CN-116854557-B - Post-treatment process and system for cyclododecatriene preparation reaction

Abstract

The invention provides a post-treatment process and a post-treatment system for cyclododecatriene preparation reaction, wherein the process comprises a termination procedure, a terminator and CDT reaction liquid are mixed for catalyst quenching to obtain a first mixed material, wherein the terminator comprises alcohols, phenols or mixed liquid of the alcohols and the phenols, primary extraction is carried out on the first mixed material after cooling operation by adopting alkali liquor, the obtained first oil phase is input into a secondary extraction procedure, secondary extraction is carried out on the first oil phase by adopting pure water, and the obtained second oil phase is input into a subsequent rectification separation procedure for purification to obtain a high-purity cyclododecatriene product. The process has the advantages of good catalyst inactivation effect, reduced loss rate of the CDT product obtained after subsequent rectification and separation, high product recovery rate, and capability of avoiding the problem of equipment corrosion in the subsequent working procedure by the CDT reaction liquid treated by the process, reducing equipment investment cost, reducing solid content and ensuring stable and continuous operation of the device.

Inventors

• WANG CONG
• YANG GUANG
• CUI YANJIE
• LONG YING
• SUN BO
• JIN QUAN
• FENG CHUANMI
• LIU XINWEI
• LI RONG
• Li Yaotou
• WANG ZHIMING
• YANG KEJIAN
• LI GUANGZHONG

Assignees

• 中国天辰工程有限公司

Dates

Publication Date

20260512

Application Date

20230707

Claims (12)

1. 1. A post-treatment process for cyclododecatriene preparation reaction is characterized by comprising the steps of termination, primary extraction and secondary extraction, wherein The method comprises the termination step of mixing a terminator with a CDT reaction solution to perform catalyst quenching to obtain a first mixed material, wherein the terminator is a mixed solution of alcohols and phenols, the alcohols are one or more of cyclohexanol and isooctanol, the phenols are p-tert-butyl catechol, and the addition amount of the terminator relative to the CDT reaction solution is 10-30 g/kg; A first extraction procedure, namely extracting the first mixed material after cooling operation by adopting alkali liquor, neutralizing a small amount of hydrogen chloride generated during quenching, and inputting the obtained first oil phase into the second extraction procedure; And a second-stage extraction procedure, namely extracting the first oil phase by pure water, and inputting the obtained second oil phase into a subsequent rectification separation procedure for purification to obtain a high-purity cyclododecatriene product.
2. 2. The post-reaction treatment process for cyclododecatriene production of claim 1, wherein the addition amount of the terminator to the CDT reaction solution is 10 to 20g/kg.
3. 3. The post-reaction treatment process for cyclododecatriene preparation according to claim 1, wherein the temperature of the termination process is 100-200 ℃ and the time is 5-10 min.
4. 4. The post-reaction treatment process for cyclododecatriene production as recited in claim 3, wherein the temperature of the termination process is 100 to 150 ℃.
5. 5. The post-reaction treatment process for cyclododecatriene production according to claim 1, wherein the temperature of the cooling operation is 40-100 ℃.
6. 6. The post-reaction treatment process for cyclododecatriene production according to claim 1, wherein the temperature of the cooling operation is 40-50 ℃.
7. 7. The post-reaction treatment process for cyclododecatriene preparation according to claim 1, wherein the mass ratio of the first oil phase to the alkali solution is 5-30.
8. 8. The post-reaction treatment process for cyclododecatriene preparation according to claim 7, wherein the mass ratio of the first oil phase to the alkali solution is 10-20.
9. 9. The post-reaction treatment process for cyclododecatriene preparation according to claim 1, wherein the alkali liquor is sodium hydroxide or calcium hydroxide solution, and the mass concentration of the alkali liquor is 10% -20%.
10. 10. The post-reaction treatment process for cyclododecatriene production according to claim 1, wherein the mass ratio of the second oil phase to the pure water is 5-15.
11. 11. The post-reaction treatment process for cyclododecatriene production of claim 10, wherein the mass ratio of the second oil phase to the pure water is 10-15.
12. 12. The post-reaction treatment process for cyclododecatriene production according to claim 1, wherein the first aqueous phase obtained in the primary extraction step and the second aqueous phase obtained in the secondary extraction step are fed to a subsequent wastewater treatment step.

