Refining method of epoxy cyclododecadiene

Abstract

The invention provides a refining method of epoxy cyclododecadiene. The method comprises the following steps: carrying out activated carbon adsorption and solid alkali adsorption on epoxy cyclododecadiene to obtain an adsorbed material; carrying out hydrogenation reaction on the adsorbed material to obtain a hydrotreated material; and carrying out gas-liquid separation on the hydrotreating material to obtain an epoxy cyclododecene product with the acidity of less than 0.1 mgKOH / g and the chromaticity of less than 20 Hazen. According to the present invention, the high-quality epoxy cyclododecadiene product is obtained by combining the activated carbon adsorption operation and the solid alkali adsorption operation with the hydrogenation reaction, and the method has advantages of simple process flow, strong operability and wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for refining epoxycyclododecadiene. Background Art

[0002] Epoxy cyclododecadiene is an important precursor for the production of cyclododecanone, which can be used to produce fine chemicals such as musk ketone, dodecanedioic acid, and lauryl lactam. Therefore, epoxy cyclododecadiene is widely used in the fields of flavors and fragrances, advanced lubricants, long-chain nylon, polyurethane, etc.

[0003] Epoxycyclododecadiene is generally prepared by oxidation of cyclododecatriene. Depending on the different oxidants, the preparation methods of epoxycyclododecadiene include chlorohydrin method, organic peracid oxidation method, hydrogen peroxide method, alkyl peroxide oxidation method, air / oxygen oxidation method, etc. At present, the industrial preparation of epoxy cyclododecadiene mainly includes alkyl peroxide oxidation method and organic peroxyacid oxidation method. For example, patents CN104650007A, CN106964337A, CN111704633A, etc. have developed a preparation method of epoxy cyclododecadiene, which uses cyclododecatriene (CDT) as a raw material and selectively epoxidizes with tert-butyl hydroperoxide (TBHP) under the action of a molybdenum catalyst to produce epoxy cyclododecadiene, while producing tert-butyl alcohol (TBA) as a by-product; for example, the preparation method of epoxy cyclododecadiene provided by patents EP0033763B1 and EP0032990A1 is mainly achieved by reacting cyclododecatriene with peroxyformic acid, wherein the peroxyformic acid is directly formed by the reaction of formic acid and hydrogen peroxide.

[0004] Regardless of the preparation method, the generated epoxy cyclododecadiene product always contains a variety of impurities. For example, patent CN117658954A mentions that when epoxy cyclododecadiene is produced by epoxidation of organic peroxide tert-butyl hydroperoxide (TBHP), 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, etc. If these impurities are not removed in time, they will accumulate in the system, which will not only cause system corrosion, but also catalyze side reactions. The product quality should be affected, so the patent obtains a product after treatment with a tert-butyl alcohol recovery tower and an impurity separation tower to remove acid and lipid impurities; Patent CN116102526A provides a post-treatment method for the reaction solution of epoxy cyclododecadiene in response to the problem that the product produced by the TBHP method contains a trace amount of TBHP (500-5000ppm); the method uses ferrocene-modified bisphenol A epoxy resin porous microspheres as adsorbents, and the microspheres can simultaneously adsorb and catalytically decompose TBHP in the reaction solution.

[0005] In addition, the use of organic peroxyacid to oxidize cyclododecatriene to prepare epoxycyclododecadiene is also one of the commonly used preparation methods. However, industrial practice shows that even after strict distillation and purification, the acidity of the generated product is greater than 1 mgKOH / g and the color is greater than 100 Hazen. Such high acidity and color index values ​​will seriously affect the subsequent reaction effect and affect the quality of the final product. Therefore, reducing the acidity and color of the epoxycyclododecadiene product is a technical problem that needs to be solved urgently. Summary of the invention

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

[0007] In order to achieve the above technical objectives, on the one hand, the present invention provides a method for refining epoxycyclododecadiene, the method comprising:

[0008] Adsorbing epoxycyclododecadiene by activated carbon and solid base to obtain an adsorbed material;

[0009] Performing a hydrogenation reaction on the adsorbed material to obtain a hydrogenated material;

[0010] The hydrogenated material is subjected to gas-liquid separation to obtain an epoxycyclododecadiene product having an acidity of less than 0.1 mgKOH / g and a chromaticity of less than 20 Hazen.

