A cyclododecatriene preparation reaction post-treatment process and system

Abstract

The application provides a cyclododecatriene preparation reaction post-processing process and system, which comprises the following steps: a termination process, in which a termination agent is mixed with a CDT reaction solution to perform catalyst quenching, so as to obtain a first mixture; wherein the termination agent comprises an alcohol, a phenol or a mixed solution of the alcohol and the phenol; a first extraction process, in which lye is used to extract the first mixture after cooling operation, so that a first oil phase is obtained and input into a second extraction process; and the second extraction process, in which pure water is used to extract the first oil phase, so that a second oil phase is obtained and input into a subsequent rectification separation process to obtain a cyclododecatriene product with high purity. The catalyst inactivation effect of the process is good, the loss rate of the CDT product obtained after the subsequent rectification separation is reduced, and the product recovery rate is high; the CDT reaction solution treated by the process avoids the equipment corrosion problem in the subsequent process, can reduce the equipment investment cost, simultaneously reduces the solid content and ensures the stable and continuous operation of the device.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, specifically to a post-reaction processing technology and system for the preparation of cyclododecanetriene. Background Technology

[0002] Cyclododecanetriene, abbreviated as CDT, usually refers to 1,5,9-cyclododecanetriene, which includes three isomers: trans-trans-cis-CDT, trans-trans-CDT, and trans-cis-cis-CDT. CDT can be used to prepare polyesters, polyamides, and plasticizers, as well as in the production of polyamide synthetic fibers, cold-resistant plasticizers, synthetic rubber, flavorings, epoxy resin crosslinking agents, fragrances, refractory additives, etc., making it an important industrial raw material.

[0003] Current CDT preparation processes use 1,3-butadiene as a raw material, polymerizing it under the action of a Ziegler-Natta catalyst system to produce a mixture of two or three isomers of CDT. The Ziegler-Natta catalyst is a directional polymerization catalyst composed of alkyl aluminum and titanium compounds. In the process of directionally preparing CDT by catalyzing the oligomerization reaction of butadiene using the Ziegler-Natta catalyst, the commonly used alkyl aluminum is sesquiethylaluminate chloride, and the titanium compound is titanium tetrachloride. After the CDT preparation reaction is completed, the catalyst must be deactivated; otherwise, the active catalyst will lead to CDT side reactions in subsequent distillation processes, reducing CDT recovery, increasing by-products, and also threatening the safety of subsequent processes.

[0004] Patent CN103420777A discloses a method for the continuous synthesis of 1,5,9-cyclododecanetriene. The deactivating agents used in this method are C1-C5 alcohols, aqueous sodium hydroxide solution, aqueous trisodium citrate solution, or sodium methoxide, and a 10%-5% aqueous sodium hydroxide solution. It is noteworthy that C1-C5 alcohols react with alkylaluminum and titanium tetrachloride to produce hydrogen chloride, the presence of which can lead to equipment corrosion; sodium hydroxide solution reacts with alkylaluminum to produce sodium chloride salt, which, if not removed, can result in salt-containing organic matter; simultaneously, titanium tetrachloride reacts with water to produce titanium oxide solid particles, causing equipment blockage; furthermore, C1-C5 alcohols are low-boiling-point substances, increasing the burden on subsequent separation processes.

[0005] Patent CN112521247A discloses a post-treatment method for a cyclododecanetriene reaction solution. This method involves mixing a thiol compound with an alkaline auxiliary agent to obtain a quencher. The quencher utilizes the characteristic that thiol groups readily form complexes with the active centers of titanium and aluminum to inactivate the catalyst. While this method adds an alkaline auxiliary agent to the quencher to neutralize the hydrogen chloride generated during the quenching reaction, it cannot prevent the alkaline auxiliary agent from reacting with alkylaluminum to form salts, further affecting the difficulty of subsequent distillation and separation, and the quality of the CDT product. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention discloses a post-processing technology and system for the preparation of cyclododecanetrienes, which is used to deactivate the catalyst in the CDT reaction solution. This avoids problems such as solid particle blockage of equipment, hydrogen chloride corrosion, and organic salt content caused by catalyst quenching. The process is reliable and suitable for continuous industrial operation.

