrogen to the epoxy cyclododecene in the feed is 1.1; the unreacted hydrogen is discharged from the top of the gas-liquid separator after the material taken out from the tower kettle of the hydrogenation refining tower enters the gas-liquid separator, and can be recycled; and the refined epoxy cyclododecene product is taken out from the bottom of the gas-liquid separator.

[0076] The product yield of the present comparative example is 99.8%, the acidity is 0.48 mgKOH / g, and the colority is 18.6 Hazen.

[0077] Comparative Example 5

[0078] The 100 kg / h epoxycyclododecene raw material, which was prepared by oxidizing cyclododecatriene with peroxyformic acid, was refined by post-treatment. The purity of the epoxycyclododecene raw material was >99.5%, the acidity was 1.54 mgKOH / g, and the colority was 167.69 Hazen:

[0079] The epoxycyclododecene raw material to be refined was first subjected to adsorption in an activated carbon fixed bed adsorption tower. The activated carbon was loaded in the tower at a loading amount of 100 kg, a bulk density of 0.35 g / ml, and a specific surface area of 900 m 2 / g. The tower was operated at a temperature of 130°C and a pressure of 0.1 Mpa, and the bed pressure drop was 40 kpa. The material taken out from the tower kettle was introduced into an alkali tower loaded with 100 kg of shaped calcium hydroxide pellets. The alkali tower was operated at a temperature of 130°C and a pressure of 0.1 Mpa, and the bed pressure drop was 10 kpa. The material taken out from the alkali tower kettle and a certain amount of hydrogen were introduced into a hydrogenation refining tower loaded with 100 kg of a refining catalyst. The catalyst was active alumina loaded with noble metal Pb, and the loading amount of Pb was 1.5%. The specific surface area of the carrier alumina was 350 m 2 / g, the pore volume was 0.78 ml / g, and the bulk density was 0.85 g / ml. The reaction temperature of the hydrogenation refining tower was 50°C, the pressure was 0.3 Mpa, and the molar ratio of hydrogen to epoxycyclododecene in the feed was 1.1. The material taken out from the hydrogenation refining tower kettle was introduced into a gas-liquid separator. The unreacted hydrogen was discharged from the top of the separator and could be recycled. The refined epoxycyclododecene product was taken out from the bottom of the gas-liquid separator.

[0080] The product yield of the present comparative example was 99.8%, the acidity was 0.68 mgKOH / g, and the colority was 25.6 Hazen.

[0081] It should be noted that the above content is a further detailed description of the present application in combination with specific embodiments, and the specific implementation of the present application should not be limited to these descriptions. The size data in the present example does not limit the technical solution, but only demonstrates one specific working condition. For ordinary skilled persons in the technical field to which the present application belongs, some simple improvements and refinements can be made without departing from the concept of the present application, and all of them should be regarded as falling within the scope of protection of the present application.

Claims

1. A method for refining epoxy cyclododecene, characterized by, The method comprises: active carbon adsorption and solid alkali adsorption are performed on the epoxy cyclododecene to obtain adsorbed material; hydrogenation reaction is performed on the adsorbed material to obtain hydrogenation treated material; the hydrogenation treated material is subjected to gas-liquid separation to obtain epoxy cyclododecene product with acidity less than 0.1 mgKOH / g and colority less than 20 Hazen.

2. The method for purifying epoxy cyclododecene according to claim 1, characterized by, The active carbon adsorption is performed in a first adsorption tower filled with active carbon, and the operation temperature of the first adsorption tower is 30-100 ℃ and the pressure is 0-0.2 Mpa. Preferably, the feed airspeed of the activated carbon adsorption operation is 0.5-1.5 h -1 .

3. The method for purifying epoxy cyclododecene according to claim 1, characterized by, The activated carbon has a specific surface area of 900-1200 m 2 / g; Preferably, the bulk density of the active carbon is 0.3-0.6 g / ml.

4. The method for purifying epoxy cyclododecene according to claim 1, wherein The solid alkali comprises one or more of calcium oxide, magnesium oxide, calcium hydroxide, sodium carbonate, sodium bicarbonate or basic ion exchange resin.

5. The method of refining epoxy cyclododecene according to claim 1, wherein The solid alkali adsorption is performed in a second adsorption tower filled with solid alkali, and the operation temperature of the second adsorption tower is 30-80 ℃ and the pressure is 0-0.1 Mpa. Preferably, the feed space velocity of the solid base adsorption operation is between 0.5 and 1 h -1 .

6. The method of refining epoxy cyclododecene according to claim 1, wherein The catalyst for the hydrogenation reaction is a supported catalyst, and the active component of the supported catalyst is one of Pd, Ru and Pb. Preferably, the loading amount of the active component is 0.1-3 wt%.

7. The method of refining epoxy cyclododecene according to claim 6, wherein The carrier of the supported catalyst is one or more of active alumina, silicon oxide, titanium oxide and zirconium oxide.

8. The method for purifying epoxy cyclododecene according to claim 7, wherein The specific surface area of the support is between 200 and 400 m 2 / g; Preferably, the pore volume of the carrier is 0.3-0.8 ml / g. Preferably, the bulk density of the carrier is 0.5-1 g / ml.

9. The method of refining epoxy cyclododecene according to claim 1, wherein The molar ratio of hydrogen to the adsorbed material in the hydrogenation reaction is (1-4):

1.

10. The method of refining epoxy cyclododecene according to claim 1, wherein The temperature of the hydrogenation reaction is 40-100 ℃, and the reaction pressure is 0-0.5 Mpa. Preferably, the feed space velocity of the adsorbed material is between 0.5 and 1 h -1 .

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