CN118894819A

CN118894819A - A production process and system for epoxycycloalkanes

Info

Publication number: CN118894819A
Application number: CN202410824138.7A
Authority: CN
Inventors: 史文涛; 王聪; 刘新伟; 靳权; 冯传密
Original assignee: China Tianchen Engineering Corp
Current assignee: China Tianchen Engineering Corp
Priority date: 2024-06-25
Filing date: 2024-06-25
Publication date: 2024-11-05

Abstract

The invention provides a production process and a system of epoxy cycloalkane, wherein the process comprises an oxidation process, a first refining process, a hydrogenation process and a second refining process, wherein the oxidation process is carried out in N reaction kettles which are connected in series, and a discharge port of the last reaction kettle is connected with a feed port of the next reaction kettle; inputting raw material cycloolefin and solvent into a feed inlet of a1 st reaction kettle, dividing oxidant hydrogen peroxide into N-1 parts, and respectively adding the N-1 st reaction kettle to the N-1 st reaction kettle; outputting a first material after the oxidation reaction from a discharge hole of the last 1 reaction kettles; the unreacted cycloolefin separated in the first refining step is returned to the oxidation step; the molar ratio of the cycloolefin to the hydrogen peroxide is (2-7): 1. the invention sets a plurality of cooperative technical characteristics to improve the effective utilization rate of hydrogen peroxide, the product yield and the complete reaction of hydrogen peroxide, is a safe and high-yield process suitable for large-scale industrial production.

Description

Production process and system of epoxy cycloalkane

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a production process and a system of epoxy cycloalkane.

Background

The epoxy cycloalkane is an important fine chemical, can be used for synthesizing high molecular prepolymer, epoxy resin curing agent, nonionic surfactant and the like, and has wide application in the fields of petroleum, chemical industry, pesticide, daily chemicals, medicine, long carbon chain nylon synthesis and the like. The epoxy cycloalkane is mainly prepared by oxidizing corresponding cycloolefin, and the preparation method of the epoxy cycloalkane comprises a chlorohydrin method, an organic peroxyacid oxidation method, a hydrogen peroxide method, an alkyl peroxide oxidation method, an air/oxygen oxidation method and the like according to different oxidants.

The chlorohydrin method is to take cycloolefin and hypochlorous acid as raw materials, generate chlorohydrin through addition reaction, and then generate elimination reaction with alkali liquor to generate corresponding epoxy cycloparaffin; the method is being phased out because it produces a large amount of chlorine-containing sewage in production and hypochlorous acid causes corrosion of equipment, thereby causing pollution problems and economic degradation. The organic peroxyacid oxidation method is one of the more common methods, and the organic peroxyacid is usually prepared by reacting hydrogen peroxide with corresponding carboxylic acid; because the organic peroxyacid has unstable chemical structure and is easy to decompose, in practical application, hydrogen peroxide and carboxylic acid are usually reacted in advance to generate peroxyacid, and then the generated peroxyacid is mixed with cycloolefin to react, so that epoxy cycloparaffin is generated. The alkyl peroxide oxidation method uses alkyl peroxide as an oxygen source, and compared with organic peroxyacid, the alkyl peroxide has higher stability and safety and is easily dissolved in an organic solvent, is commonly used as an oxidant for olefin epoxidation, and is commonly used in the prior art, and comprises Cumene Hydroperoxide (CHP), tert-butyl hydroperoxide (TBHP) and the like.

In addition, the cycloolefin oxidation method using hydrogen peroxide as an oxygen source is green and pollution-free, no impurity ions are introduced in the reaction process, only water and oxygen are generated after the decomposition, equipment corrosion and environmental pollution are not caused, the raw materials are low in cost, and the competitiveness is strong; classical oxydol direct oxidation process (HPPO) for preparing propylene oxide has been used industrially. There have been a great deal of research on cycloolefin oxidation methods using hydrogen peroxide as a raw material:

Patent CN105315140A relates to a preparation method of cyclododecane, which takes cyclododecene as a raw material and takes hydrogen peroxide as an oxidant to perform oxidation reaction under an acidic environment to obtain cyclododecane; in the method, hydrogen peroxide used in the epoxidation reaction is a water phase, CDEN is an oil phase, and the mixing effect of the two phases is poor; to enhance the reaction, the process employs a phase transfer catalyst and a metal salt to promote the oxidation process; the phase transfer catalyst is generally a compound such as a quaternary ammonium salt or an organic phosphine, which is expensive and increases the complexity of the reaction operation.