[0007] To achieve the above technical objectives, this invention proposes a post-reaction processing method for the preparation of cyclododecanetriene. This process includes termination, primary extraction, and secondary extraction steps. The termination step involves mixing a terminator with a CDT reaction solution to quench the catalyst, resulting in a first mixture. The terminator includes alcohols, phenols, or a mixture of alcohols and phenols. The primary extraction step involves extracting the cooled first mixture with an alkaline solution, resulting in a first oil phase that is input into the secondary extraction step. The secondary extraction step involves extracting the first oil phase with pure water, resulting in a second oil phase that is input into a subsequent distillation separation process for purification to obtain a high-purity cyclododecanetriene product.

[0008] The technical solution of this invention uses an alcohol, phenol, or a mixture of alcohol and phenol as a terminator. The hydroxyl groups of the alcohol or phenol terminate the activity of the Ziegler-Natta catalyst. No alkaline additives are added to this terminator, which can avoid the formation of impurity salts due to the reaction of alkaline substances with alkyl aluminum. In addition, by using the terminator of this invention, the use of aqueous solutions of alkaline substances as alkaline additives can be avoided, preventing the formation of titanium oxide solid particles due to the reaction of titanium tetrachloride with water, which could cause equipment blockage and affect the overall safety of the process.

[0009] In a further preferred embodiment of the present invention, the alcohols and phenols selected as terminators have been optimized, and the amount of terminator added relative to the CDT reaction solution has been optimized, which can further reduce the operational difficulty of subsequent distillation and separation processes and improve product quality.

[0010] This invention employs a combined process of termination-condensation-primary extraction and secondary extraction to post-treat the CDT reaction solution after the 1,3-butadiene oligomerization reaction, deactivating the Ziegler-Natta catalyst used in the reaction. Specifically, in the termination step, a terminating agent comprising alcohols, phenols, or a mixture of alcohols and phenols is used to quench the catalyst. This process generates a small amount of hydrogen chloride. To avoid equipment corrosion damage in subsequent distillation and separation processes, this invention cools the first mixture after the termination step and incorporates a primary extraction step using alkali as the extractant to neutralize the hydrogen chloride in the first mixture. Subsequently, a secondary extraction step is performed after the primary extraction step, using pure water as the extractant to further wash the first oil phase obtained from the primary extraction step, removing residual alkali, salts, and other water-soluble substances, thereby improving the purity of CDT in the CDT reaction solution. The resulting second oil phase is then fed into the subsequent distillation and separation process to obtain a high-purity CDT product through separation and purification.

[0011] In a further preferred embodiment of the present invention, the parameters and process conditions of each step are optimized, which further improves the technical effect of quenching the catalyst in the CDT reaction solution.

[0012] Specifically, on the other hand, this invention proposes a post-processing system for the preparation of cyclododecanetriene, comprising: a jet mixer, with a CDT reaction liquid inlet pipe and a terminator inlet pipe respectively connected to the high-pressure fluid inlet and low-pressure fluid inlet of the jet mixer; a condenser, with the outlet of the jet mixer connected to the inlet of the condenser via a pipeline; a first extraction column, with the outlet of the condenser connected to the lower feed inlet of the first extraction column via a pipeline; an alkali inlet pipe connected to the upper feed inlet of the first extraction column, the first extraction column also having an upper outlet; a second extraction column, with the upper outlet of the first extraction column connected to the lower feed inlet of the second extraction column via a pipeline; a pure water inlet pipe connected to the upper feed inlet of the second extraction column, and a pipeline connected to the upper outlet of the second extraction column connected to a subsequent distillation and separation unit.

[0013] In a further preferred embodiment of the present invention, the structures of the first extraction tower and the second extraction tower are optimized, which further improves the extraction effect and increases the purity of CDT in the CDT reaction solution input into the subsequent distillation and separation unit.