[0011] Based on mass production and industrial practice, the research and development team of the present invention found that the epoxy cyclododecadiene prepared by cyclododecatriene as raw material and oxidation with organic peroxy acid has a high acid value and chromaticity. Even after distillation and purification to a purity of more than 99.5%, the acidity of the product is still greater than 1 mgKOH / g and the chromaticity is greater than 100 Hazen. Through exploratory experiments on the process and the results of the research and development team, it is speculated that the high acidity of high-purity epoxy cyclododecadiene may be due to the fact that during the process, epoxy cyclododecadiene generates some high-boiling fatty acids under the action of organic acids. The possible reaction formula is as follows:

[0012]

[0013] The high color value of high-purity epoxycyclododecadiene may be mainly due to over-oxidation to generate unsaturated hydrocarbons or unsaturated aldehydes. The possible reaction formula is as follows:

[0014]

[0015] It is worth noting that during the oxidation reaction of cyclododecatriene, polymerization reactions will occur between the reaction products to generate some oligomers, such as:

[0016]

[0017] These macromolecular oligomers may still exist in the high-purity epoxycyclododecadiene product after distillation and purification and affect the acidity and color. The presence of these oligomers will affect the subsequent reactions and therefore need to be removed as much as possible.

[0018] Based on the above speculation, the research and development team of the present invention tried to use activated carbon adsorption to remove the macromolecular polymer impurities in the epoxy cyclododecadiene product, and combined it with solid base adsorption to neutralize and adsorb the acidic impurities, but the exploration results were surprising: although the acidity of the epoxy cyclododecadiene product was significantly reduced to a lower value, the chromaticity was still high. Even if the conditions of the activated carbon adsorption operation were optimized or the activated carbon adsorption treatment time was increased, the chromaticity of the epoxy cyclododecadiene product remained at a certain level. Based on the results of the exploratory experiment, the research and development team further tried to add a hydrogenation reaction process on the basis of activated carbon adsorption and solid base adsorption to reduce the acidity and chromaticity of the epoxy cyclododecadiene product. The experiment achieved unexpectedly excellent results: the chromaticity of the epoxy cyclododecadiene obtained after refining was less than 20 Hazen. It is speculated that it may be due to the hydrogenation reaction that reduces the trace unsaturated impurities remaining in the high-purity epoxy cyclododecadiene product after the activated carbon adsorption operation, so that the chromaticity of the epoxy cyclododecadiene can be further reduced to a lower value; in addition, the synergistic effect of activated carbon adsorption and solid base adsorption makes the acidity of epoxy cyclododecadiene less than 0.1 mgKOH / g. The embodiments of the present invention and the comparative examples show the above exploration process. Based on the above findings, the research and development team of the present invention proposed the above technical solution.

[0019] It should be noted that the present invention does not limit the order of the activated carbon adsorption operation and the solid base adsorption operation, and the order of the activated carbon adsorption operation and the solid base adsorption operation can be interchanged. For example, epoxy cyclododecadiene can be optionally adsorbed on activated carbon to obtain a first material, the first material is adsorbed on a solid base to obtain a second material, the second material is subjected to a hydrogenation reaction to obtain a third material, and the third material is subjected to gas-liquid separation to obtain an epoxy cyclododecadiene product having an acidity of less than 0.1 mgKOH / g and a chromaticity of less than 20 Hazen; or epoxy cyclododecadiene can be optionally adsorbed on a solid base to obtain a fourth material, the fourth material is subjected to activated carbon adsorption to obtain a fifth material, the fifth material is subjected to a hydrogenation reaction to obtain the third material, and the third material is subjected to gas-liquid separation to obtain an epoxy cyclododecadiene product having an acidity of less than 0.1 mgKOH / g and a chromaticity of less than 20 Hazen.