Description

Post-treatment process and system for cyclododecatriene preparation reaction Technical Field The invention relates to the technical field of chemical synthesis, in particular to a post-treatment process and a post-treatment system for cyclododecatriene preparation reaction. Background Cyclododecatriene is abbreviated as CDT and generally refers to 1,5, 9-cyclododecatriene, which includes three isomers, i.e., trans-CDT, trans-CDT, and trans-cis-CDT. CDT can be used for preparing polyesters, polyamides and plasticizers, and for producing polyamide synthetic fibers, cold-resistant plasticizers, elastomers, flavoring agents, epoxy resin crosslinking agents, fragrances, fire-resistant additives and the like, and is an important industrial raw material. In the existing CDT preparation process, 1, 3-butadiene is adopted as a raw material, and is polymerized under the action of a Ziegler-Natta catalyst system to generate a mixture of two or three isomers of CDT. Wherein the Ziegler-Natta catalyst is a directional polymerization catalyst composed of aluminum alkyl and titanium compound, and in the process of preparing CDT by oligomerization of butadiene under the catalysis of the Ziegler-Natta catalyst, the common aluminum alkyl is aluminum sesquiethoxide chloride, and the titanium compound is titanium tetrachloride. After the CDT preparation reaction is finished, the catalyst must be deactivated, otherwise, the catalyst with activity will cause CDT side reaction in the subsequent rectification process, reduce CDT recovery rate and increase byproducts, and also threaten the safety of the subsequent process. Patent CN103420777a proposes a method for continuously synthesizing 1,5, 9-cyclododecatriene, wherein the deactivator adopted in the method is C1-C5 alcohols, sodium hydroxide aqueous solution, trisodium citrate aqueous solution, or sodium methoxide, 10% -5% sodium hydroxide aqueous solution. It is worth noting that the C1-C5 alcohols react with aluminum alkyl and titanium tetrachloride to generate hydrogen chloride, the existence of the hydrogen chloride can cause corrosion of equipment, the sodium hydroxide solution reacts with the aluminum alkyl to generate sodium chloride salt, if organic matters are not removed, titanium oxide solid particles are generated by the reaction of the titanium tetrachloride and water to cause blockage of the equipment, and in addition, the C1-C5 alcohols belong to low-boiling-point substances, so that the subsequent separation burden is increased. Patent CN112521247a discloses a post-treatment method of cyclododecatriene reaction solution, which mixes thiol compound with alkaline auxiliary agent to obtain quencher, and uses the characteristic that mercapto group is easy to form complex with active center of titanium and aluminum to inactivate catalyst. In the method, an alkaline auxiliary agent is added into the quenching agent to neutralize hydrogen chloride generated by the quenching reaction, but the alkaline auxiliary agent and alkyl aluminum react to generate salt, so that the subsequent rectifying and separating difficulty and the quality of CDT products are further influenced. Disclosure of Invention Aiming at the defects in the prior art, the invention discloses a post-treatment process and a post-treatment system for cyclododecatriene preparation reaction, which are used for inactivating a catalyst in CDT reaction liquid, can avoid the problems of equipment blockage, hydrogen chloride corrosion and organic matter salt content caused by quenching of the catalyst, and are reliable in process and suitable for continuous industrial operation. In order to achieve the technical aim, on the one hand, the invention provides a post-treatment process for cyclododecatriene preparation reaction, which comprises a termination process, a first-stage extraction process and a second-stage extraction process, wherein the termination process comprises the steps of mixing a terminator with CDT reaction liquid to perform catalyst quenching to obtain a first mixed material, the terminator comprises alcohols, phenols or mixed liquid of the alcohols and the phenols, the first-stage extraction process comprises the steps of extracting the first mixed material after cooling operation by alkali liquor, inputting the obtained first oil phase into the second-stage extraction process, extracting the first oil phase by pure water, and inputting the obtained second oil phase into the subsequent rectification separation process to purify to obtain a high-purity cyclododecatriene product. The technical scheme of the invention adopts alcohol, phenol or mixed solution of alcohol and phenol as a terminator, utilizes hydroxyl of alcohol or phenol to terminate the activity of the Ziegler-Natta catalyst, does not add alkaline auxiliary agent, can avoid generating impurity salt due to the reaction of alkaline substance and aluminum alkyl, and can avoid using alkaline substance aqueous solution as alkaline auxil