[0014] Compared with existing technologies, the post-treatment process for the preparation of cyclododecanetrienes (CDT) in this invention uses an alcohol, phenol, or a mixture of alcohol and phenol as a terminator to quench the Ziegler-Natta catalyst in the CDT reaction solution. Combined with alkaline extraction and pure water extraction processes, the deactivated catalyst material is subsequently neutralized and washed. This invention achieves good catalyst deactivation, resulting in reduced CDT product loss and high product recovery after subsequent distillation. The CDT reaction solution treated by this process avoids equipment corrosion problems in subsequent distillation processes, reducing equipment investment costs. It also reduces solids content to prevent equipment blockage, ensuring stable and continuous operation of the unit and minimizing CDT product loss caused by periodic solids discharge in subsequent distillation processes. The post-treatment process and system flow for the preparation of cyclododecanetrienes in this invention are simple, improve production efficiency, and are suitable for continuous industrial production. Attached Figure Description

[0015] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0016] Figure 1 This diagram shows the structure of the post-reaction processing system for the preparation of cyclododecanetriene according to the present invention.

[0017] Figure 2 This diagram shows another structural diagram of the post-reaction processing system for the preparation of cyclododecanetriene according to the present invention.

[0018] The above figures include the following reference numerals:

[0019] 1-Jet mixer, 2-Condenser, 3-First extraction tower, 4-Second extraction tower, 51-CDT reaction liquid inlet pipe, 52-Terminator inlet pipe, 53-Alkali inlet pipe, 54-Pure water inlet pipe, 61-Wastewater buffer tank, 62-Oil phase buffer tank, 7-Oil phase transfer pump. Detailed Implementation

[0020] To facilitate understanding of the present invention, a more comprehensive description will be provided below, along with preferred embodiments. However, it should be understood that these embodiments are merely for more detailed explanation and should not be construed as limiting the invention in any way, i.e., not intended to limit the scope of protection of the invention.

[0021] It should be noted that, unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art to which this invention pertains. In this embodiment, relational terms such as "first," "second," "primary," and "secondary" are merely used to distinguish one component from another with the same name, and do not necessarily require or imply any such actual relationship or order between these components. Features defined with "first," "second," "primary," "secondary," etc., may explicitly or implicitly include one or more of these features.

[0022] In the description of this invention, unless otherwise explicitly specified and limited, the term "connection" should be interpreted broadly. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be a connection within two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0023] Example 1

[0024] A post-processing system for the preparation of cyclododecanetriene, such as Figure 1 As shown, the system includes:

[0025] The jet mixer 1 is connected to the high-pressure fluid inlet and the low-pressure fluid inlet of the CDT reaction solution 51 and the terminator inlet 52, respectively; the jet mixer 1 is used to mix the terminator and the COD reaction solution.

[0026] The outlet of the mixture from the jet mixer 1 is connected to the inlet of the condenser 2 via a pipeline;

[0027] The outlet of the condenser 2 in the first extraction tower 3 is connected to the lower feed inlet of the first extraction tower 3 via a pipeline; the alkaline solution input pipe 53 is connected to the upper feed inlet of the first extraction tower 3, and the first extraction tower 3 is also provided with an upper discharge outlet; the first extraction tower 3 is used to neutralize the hydrogen chloride generated after the catalyst quenching in the COD reaction solution.

[0028] The second extraction tower 4 is connected to the lower inlet of the first extraction tower 3 via a pipeline; the pure water input pipe 54 is connected to the upper inlet of the second extraction tower 4, and the pipeline connected to the upper outlet of the second extraction tower 4 is connected to the subsequent distillation and separation unit; the second extraction tower 4 is used to further wash and remove the residual alkali, salts and other water-soluble substances in the CDT reaction solution after catalyst quenching.

[0029] It should be noted that the structure of the first extraction tower 3 and the second extraction tower 4 is not limited in this embodiment. Optionally, the first extraction tower 3 and the second extraction tower 4 can be plate towers or packed towers, thereby promoting sufficient contact between the extractant and the material and enhancing the extraction effect. The structure of the selected plate tower and packed tower is not limited in this embodiment. Those skilled in the art can select plate towers or packed towers suitable for the post-processing of cyclododecanetriene preparation reactions through non-inventive means, and the resulting technical solutions are all within the scope of protection of this invention.