[0020] In a further example of the present invention, 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, the operating temperature of the first adsorption tower is 30-100°C and the pressure is 0-0.2Mpa. The activated carbon adsorption operation of the present invention has mild conditions, saves energy consumption, and has strong operability. Optionally, the feed air velocity of the epoxycyclododecadiene relative to the activated carbon is 0.5-1.5h -1 , to obtain better adsorption effect.

[0021] It should be noted that the present invention is not limited to the specific structure of the first adsorption tower, which may be a fixed bed adsorption tower or a moving bed adsorption tower, etc. The technicians in this field can select an adsorption tower with a suitable structure based on the technical solution of the present invention and according to the actual working conditions, and the technical solutions thus formed are all within the protection scope of the present invention.

[0022] In a further example of the present invention, optionally, 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 invention; optionally, the stacking density of the activated carbon is 0.3-0.6g / ml, thereby improving the mass transfer effect and increasing the production efficiency.

[0023] In a further example of the present invention, the type of solid base used for the solid base adsorption is explored and optimized, and a weak base base adsorbent can be selected, and further one or more of calcium oxide, magnesium oxide, calcium hydroxide, sodium carbonate, sodium bicarbonate or alkaline ion exchange resin can be selected. The present invention ensures the stability and high yield of the process by adopting a weak base catalyst.

[0024] In a further example of the present invention, the control conditions of the solid alkali adsorption operation are explored and optimized. Optionally, the solid alkali adsorption operation is carried out in a second adsorption tower filled with solid alkali, the operating temperature of the second adsorption tower is 30-80°C, and the pressure is 0-0.1Mpa. The relatively mild operating conditions of the present invention can obtain a better deacidification effect, which is suitable for industrial application. Optionally, in the solid alkali adsorption operation, the feed air velocity of the material input into the second adsorption tower relative to the solid alkali is 0.5-1h -1 , the adjustment of the first material feed space velocity optimizes the deacidification effect.

[0025] The present invention does not limit the type of catalyst for the hydrogenation reaction. In a further example of the present invention, the type of catalyst used 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 invention, the use of a noble metal catalyst to catalyze the hydrogenation of trace unsaturated impurities is more effective, and the chromaticity of the epoxycyclododecadiene product can be significantly reduced. Optionally, the loading amount of the active component is 0.1-3wt%, and a better catalyst hydrogenation effect can be obtained.

[0026] It should be noted that the specific preparation process of the catalyst used in the present invention can be selected: first loading the precious metal onto a carrier in the form of a nitrate or chloride salt, and then drying and calcining to form a finished catalyst, in which case the precious metal exists in an oxidized state; the finished catalyst is loaded into a reactor, and pre-reduced using hydrogen before use to reduce the oxidized state to a metallic state.

[0027] In a further example of the present invention, optionally, the carrier of the supported catalyst is one or more of activated alumina, silicon oxide, titanium oxide, and zirconium oxide. The catalyst carrier has a variety of choices, reflecting the flexibility and applicability of the process of the present invention.

[0028] In a further example of the present invention, the specific surface area of ​​the carrier is 200-400m 2 / g. Optionally, the pore volume of the carrier is 0.3-0.8 ml / g. Optionally, the bulk density of the carrier is 0.5-1 g / ml. The exploration and optimization of parameters related to the catalyst carrier improves the activity and selectivity of the supported catalyst and enhances the catalytic effect of the hydrogenation catalyst.

[0029] It should be noted that the present invention is not limited to the specific equipment for the hydrogenation reaction, which can be selected as a fixed bed reactor, and further selected as a shell-and-tube fixed bed reactor. Those skilled in the art can select hydrogenation reaction equipment and facilities of appropriate structure based on the technical solution of the present invention and according to actual working conditions, and the technical solutions thus formed are all within the protection scope of the present invention.

[0030] In a further example of the present invention, 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°C and the reaction pressure is 0-0.5Mpa. The operating conditions are relatively mild and have better operability. Optionally, the feed space velocity of the adsorbed material relative to the catalyst of the hydrogenation reaction is 0.5-1h -1 , the control of the feed of hydrogenation reaction materials is convenient for regulation to improve the hydrogenation reaction effect.

