阅读说明：本技术 一种连续制备二环己基并-18-冠-6-醚及其衍生物的方法 (Method for continuously preparing dicyclohexyl-18-crown-6-ether and derivative thereof ) 是由 叶钢 贾建峰 王建晨 陈靖 于 2020-06-24 设计创作，主要内容包括：本发明公开了一种连续制备二环己基并-18-冠-6-醚及其衍生物的方法,包括,将二苯并-18-冠-6-醚类化合物溶于有机溶剂得到反应料液,加入到填充有负载型催化剂的固定床反应器中,通入氢气后连续加氢反应,回收固定床反应器的出口料液中的有机溶剂即可；有机溶剂的加入量为控制所述反应料液的浓度为1-200g/L,加氢反应的反应温度和反应压力分别为50-200℃和1-10Mpa。本发明通过利用填充有负载型催化剂的固定床反应器连续流加氢,能有效提高二苯并-18-冠-6-醚类化合物的加氢效率,反应安全性和反应效率大幅度提高；通过优化负载型催化剂的种类,可提高产物中顺式异构体的比例。(The invention discloses a method for continuously preparing dicyclohexyl-18-crown-6-ether and derivatives thereof, which comprises the steps of dissolving a dibenzo-18-crown-6-ether compound in an organic solvent to obtain a reaction liquid, adding the reaction liquid into a fixed bed reactor filled with a supported catalyst, introducing hydrogen, carrying out continuous hydrogenation reaction, and recovering the organic solvent in the outlet liquid of the fixed bed reactor; the adding amount of the organic solvent is controlled to control the concentration of the reaction feed liquid to be 1-200g/L, and the reaction temperature and the reaction pressure of the hydrogenation reaction are respectively 50-200 ℃ and 1-10 Mpa. According to the invention, the hydrogenation efficiency of the dibenzo-18-crown-6-ether compound can be effectively improved by utilizing the continuous flow hydrogenation of the fixed bed reactor filled with the supported catalyst, and the reaction safety and the reaction efficiency are greatly improved; by optimizing the type of supported catalyst, the proportion of cis-isomers in the product can be increased.)

1. A method for continuously preparing dicyclohexyl-18-crown-6-ether and derivatives thereof is characterized in that,

dissolving a dibenzo-18-crown-6-ether compound in an organic solvent to obtain a reaction feed liquid, adding the reaction feed liquid into a fixed bed reactor filled with a supported catalyst, introducing hydrogen to carry out continuous hydrogenation reaction, and recovering the organic solvent in the feed liquid at the outlet of the fixed bed reactor;

the supported catalyst comprises active metal and a carrier for loading the active metal, wherein the active metal is ruthenium and/or rhodium, and the carrier is active carbon or a metal oxide porous material.

2. The method of claim 1,

the organic solvent is one or more of tetrahydrofuran, n-butanol, n-octanol, ethylene glycol, dichloromethane, trichloromethane, dichloroethane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and toluene;

preferably, the adding amount of the organic solvent is controlled to control the concentration of the reaction feed liquid to be 1-200g/L, and preferably 50-100 g/L.

3. The method according to claim 1 or 2,

the reaction temperature of the hydrogenation reaction is 50-200 ℃, and preferably 100-140 ℃;

and/or the reaction pressure of the hydrogenation reaction is 1-10Mpa, preferably 3-6 Mpa.

4. The method of claim 3,

the introduction amount of the hydrogen is 10-200 times of that of the dibenzo-18-crown-6-ether compound by controlling the amount of the hydrogen.

5. The method of claim 1,

in the supported catalyst, the loading amount of the active metal is 1-20 wt%, preferably 5-15 wt%;

preferably, the supported catalyst further comprises an additive supported on the carrier, the additive being an alkali metal salt and/or an alkaline earth metal salt.

6. The method of claim 5,

the loading amount of the additive is controlled to be 0.1 to 10 times, preferably 0.5 to 2 times of the molar amount of the active metal.

7. The method according to any one of claims 1 to 6,

the supported catalyst is prepared by the following method:

weighing an active metal precursor and a carrier according to a proportion, adding water to the active metal precursor for dissolving, uniformly mixing, dipping the active metal precursor on the carrier, drying, and then heating and reducing in an atmosphere furnace;

wherein, the atmosphere in the atmosphere furnace is at least one of nitrogen, argon, hydrogen and helium, and preferably nitrogen or argon.