Patent CN113444058a provides a method for continuously oxidizing alicyclic epoxy compounds by using a micro-channel reactor, which comprises emulsifying alicyclic olefins and hydrogen peroxide in an emulsifier to form an emulsion, and continuously introducing the emulsion into the micro-reactor to perform oxidation reaction to obtain the corresponding target product. The method ensures the uniformity of a reaction system through the combination of the micro-emulsifier and the micro-reactor, avoids the problem of poor mixing effect, realizes higher reaction conversion rate and yield of the preparation of the alicyclic epoxy compound, but has smaller reaction flux of the micro-channel reactor and is difficult to adapt to the production of da Zong chemicals.

Patent CN112321539a provides a method for epoxidation of macrocyclic olefins using hydrogen peroxide as the oxidant. In the method, hydrogen peroxide, a stabilizer, a catalyst, a solvent and macrocyclic olefin are placed into an oxidation reactor to form a mixed solution for reaction, and the problems of low hydrogen peroxide utilization rate, multiple side reactions, complex catalyst recovery and the like in the traditional process are solved, but the method has the advantages of numerous reaction components, complex components and difficult subsequent separation.

Patent EP0033763B1 provides a process for the preparation of cyclododecadiene of epoxy type, mainly by reaction of cyclododecatriene with peroxyformic acid, which is directly formed by the reaction of formic acid with hydrogen peroxide. In the method, hydrogen peroxide is added in excess relative to cyclododecatriene, so that the conversion rate of raw materials can be improved, but the effective utilization rate of hydrogen peroxide is reduced. Notably, hydrogen peroxide is unstable and self-decomposition occurs during use to produce pure oxygen; in the organic matter production process, pure oxygen enrichment may bring fire or explosion risks to the production system, so that excessive hydrogen peroxide is added in the method, the explosion risks in the process are increased, and the production safety is reduced.

Disclosure of Invention

Aiming at the defects in the prior art, the invention discloses a production process and a production system of epoxy cycloalkane, wherein cycloolefin is used as a raw material, hydrogen peroxide is used as an oxidant, the full reaction of hydrogen peroxide can be promoted, the process safety is ensured, the product yield is improved, and the production process and the production system are suitable for large-scale industrial production.

In order to achieve the above technical object, in one aspect, the present invention provides a process for producing an epoxycycloalkane, comprising the steps of

Oxidation procedure: the oxidation process is carried out in N reaction kettles connected in series, and a discharge port of the last reaction kettle is connected with a feed port of the next reaction kettle; inputting raw material cycloolefin and solvent into a feed inlet of a1 st reaction kettle, dividing oxidant hydrogen peroxide into N-1 parts, and respectively adding the N-1 st reaction kettle to the N-1 st reaction kettle; outputting a first material after the oxidation reaction from a discharge hole of the last 1 reaction kettles, wherein N is at least 2;

a first refining procedure: separating the solvent, unreacted cycloolefin and first heavy component from the first material through a first rectifying operation to obtain a second material;

Hydrogenation procedure: the second material undergoes hydrogenation reaction under the action of a hydrogenation catalyst to obtain a third material;

and a second refining procedure: the third material is subjected to gas-liquid separation in sequence to discharge unreacted hydrogen, and light components and second heavy components are separated through second rectification operation to obtain a high-purity epoxy cycloparaffin product;

wherein the unreacted cycloolefin separated in the first purification step is returned to the oxidation step; the molar ratio of the cycloolefin to the hydrogen peroxide in the hydrogen peroxide is (2-7): 1.