[0031] It is also worth noting that, taking into account the interference of impure acids, oligomers, etc. in the refined epoxy cyclododecadiene product on the catalytic activity of the hydrogenation catalyst, and in order to improve industrial operability and save process costs, the R&D team optimized the hydrogenation reaction after completing activated carbon adsorption and solid base adsorption.

[0032] Compared with the prior art, the invention has the following beneficial effects: the invention obtains high-quality epoxycyclododecadiene product by combining activated carbon adsorption operation and solid base adsorption operation with hydrogenation reaction, and the acidity of the product is less than 0.1 mgKOH / g and the chromaticity is less than 20 Hazen, and the product has wide application value. The method of the invention has simple process flow and strong operability, and is suitable for industrial promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0034] Figure 1 A comparison chart showing the epoxy cyclododecadiene to be purified and the epoxy cyclododecadiene product obtained after purification in Example 1 of the present invention is shown. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below, and preferred embodiments of the present invention 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 invention in any form, i.e., not intended to limit the scope of protection of the present invention.

[0036] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0037] It should be noted that, in the description of the preferred embodiment, unless otherwise clearly specified and limited, the terms "first", "second", "third", "fourth", "fifth", etc. are only used for descriptive purposes. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to the specific circumstances, and therefore cannot be understood as limitations on the present invention.

[0038] It should be noted that the method for determining acidity in the embodiments of the present invention refers to GB / T264-83; the method for measuring chromaticity is: a suitable amount of sample solution is measured by a spectrophotometer at a wavelength of 390nm, and compared with a platinum-cobalt standard solution to calculate the chromaticity of the sample; wherein Hazen units are: the chromaticity 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.

[0039] Example 1

[0040] A method for refining epoxy cyclododecadiene, specifically, post-treating 100 kg / h of epoxy cyclododecadiene raw material, wherein the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, and has a purity of more than 99.5%, an acidity of 1.54 mgKOH / g, and a chromaticity of 167.69 Hazen:

[0041] The epoxycyclododecadiene raw material to be refined is input into the 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, and the specific surface area is 900 m 2 / g, the tower operating temperature is 30°C, the pressure is 0.1Mpa, and the bed pressure drop is 40kpa; the first material is obtained from the bottom of the first adsorption tower. The first material enters the second adsorption tower, and the second adsorption tower is filled with 100kg of formed calcium hydroxide balls. The tower operating temperature is 50°C, the pressure is 0.1Mpa, and the bed pressure drop is 10kpa; the second material is obtained from the bottom of the second adsorption tower. The second material and hydrogen enter the hydrogenation refining tower, and the refining tower is filled with 100kg of catalyst, which is activated alumina loaded with precious metal Pb, wherein the Pb loading is 1.5%, and the specific surface area of ​​the carrier alumina is 350m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the refining tower is 50°C, the pressure is 0.3Mpa, 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, enters the gas-liquid separator for gas-liquid separation, and the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is taken from the bottom of the gas-liquid separator.

[0042] The yield of this embodiment is 99.93%, and the acidity of the obtained epoxycyclododecadiene product is 0.06 mgKOH / g, and the chromaticity is 13.57 Hazen; Figure 1 The chromaticity comparison between the epoxy cyclododecadiene to be purified and the purified epoxy cyclododecadiene product in this example is shown.

[0043] Example 2

[0044] A method for refining epoxy cyclododecadiene, specifically, post-treating 100 kg / h of epoxy cyclododecadiene raw material, wherein the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, has a purity of more than 99.5%, an acidity of 1.54 mgKOH / g, and a chromaticity of 167.69 Hazen:

[0045] The epoxy cyclododecadiene raw material to be refined is input into the first adsorption tower, in which the activated carbon loading amount is 70kg, the bulk density is 0.35g / ml, the specific surface area is 900m2 / g, the tower operating temperature is 100℃, the pressure is 0.01Mpa, the bed pressure drop is 30kpa, and the first material is obtained from the bottom of the first adsorption tower. The first material enters the second adsorption tower, in which 200kg of formed calcium oxide balls are loaded, the tower operating temperature is 80℃, the pressure is 0.01Mpa, and the bed pressure drop is 25kpa; the second material is obtained from the bottom of the second adsorption tower. The second material and hydrogen enter the hydrogenation refining tower, in which 100kg of catalyst is loaded, and the catalyst is activated alumina loaded with precious metal Pd, wherein the loading amount of Pd is 1%; the specific surface area of ​​the carrier alumina is 350m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 40°C, 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. The unreacted hydrogen is discharged from the top of the separator and can be recycled. The refined epoxy cyclododecadiene product is taken from the bottom of the gas-liquid separator.