8. The method of claim 7,

in the preparation process of the supported catalyst, the method further comprises the steps of weighing additives in proportion, uniformly mixing the additives with the active metal precursor solution, and dipping the mixture onto the carrier.

9. The method according to claim 7 or 8,

during the preparation of the supported catalyst,

the temperature and the time of the heating reduction reaction are respectively 200-800 ℃ and 1-10 h;

preferably, the temperature and time of the heating reduction reaction are 500 ℃ and 2-5h respectively.

10. The method according to any one of claims 5 to 9,

the active metal precursor is one or more of ruthenium chloride, ruthenium acetate, potassium ruthenate, ruthenium nitrate, rhodium chloride, rhodium acetate and rhodium nitrate;

preferably, the additive is one or more of salts of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba.

Technical Field

The invention relates to the technical field of synthesis of crown ether compounds, in particular to a method for continuously preparing dicyclohexyl-18-crown-6-ether and derivatives thereof.

Background

Crown ethers, which have been discovered and synthesized by Pederson in 1967 due to their excellent ability to complex alkali and alkaline earth metal cations, have been widely used in many fields such as coordination chemistry, extractive chemistry, organic catalysis, and nuclear fuel reprocessing.

Bicyclohexylo-18-crown-6-ethers and derivatives thereof⁹⁰Sr²⁺The extractive separation of (2) shows great advantages; particularly, di-tert-butyl dicyclohexyl-18-crown-6-ether has more practical application value in the aspect of radioactive waste liquid post-treatment due to excellent extraction and separation capacity and good oil solubility and stability.

Currently, dicyclohexyl-18-crown-6-ether compounds are mainly produced by catalytic hydrogenation of dibenzo-18-crown-6-ether compounds.

Chinese patent application publication No. CN102516222A discloses that di-tert-butyldibenzo-18-crown-6-ether is subjected to hydrogenation reduction in a reaction kettle using a carbon-supported ruthenium catalyst, and reacted at 130 ℃ under 7MPa for 8 hours to obtain di-tert-butyldicyclohexyl-18-crown-6-ether, the yield of which is 94%.

Chinese patent application publication No. CN102336737A discloses that hydrogenation reduction is performed on alkyl-substituted benzo crown ether in a low-reducing solvent by using a Pichler ruthenium catalyst, so that the problem that the catalyst is difficult to separate from the product due to particle refinement under high temperature and high pressure conditions is avoided, and a series of alkyl-substituted dicyclohexyl crown ether products with purity of more than 90% are obtained.

The Chinese patent application with the publication number of CN104710402A discloses the use of a supported Ni-Ru/gamma-Al₂O₃The catalyst reacts for 30 hours under the pressure of 8MPa to obtain the di-tert-butyl dicyclohexyl-18-crown-6-ether with the yield of about 92 percent, hydrogen needs to be continuously supplemented during the reaction period to ensure the reaction pressure, and the activity of the catalyst is obviously reduced after the catalyst is circularly reused for two times.

So far, no report about the continuous preparation of dicyclohexyl-18-crown-6-ether and its derivatives is available.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention makes up the defects of the prior art, provides a method for continuously preparing dicyclohexyl-18-crown-6-ether and derivatives thereof, and aims to improve the synthesis efficiency of the dicyclohexyl-18-crown-6-ether and the derivatives thereof based on a stable and efficient supported catalyst and combined with continuous flow catalytic hydrogenation reaction, and simultaneously avoid the problems of high kettle type reaction pressure, long reaction time, large product batch difference, flammability of the catalyst, low reuse rate and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a process for the continuous preparation of dicyclohexyl-18-crown-6-ether and its derivatives, comprising,

dissolving dibenzo-18-crown-6-ether compounds in an organic solvent to obtain a reaction feed liquid, adding the reaction feed liquid into a fixed bed reactor filled with a supported catalyst, introducing hydrogen to carry out continuous hydrogenation reaction, and recovering the organic solvent from the feed liquid at the outlet of the fixed bed reactor.

Specifically, the supported catalyst comprises an active metal and a carrier for supporting the active metal, wherein the active metal is ruthenium and/or rhodium, and the carrier is an active carbon or metal oxide porous material.