[0030] In addition, such as Figure 2 As shown, optionally, the lower outlets of the first extraction tower 3 and the second extraction tower 4 are respectively connected to the subsequent wastewater treatment unit via pipelines. Further optionally, a wastewater buffer tank 61 can be installed in the specific process, with the lower outlets of the first extraction tower 3 and the second extraction tower 4 connected separately or together to the inlet of the wastewater buffer tank 61, and the outlet of the wastewater buffer tank 61 connected to the subsequent wastewater treatment unit, thereby improving the operability of the process and increasing production efficiency.

[0031] Optionally, in the specific process, an oil phase buffer tank 62 connected to the upper outlet of the second extraction tower 4 can be set up. The outlet of the oil phase buffer tank 62 is connected to the subsequent distillation and separation unit, thereby buffering the oil phase output from the second extraction tower 4, improving the operability of the subsequent CDT distillation and separation process, and improving production efficiency.

[0032] Optionally, an oil phase transfer pump 7 can be installed on the pipeline connecting the first extraction tower 3 and the second extraction tower 4. In the specific process, the oil phase separated by the first extraction tower 3 can be input into the second extraction tower 4, which is beneficial to the control of the process flow.

[0033] It should be noted that the structure of the condenser 2 used in this embodiment is not limited. Different people skilled in the art can select a condenser suitable for the post-processing of the cyclododecanetriene preparation reaction through non-creative labor, and the resulting technical solutions are all within the protection scope of this invention.

[0034] It should be noted that, such as Figure 2 As shown, those skilled in the art can, through non-creative labor, install corresponding flow controllers and interlocked switching valves on the flow input pipeline, and install corresponding level gauges and interlocked switching valves on the discharge pipeline. The resulting technical solutions are all within the protection scope of this invention.

[0035] Example 2

[0036] A post-reaction processing method for the preparation of cyclododecanetrienes is described in this embodiment, which will be illustrated with reference to the system shown in Example 1. Specifically, the process includes termination, primary extraction, and secondary extraction steps, wherein...

[0037] Termination process: The terminator is mixed with the CDT reaction solution to quench the catalyst, resulting in a first mixture; wherein the terminator includes alcohols, phenols, or a mixture of alcohols and phenols. Specifically, the CDT reaction solution from the butadiene oligomerization reaction is fed into the high-pressure fluid inlet of the jet mixer 1, where it is thoroughly mixed and contacted with the terminator fed through the high-pressure fluid inlet. The terminator reacts with the Ziegler-Natta catalyst in the CDT reaction solution, causing catalyst deactivation.

[0038] In this embodiment, the alcohols and phenols included in the terminator, as well as the amount of the terminator, were optimized. Optionally, the alcohols are C6-C9 alcohols, preferably one or more of cyclohexanol, n-hexanol, isooctanol, n-octanol, and n-heptanol; the phenols include one or more of p-tert-butylcatechol, hydroquinone, and naphthol. Optionally, the amount of the terminator added relative to the CDT reaction solution is 10-30 g / kg, preferably 10-20 g / kg.

[0039] In the specific process of this embodiment, an excess of terminator can be added to fully deactivate the catalyst. The preferred alcohols in this embodiment have boiling points between 150 and 180°C, which are light components relative to cyclododecanetriene; phenols have boiling points between 260 and 300°C, which are heavy components relative to cyclododecanetriene; and CDT has a boiling point of 240°C. Therefore, the boiling point difference between the terminator components and CDT is large, making them easy to separate. The excess alcohols and / or phenols in the terminator can be separated out in the light and heavy component removal towers of the subsequent distillation separation unit without adding unnecessary separation equipment or increasing the process difficulty, and without affecting the purity of the final CDT product.

[0040] In this embodiment, the temperature and time of the termination process were optimized. Optionally, the temperature of the termination process is 100–200°C. At higher deactivation temperatures, the catalyst quenching reaction proceeds faster; therefore, the preferred operating temperature for the termination process is 100–150°C. The duration of the termination process is 5–10 minutes. In the specific process, a pipeline of appropriate length can be installed between the jet mixer 1 and the first extraction tower 3 to ensure a residence time of 5–10 minutes between the terminating agent and the CDT reaction solution output from the upstream process, thereby ensuring complete catalyst deactivation. It should be noted that, in the specific process, the pipeline between the jet mixer 1 and the first extraction tower 3 can be heated to ensure the reaction temperature of the termination process and promote efficient catalyst quenching reaction.