[0046] The yield of this embodiment is 99.93%. The acidity of the obtained epoxycyclododecadiene product is 0.09 mgKOH / g and the chromaticity is 12.17 Hazen.

[0047] Example 3

[0048] A method for refining epoxy cyclododecadiene, specifically, post-treating 100 kg / h of epoxy cyclododecadiene raw material, wherein the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, has a purity of more than 99.5%, an acidity of 1.99 mgKOH / g, and a chromaticity of 145.06 Hazen:

[0049] The epoxycyclododecadiene raw material to be purified is fed into the first adsorption tower, in which the activated carbon loading amount is 200 kg, the bulk density is 0.6 g / ml, and the specific surface area is 1200 m 2 / g, the tower operating temperature is 50°C, the pressure is 0.2Mpa, and the bed pressure drop is 80kpa; the first material is obtained from the bottom of the first adsorption tower. The first material enters the second adsorption tower, which is filled with 200kg of formed magnesium oxide balls, the tower operating temperature is 30°C, the pressure is 0.05Mpa, and the bed pressure drop is 30kpa; the second material is obtained from the bottom of the second adsorption tower.

[0050] The second material and hydrogen enter into a hydrogenation refining tower, in which 100 kg of catalyst is loaded. The catalyst is activated alumina loaded with precious metal Pd, wherein the loading amount of Pd is 0.3%; the specific surface area of ​​the carrier alumina is 400 m 2 / g, pore volume is 0.56ml / g, bulk density is 0.62g / ml; the reaction temperature of the hydrogenation refining tower is 100°C, the pressure is 0.5Mpa, and the molar ratio of hydrogen to the second material is 4. The third material flows out from the bottom outlet of the refining tower and enters the gas-liquid separator for gas-liquid separation. The unreacted hydrogen is discharged from the top of the separator and can be recycled. The refined epoxy cyclododecadiene product is taken from the bottom of the gas-liquid separator.

[0051] The yield of this embodiment is 99.97%, and the acidity of the obtained epoxycyclododecadiene product is 0.09 mgKOH / g and the chromaticity is 12.73 Hazen.

[0052] Example 4

[0053] A method for refining epoxy cyclododecadiene, specifically, post-treating 100 kg / h of epoxy cyclododecadiene raw material, wherein the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, has a purity of more than 99.5%, an acidity of 1.99 mgKOH / g, and a chromaticity of 145.06 Hazen:

[0054] The epoxy cyclododecadiene raw material to be refined is fed into the second adsorption tower, which is filled with 200 kg of formed magnesium oxide balls. The tower operates at a temperature of 30°C, a pressure of 0.05 MPa, and a bed pressure drop of 30 kPa. The fourth material is obtained from the bottom of the second adsorption tower. The fourth material is fed into the first adsorption tower, in which the activated carbon loading amount is 200 kg, the bulk density is 0.6 g / ml, and the specific surface area is 1200 m 2 / g, the tower operating temperature is 50°C, the pressure is 0.2Mpa, and the bed pressure drop is 80kpa; the fifth material is obtained from the bottom of the first adsorption tower. The fifth material and hydrogen enter the hydrogenation refining tower, and the tower is filled with 100kg of refined catalyst, which is activated alumina loaded with precious metal Pd, wherein the Pd loading is 0.3%; the specific surface area of ​​the carrier alumina is 400m 2 / g, pore volume is 0.56ml / g, bulk density is 0.62g / ml; the reaction temperature of the refining tower is 100°C, the pressure is 0.5Mpa, and the molar ratio of hydrogen to the fifth material is 4. The third material flows out from the bottom outlet of the refining tower and enters the gas-liquid separator for gas-liquid separation. The unreacted hydrogen is discharged from the top of the separator and can be recycled. The refined epoxy cyclododecadiene product is taken from the bottom of the gas-liquid separator.