Specifically, the dicyclohexyl-18-crown-6-ether compound has the following general formula:

wherein R is₁And R₂Can be respectively-H and-NH₂、-NO₂、-OCH₃And alkyl groups having 3 to 8 carbon atoms.

In the technical scheme, the organic solvent is one or more of tetrahydrofuran, n-butanol, n-octanol, ethylene glycol, dichloromethane, trichloromethane, dichloroethane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and toluene.

Preferably, in the above technical solution, the adding amount of the organic solvent is to control the concentration of the reaction feed liquid to be 1-200g/L, preferably 50-100 g/L.

Further, in the above technical scheme, the reaction temperature of the hydrogenation reaction is 50-200 ℃, preferably 100-140 ℃.

Further, in the above technical scheme, the reaction pressure of the hydrogenation reaction is 1-10Mpa, preferably 3-6 Mpa.

In another preferred embodiment of the present invention, the amount of the hydrogen gas is controlled to be 10 to 200 times that of the dibenzo-18-crown-6-ether compound.

In the above technical solution, in the supported catalyst, the supported amount of the active metal is 1 to 20 wt%, preferably 5 to 15 wt%.

Preferably, in the above technical solution, the supported catalyst further comprises an additive supported on the carrier, and the additive is an alkali metal salt and/or an alkaline earth metal salt.

Further, in the above technical solution, the loading amount of the additive is controlled to be 0.1 to 10 times, preferably 0.5 to 2 times of the molar amount of the active metal.

Still further, in the above technical solution, the supported catalyst is prepared by the following method:

weighing the active metal precursor and the carrier according to the proportion, adding water to the active metal precursor for dissolving, uniformly mixing, dipping the active metal precursor on the carrier, drying, and then heating and reducing in an atmosphere furnace.

Wherein, the atmosphere in the atmosphere furnace is at least one of nitrogen, argon, hydrogen and helium, and preferably nitrogen or argon.

Still further, in the above technical solution, in the preparation process of the supported catalyst, the method further comprises weighing additives in proportion, mixing the additives with the active metal precursor solution uniformly, and impregnating the mixture onto the carrier.

Specifically, in the above technical scheme, in the preparation process of the supported catalyst, the temperature and time of the heating reduction reaction are 200-.

In a preferred embodiment, the temperature and time of the heating reduction reaction during the preparation of the supported catalyst are 500 ℃ and 2-5h, respectively.

Still further, in the above technical solution, the active metal precursor is one or more of ruthenium chloride, ruthenium acetate, potassium ruthenate, ruthenium nitrate, rhodium chloride, rhodium acetate, and rhodium nitrate.

Preferably, in the above technical solution, the additive is one or more of salts of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba.

The invention also provides the application of the method in radioactive waste liquid treatment.

The invention has the following advantages:

(1) the invention provides a preparation method of a supported catalyst, and the prepared supported catalyst has excellent catalytic activity, so that a plurality of high-efficiency catalysts which can be stably catalyzed for a long time and have the conversion rate of more than 95 percent are provided, and the conversion efficiency of a dibenzo-18-crown-6-ether compound in the catalytic hydrogenation process is improved;

(2) according to the invention, the hydrogenation efficiency of the dibenzo-18-crown-6-ether compound can be effectively improved by utilizing the continuous flow hydrogenation of the fixed bed reactor filled with the supported catalyst, compared with the kettle type reaction in the prior art, the reaction safety and the reaction efficiency are greatly improved, and in addition, the fixed bed mode is adopted to be fixed in the reactor, so that the problem of separation and recovery of the catalyst is avoided;

(3) the preparation method of the supported catalyst provided by the invention is simple and can be repeatedly used, the repeated utilization rate is greatly improved, and the reaction cost is reduced, so that the requirement of industrial production can be met;

(4) the method for continuously preparing dicyclohexyl-18-crown-6-ether and the derivatives thereof can effectively improve the proportion of cis-isomers in hydrogenation products, and has important theoretical and practical application.

Drawings

FIG. 1 is a gas chromatogram of di-tert-butyldicyclohexyl-18-crown-6 ether prepared in example 4 of the present invention;

FIG. 2 is a gas chromatogram of di-t-butyldicyclohexyl-18-crown-6 ether prepared in example 6 of the present invention.

Detailed Description

The following describes the embodiments of the present invention in further detail with reference to specific examples.

The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

The experimental procedures used in the following examples are conventional unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.