[0041] Primary extraction process: The first mixture after cooling is extracted using an alkaline solution, and the resulting first oil phase is fed into the secondary extraction process. Specifically, the Ziegler-Natta catalyst in the first mixture is completely deactivated, and a small amount of hydrogen chloride is generated during the catalyst quenching reaction. In this embodiment, the first mixture is fed into the lower part of the first extraction tower 3 after heat exchange, while the alkaline solution is fed into the upper part of the extraction tower. The alkaline solution and the first mixture are in countercurrent contact within the tower to neutralize the hydrogen chloride generated in the termination process. The first oil phase obtained from phase separation in the first extraction tower 3 is collected from the upper part and fed into the lower inlet of the second extraction tower 4; the first liquid phase obtained from phase separation is collected from the lower part of the first extraction tower 3 and fed into the subsequent wastewater treatment unit.

[0042] In this embodiment, the temperature of the condensation operation has been optimized. Optionally, the temperature of the cooling operation, i.e. the outlet temperature of the condenser 2, is 40 to 100°C, preferably 40 to 50°C.

[0043] In this embodiment, the amount and type of alkali solution used in the primary extraction step were optimized. Optionally, the mass ratio of the first oil phase to the alkali solution is 5–30, preferably 10–20. Optionally, the alkali solution is a sodium hydroxide or calcium hydroxide solution, and the mass concentration of the alkali solution is 10%–20%.

[0044] Secondary extraction process: Pure water is used to extract the first oil phase. The resulting second oil phase is then fed into a subsequent distillation separation process for purification to obtain a high-purity cyclododecanetriene product. Specifically, pure water entering from the top of the second extraction tower 4 comes into countercurrent contact with the first oil phase entering from the bottom feed inlet of the second extraction tower 4. This washes away residual alkali, salts, and other water-soluble substances in the first oil phase. The resulting second liquid phase is collected from the bottom of the second extraction tower 4 and fed into a subsequent wastewater treatment unit. The second oil phase obtained from the secondary extraction flows by gravity from the top of the second extraction tower 4 into an oil phase buffer tank 62 and is then fed into the subsequent distillation separation process.

[0045] In this embodiment, the amount of pure water used in the secondary extraction process was optimized. Optionally, the mass ratio of the second oil phase to pure water is 5 to 15, preferably 10 to 15.

[0046] It should be noted that the CDT reaction solution from the butadiene oligomerization reaction in this embodiment contains solvents for the oligomerization reaction, cyclooctadiene, tetravinylcyclohexene, catalysts and heavy components, etc., wherein the content of titanium tetrachloride is 100-1000 ppm and the content of sesquiethylaluminum chloride is 100-5000 ppm.

[0047] Example 3

[0048] This embodiment demonstrates the deactivation of the olefin Ziegler-Natta catalyst in the CDT reaction solution of butadiene oligomerization using the post-reaction treatment system for the preparation of cyclododecanetriene as shown in Example 1 under specific operating conditions. It should be noted that these process flows are merely demonstrations of preferred procedures and do not limit the scope of protection of this invention.

[0049] The composition of the CDT reaction solution in this embodiment is shown in Table 1.

[0050] Table 1

[0051]

[0052] Example 3.1

[0053] Taking the processing of 1000 kg of CDT reaction solution as an example, the CDT reaction solution is input through the high-pressure fluid inlet of jet mixer 1. Cyclohexanol is used as the terminator, with 12 kg of cyclohexanol added through the low-pressure fluid inlet of jet mixer 1. After the CDT reaction solution and the terminator are mixed, a Ziegler-Natta catalyst deactivation reaction occurs, yielding a first mixture. The termination temperature is 100°C, and the first mixture is transported in the pipeline between jet mixer 1 and the first extraction tower 3 for 5 minutes. After the catalyst is fully quenched, the condensation temperature of the first mixture is 40°C.

[0054] In the first extraction tower 3, 50 kg of 10% sodium hydroxide solution is used to separate the first mixture. The first oil phase obtained by phase separation is collected from the top of the first extraction tower 3 and fed into the second extraction tower 4. The aqueous phase obtained is collected from the bottom of the tower and fed into the subsequent wastewater treatment process.