[0055] The yield of this embodiment is 99.97%, and the acidity of the obtained epoxycyclododecadiene product is 0.085 mgKOH / g and the chromaticity is 13.56 Hazen.

[0056] Example 5

[0057] A method for refining epoxy cyclododecadiene, specifically, post-treating 100 kg / h of epoxy cyclododecadiene raw material, wherein the epoxy cyclododecadiene raw material is prepared by oxidation reaction of cyclododecatriene and peroxyformic acid, has a purity of more than 99.5%, an acidity of 1.12 mgKOH / g, and a chromaticity of 145.92 Hazen:

[0058] The epoxycyclododecadiene raw material to be purified is fed into the first adsorption tower, in which the activated carbon loading amount is 150 kg, the bulk density is 0.55 g / ml, and the specific surface area is 1140 m 2 / g, the tower operating temperature is 100℃, the pressure is 0.05Mpa, and the bed pressure drop is 50kpa; the first material is obtained from the bottom of the first adsorption tower. The first material enters the second adsorption tower, and the second adsorption tower is filled with 200kg of molded magnesium oxide balls. The tower operating temperature is 80℃, the pressure is 0.01Mpa, and the bed pressure drop is 30kpa; the second material is obtained from the bottom of the second adsorption tower. The second material and hydrogen enter the hydrogenation refining tower, and the tower is filled with 200kg of refined catalyst, which is activated alumina loaded with precious metal Ru, wherein the Ru loading amount is 0.1%; the specific surface area of ​​the carrier alumina is 220m 2 / g, pore volume is 0.38ml / g, bulk density is 0.53g / ml; the reaction temperature of the hydrogenation refining tower is 100℃, the pressure is 0.3Mpa, and the molar ratio of hydrogen to the second material is 3.4. The third material flows out from the bottom outlet of the refining tower and enters the gas-liquid separator for gas-liquid separation. The unreacted hydrogen is discharged from the top of the separator and can be recycled. The refined epoxy cyclododecadiene product is extracted from the bottom of the gas-liquid separator.

[0059] The yield of this embodiment is 99.98%, and the acidity of the obtained epoxycyclododecadiene product is 0.089 mgKOH / g and the chromaticity is 11.59 Hazen.

[0060] Comparative Example 1

[0061] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0062] The epoxycyclododecadiene raw material to be purified is firstly subjected to activated carbon adsorption in an activated carbon fixed bed adsorption tower. The activated carbon loading 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 0.1Mpa, and the bed pressure drop is 40kpa; the first material is obtained from the bottom of the activated carbon fixed bed adsorption tower. The first material enters the alkali tower filled with 100kg of formed calcium hydroxide balls, the alkali tower operating temperature is 50°C, the pressure is 0.1Mpa, the bed pressure drop is 10kpa, and the refined epoxy cyclododecadiene product is obtained from the bottom of the alkali tower.

[0063] The product yield of this comparative example is 99.93%, and the acidity of the obtained epoxycyclododecadiene product is 0.06 mgKOH / g and the chromaticity is 148.71 Hazen.

[0064] Comparative Example 2

[0065] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0066] The epoxycyclododecadiene raw material to be purified is firstly subjected to activated carbon adsorption in an activated carbon fixed bed adsorption tower. The activated carbon loading in the tower is 200 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 0.1Mpa, and the bed pressure drop is 70kpa; the first material is obtained from the bottom of the activated carbon fixed bed adsorption tower. The first material enters the alkali tower filled with 100kg of formed calcium hydroxide balls, the alkali tower has an operating temperature of 50°C, a pressure of 0.1Mpa, and a bed pressure drop of 10kpa; the refined epoxy cyclododecadiene product is obtained from the bottom of the alkali tower.