[0055] In the second extraction tower 4, 100 kg of pure water is used to extract and wash the first oil phase. The aqueous phase obtained by phase separation is collected from the bottom of the tower and fed into the subsequent wastewater treatment process. The second oil phase is distilled and heated for more than 10 hours to obtain a CDT product recovery rate of 99.88%.

[0056] Example 3.2

[0057] Taking the processing of 1000 kg of CDT reaction solution as an example, the CDT reaction solution is input through the high-pressure fluid inlet of jet mixer 1. Isooctyl alcohol is used as the terminator, with 20 kg of isooctyl alcohol added through the low-pressure fluid inlet of jet mixer 1. After the CDT reaction solution and the terminator are mixed, a Ziegler-Natta catalyst deactivation reaction occurs, yielding the first mixture. The termination temperature is 150°C, and the first mixture is transported in the pipeline between jet mixer 1 and the first extraction tower 3 for 5 minutes. After the catalyst is fully quenched, the condensation temperature of the first mixture is 45°C.

[0058] In the first extraction tower 3, 50 kg of 10% sodium hydroxide solution is used to separate the first mixture. The first oil phase obtained by phase separation is collected from the top of the first extraction tower 3 and fed into the second extraction tower 4. The aqueous phase obtained is collected from the bottom of the tower and fed into the subsequent wastewater treatment process.

[0059] In the second extraction tower 4, 100 kg of pure water is used to extract and wash the first oil phase. The aqueous phase obtained by phase separation is collected from the bottom of the tower and input into the subsequent wastewater treatment process. The second oil phase is distilled and heated for more than 10 hours to obtain CDT product with a recovery rate of 99.85%.

[0060] Example 3.3

[0061] Taking the processing of 1000 kg of CDT reaction solution as an example, the CDT reaction solution is input through the high-pressure fluid inlet of jet mixer 1. Isooctyl alcohol is used as the terminator, with 20 kg of isooctyl alcohol added through the low-pressure fluid inlet of jet mixer 1. After the CDT reaction solution and the terminator are mixed, a Ziegler-Natta catalyst deactivation reaction occurs, yielding the first mixture. The termination temperature is 150°C, and the first mixture is transported in the pipeline between jet mixer 1 and the first extraction tower 3 for 5 minutes. After the catalyst is fully quenched, the condensation temperature of the first mixture is 45°C.

[0062] In the first extraction tower 3, 23 kg of 20% calcium hydroxide solution is used to separate the first mixture. The first oil phase obtained by phase separation is collected from the top of the first extraction tower 3 and fed into the second extraction tower 4. The aqueous phase obtained is collected from the bottom of the tower and fed into the subsequent wastewater treatment process.

[0063] In the second extraction tower 4, 100 kg of pure water is used to extract and wash the first oil phase. The aqueous phase obtained by phase separation is collected from the bottom of the tower and fed into the subsequent wastewater treatment process. The second oil phase is heated by distillation for more than 10 hours, and the recovery rate of CDT is 99.85%.

[0064] Example 3.4

[0065] Taking the processing of 1000 kg of CDT reaction solution as an example, the CDT reaction solution is input through the high-pressure fluid inlet of jet mixer 1. The terminator used is a 5-20% solution of isooctanol or cyclohexanol mixed with p-tert-butylcatechol. 15 kg of terminator is added through the low-pressure fluid inlet of jet mixer 1. After the CDT reaction solution and terminator are mixed, a Ziegler-Natta catalyst deactivation reaction occurs, yielding the first mixture. The termination temperature is 120°C, and the first mixture is transported in the pipeline between jet mixer 1 and the first extraction tower 3 for 10 minutes. After the catalyst is fully quenched, the condensation temperature of the first mixture is 50°C.

[0066] In the first extraction tower 3, 50 kg of 10% sodium hydroxide solution is used to separate the first mixture. The first oil phase obtained by phase separation is collected from the top of the first extraction tower 3 and fed into the second extraction tower 4. The aqueous phase obtained is collected from the bottom of the tower and fed into the subsequent wastewater treatment process.