[0067] The product yield of this comparative example is 99.93%, the acidity is 0.06 mgKOH / g, and the chromaticity is 128.32 Hazen.

[0068] Comparative Example 3

[0069] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0070] The epoxy cyclododecadiene raw material to be refined first enters the alkali tower, which is filled with 100 kg of formed calcium hydroxide balls. 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 the tower and a certain amount of hydrogen enter the hydrogenation refining tower, which is filled with 100 kg of refined catalyst, which is activated alumina loaded with precious metal Pb, where the Pb loading is 1.5%. The specific surface area of ​​the carrier alumina is 350 m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 50℃, the pressure is 0.3Mpa, and the molar ratio of hydrogen to epoxycyclododecadiene in the feed is 1.1. After the material extracted from the hydrogenation refining tower kettle enters the gas-liquid separator, the unreacted hydrogen is discharged from the top of the separator for recycling, and the refined epoxycyclododecadiene product is discharged from the bottom of the gas-liquid separator.

[0071] The product yield of this comparative example is 99.93%, the acidity is 0.55 mgKOH / g, and the chromaticity is 13.57 Hazen.

[0072] Comparative Example 4

[0073] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0074] The epoxycyclododecadiene raw material to be purified is firstly adsorbed in an activated carbon fixed bed adsorption tower. The activated carbon loading 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 130℃, the pressure is 0.1Mpa, and the bed pressure drop is 40kpa; the material extracted from the bottom of the activated carbon fixed bed adsorption tower enters the alkali tower filled with 100kg of formed calcium hydroxide balls, the operating temperature of the alkali tower is 50℃, the pressure is 0.1Mpa, and the bed pressure drop is 10kpa; the material extracted from the bottom of the alkali tower and a certain amount of hydrogen enter the hydrogenation refining tower, and the hydrogenation refining tower is filled with 100kg of refined catalyst, which is activated alumina loaded with precious metal Pb, where the Pb loading is 1.5%. The specific surface area of ​​the carrier alumina is 350m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 50°C, the pressure is 0.3Mpa, and the molar ratio of hydrogen to epoxy cyclododecadiene in the feed is 1.1; after the material taken out from the kettle of the hydrogenation refining tower enters the gas-liquid separator, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is taken out from the bottom of the gas-liquid separator.

[0075] The product yield of this comparative example is 99.8%, the acidity is 0.14 mgKOH / g, and the chromaticity is 25.1 Hazen.

[0076] Comparative Example 5

[0077] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0078] The epoxycyclododecadiene raw material to be purified is firstly adsorbed in an activated carbon fixed bed adsorption tower. The activated carbon loading 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℃, the pressure is 0.1Mpa, and the bed pressure drop is 40kpa; the material extracted from the kettle of the activated carbon fixed bed adsorption tower enters the alkali tower filled with 100kg of formed calcium hydroxide balls, the alkali tower operating temperature is 130℃, the pressure is 0.1Mpa, and the bed pressure drop is 10kpa; the extracted material from the kettle of the alkali tower and a certain amount of hydrogen enter the hydrogenation refining tower, and the hydrogenation refining tower is filled with 100kg of refined catalyst, which is activated alumina loaded with precious metal Pb, wherein the Pb loading amount is 1.5%; the specific surface area of ​​the carrier alumina is 350m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 50°C, the pressure is 0.3Mpa, and the molar ratio of hydrogen to epoxy cyclododecadiene in the feed is 1.1; after the material taken out from the kettle of the hydrogenation refining tower enters the gas-liquid separator, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is taken out from the bottom of the gas-liquid separator.

[0079] The product yield of this comparative example is 99.8%, the acidity is 0.48 mgKOH / g, and the chromaticity is 18.6 Hazen.

[0080] Comparative Example 5

[0081] 100 kg / h of epoxy cyclododecadiene raw material was post-processed and refined. The epoxy cyclododecadiene raw material was prepared by oxidation reaction of cyclododecatriene and peroxyformic acid. The purity was >99.5%, the acidity was 1.54 mgKOH / g, and the color was 167.69 Hazen:

[0082] The epoxycyclododecadiene raw material to be purified is firstly adsorbed in an activated carbon fixed bed adsorption tower. The activated carbon loading 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 130℃, the pressure is 0.1Mpa, and the bed pressure drop is 40kpa. The materials extracted from the bottom of the activated carbon fixed bed adsorption tower enter the alkali tower filled with 100kg of formed calcium hydroxide balls. The alkali tower operates at 130℃, the pressure is 0.1Mpa, and the bed pressure drop is 10kpa; the materials extracted from the bottom of the alkali tower and a certain amount of hydrogen enter the hydrogenation refining tower, which is filled with 100kg of refined catalyst, which is activated alumina loaded with precious metal Pb, where the Pb loading is 1.5%; the specific surface area of ​​the carrier alumina is 350m 2 / g, pore volume is 0.78ml / g, bulk density is 0.85g / ml; the reaction temperature of the hydrogenation refining tower is 50°C, the pressure is 0.3Mpa, and the molar ratio of hydrogen to epoxy cyclododecadiene in the feed is 1.1; after the material taken out from the kettle of the hydrogenation refining tower enters the gas-liquid separator, the unreacted hydrogen is discharged from the top of the separator and can be recycled, and the refined epoxy cyclododecadiene product is taken out from the bottom of the gas-liquid separator.

[0083] The product yield of this comparative example is 99.8%, the acidity is 0.68 mgKOH / g, and the chromaticity is 25.6 Hazen.

[0084] It should be noted that the above contents are further detailed descriptions of the present invention in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions; the dimensional data of this embodiment does not necessarily limit the technical solution, but only shows one of the specific working conditions. For ordinary technicians in the technical field to which the present invention belongs, several simple improvements and modifications can be made without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. A method for refining epoxycyclododecadiene, characterized in that: The method comprises: Adsorbing epoxycyclododecadiene by activated carbon and solid base to obtain an adsorbed material; Performing a hydrogenation reaction on the adsorbed material to obtain a hydrogenated material; The hydrogenated material is subjected to gas-liquid separation to obtain an epoxycyclododecadiene product having an acidity of less than 0.1 mgKOH / g and a chromaticity of less than 20 Hazen.

2. The method for refining epoxycyclododecadiene according to claim 1, characterized in that: The activated carbon adsorption operation is carried out in a first adsorption tower filled with activated carbon, wherein the operating temperature of the first adsorption tower is 30-100°C and the pressure is 0-0.2Mpa; Preferably, the feed space velocity of the activated carbon adsorption operation is 0.5-1.5h -1 .

3. The method for refining epoxycyclododecadiene according to claim 1, characterized in that: The specific surface area of ​​the activated carbon is 900-1200m 2 / g; Preferably, the bulk density of the activated carbon is 0.3-0.6 g / ml.

4. The method for refining epoxycyclododecadiene according to claim 1, characterized in that: The solid base includes one or more of calcium oxide, magnesium oxide, calcium hydroxide, sodium carbonate, sodium bicarbonate or alkaline ion exchange resin.

5. The method for refining epoxycyclododecadiene according to claim 1, characterized in that: 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°C and the pressure is 0-0.1Mpa; Preferably, the feed space velocity of the solid base adsorption operation is 0.5-1h -1 .

6. The method for refining epoxycyclododecadiene according to claim 1, characterized in that: 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 for refining epoxycyclododecadiene according to claim 6, characterized in that: The carrier of the supported catalyst is one or more of activated alumina, silicon oxide, titanium oxide and zirconium oxide.

8. The method for refining epoxycyclododecadiene according to claim 7, characterized in that: The specific surface area of ​​the carrier is 200-400m 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 for purifying epoxycyclododecadiene according to claim 1, characterized in that: The molar ratio of hydrogen to the adsorbed material in the hydrogenation reaction is (1-4):

1.

10. The method for purifying epoxycyclododecadiene according to claim 1, characterized in that: The temperature of the hydrogenation reaction is 40-100°C and the reaction pressure is 0-0.5Mpa; Preferably, the feed space velocity of the adsorbed material is 0.5-1h -1 .

Images