[0067] In the second extraction tower 4, 100 kg of pure water is used to extract and wash the first oil phase. The aqueous phase obtained by phase separation is collected from the bottom of the tower and fed into the subsequent wastewater treatment process. The second oil phase is distilled and heated for more than 10 hours to obtain a CDT product with a recovery rate of 99.9%.

[0068] Comparative Example 1

[0069] Taking the processing of 1000 kg of CDT reaction solution as an example, the CDT reaction solution was post-processed using the cyclododecanetriene preparation post-processing system shown in Example 1. However, no terminator was added in this comparative example. After the CDT reaction solution was processed, it was then distilled and heated for more than 10 hours to obtain a CDT recovery rate of 96%.

[0070] Comparative Example 2

[0071] Taking the processing of 1000 kg of CDT reaction solution as an example, the post-processing system for the preparation of cyclododecanetriene shown in Example 1 was used for the post-processing of CDT reaction solution. The terminator used was cyclohexanol. 5 kg of cyclohexanol was added to the low-pressure fluid inlet of the jet mixer 1. After the catalyst was fully quenched, the first-stage extraction process and the second-stage extraction process were not performed. The terminated reaction solution was heated by distillation for more than 10 hours to obtain a CDT recovery rate of 99%.

[0072] Comparative Example 3

[0073] Taking the processing of 1000 kg of reaction liquid as an example, the CDT reaction liquid post-processing system shown in Example 1 was used for CDT reaction liquid post-processing. The terminator used was a mixed solution of isooctanol or cyclohexanol containing 5-20% p-tert-butylcatechol. 5 kg of terminator was added to the low-pressure fluid inlet of the jet mixer 1. After the catalyst was fully quenched, no primary or secondary extraction was performed. The terminated reaction liquid was heated by distillation for more than 10 hours to obtain a CDT product recovery rate of 99.5%.

[0074] It should be noted that the above description is a further detailed explanation of the present invention in conjunction with specific embodiments, and should not be construed as limiting the specific implementation of the present invention to these descriptions; the dimensional data in this embodiment do not necessarily limit the technical solution, but merely illustrate one specific working condition. For those skilled in the art, various simple improvements and modifications can be made without departing from the concept of the present invention, and all such improvements and modifications should be considered to fall within the scope of protection of the present invention.

Claims

1. A post-reaction processing method for the preparation of cyclododecanetriene, characterized in that, This includes termination, primary extraction, and secondary extraction processes, among which... Termination process: The terminating agent is mixed with the CDT reaction solution to quench the catalyst, resulting in a first mixture; wherein the terminating agent is a mixture of alcohols and phenols; the alcohols are selected from one or more of cyclohexanol and isooctanol; the phenols are p-tert-butylcatechol; the amount of the terminating agent added relative to the CDT reaction solution is 10~30g / kg; Primary extraction process: The first mixture after cooling is extracted with alkaline solution to neutralize the small amount of hydrogen chloride generated during quenching. The resulting first oil phase is input into the secondary extraction process. Secondary extraction process: The first oil phase is extracted with pure water, and the resulting second oil phase is fed into the subsequent distillation and separation process for purification to obtain a high-purity cyclododecanetriene product.

2. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The amount of the terminator added relative to the CDT reaction solution is 10~20g / kg.

3. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The temperature of the termination process is 100~200℃; the time is 5~10min.

4. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 3, characterized in that, The temperature of the termination process is 100~150℃.

5. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The temperature for the cooling operation is 40~100℃.

6. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The cooling operation is performed at a temperature of 40~50℃.

7. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The mass ratio of the first oil phase to the alkali solution is 5~30.

8. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 7, characterized in that, The mass ratio of the first oil phase to the alkali solution is 10~20.

9. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The alkaline solution is a sodium hydroxide or calcium hydroxide solution, and the mass concentration of the alkaline solution is 10%~20%.

10. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The mass ratio of the second oil phase to pure water is 5~15.

11. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 10, characterized in that, The mass ratio of the second oil phase to pure water is 10-15.

12. The post-reaction processing method for the preparation of cyclododecanetriene according to claim 1, characterized in that, The first aqueous phase obtained from the primary extraction process and the second aqueous phase obtained from the secondary extraction process are input into the subsequent wastewater treatment process.

Images