In the technical scheme, the raw material cycloolefin is subjected to an epoxidation reaction of olefin double bonds in an oxidation process, the raw material cycloolefin is subjected to an oxidation reaction with hydrogen peroxide to obtain an epoxy primary product, and the epoxy primary product is subjected to a hydrogenation saturation reaction of residual double bonds in a hydrogenation process to form saturated carbon-carbon bonds. According to the technical scheme, the technical characteristics of improving the effective utilization rate of the hydrogen peroxide in a cooperative manner, improving the product yield and promoting the complete reaction of the hydrogen peroxide are set:

Firstly, the oxidation reaction procedure is carried out in a plurality of reaction kettles, and the raw material cycloolefin is input from the 1 st reaction kettle, the oxidant hydrogen peroxide required by the reaction is input into each (except the last 1 reaction kettle) reaction kettle in batches, in the process, the material after the reaction of the previous reaction kettle is input into the next reaction kettle to continue the oxidation reaction with the newly input hydrogen peroxide, so that the raw material cycloolefin in each stage of reaction kettles is excessive relative to the input hydrogen peroxide, the effective utilization rate of the hydrogen peroxide is improved, and the complete reaction of the hydrogen peroxide is effectively promoted.

Further, hydrogen peroxide is only input into the 1 st to N-1 st reaction kettles, and a new oxidant is not added into the last reaction kettle, but the oxidation reaction in the N-1 st reaction kettle is continuously enhanced, so that the condition that the hydrogen peroxide in the first material is not completely reacted can be avoided, and the condition that safety accidents are caused by the fact that oxygen generated by decomposing the unreacted hydrogen peroxide in the subsequent working procedures is further avoided.

Furthermore, the research and development team of the invention discovers that the feeding mole ratio of raw material cycloolefin and hydrogen peroxide directly affects the effective utilization rate of hydrogen peroxide based on a large number of small heuristic rope experiments, and the effective utilization rate of hydrogen peroxide can be effectively improved by controlling the feeding mole ratio of cycloolefin and hydrogen peroxide to be not less than 2 (the stoichiometric relation of the cycloolefin and hydrogen peroxide is 1); based on the findings, the molar ratio of the cycloolefin to the hydrogen peroxide in the hydrogen peroxide is optimized to be (2-7) in the technical scheme: 1, the hydrogen peroxide can be promoted to react completely by excessively adding raw material cycloolefin at the beginning of the feeding in the oxidation process; furthermore, in order to improve the product yield on the premise of the excessive feeding ratio of the cycloolefin to the hydrogen peroxide, the technical scheme also sets the technical characteristics of cyclic utilization of the raw material cycloolefin, namely, the unreacted cycloolefin separated in the first refining process is returned to the oxidation process, so that the excessive cycloolefin can be used as the raw material to continuously participate in the reaction, the production cost is reduced by the cyclic utilization of the raw material, and the conversion rate of the raw material is improved, thereby simultaneously realizing high hydrogen peroxide utilization rate and high product yield.

Furthermore, the technical proposal is provided with refining procedures after the oxidation procedure and the hydrogenation procedure, and the high-purity epoxy cycloparaffin product is obtained by progressive refining, so the process flow is simple, the operability is strong, and the method is suitable for industrial production.

In a further example of the present invention, the addition amounts of the cycloolefin and the hydrogen peroxide are optimized. Optionally, the molar ratio of the cycloolefin to the hydrogen peroxide in the hydrogen peroxide is (2-3): 1, thereby realizing better hydrogen peroxide utilization rate.

In a further example of the present invention, the control conditions of the oxidation step are optimized. Optionally, the reaction temperature of the oxidation procedure is 80-110 ℃ and the pressure is 3000-6000Pa; in the oxidation process, the residence time of the reaction materials in each reaction kettle is 1-3h, so that the reaction process is controlled, and the process production efficiency is improved.

It should be noted that the catalyst used in the oxidation process is not limited in the invention, and the technical scheme formed by the method is within the scope of the invention by controlling the technological process, the raw materials and the feeding ratio of the oxidant in the production process so as to promote the complete reaction of the hydrogen peroxide and obtain high product yield, and a person skilled in the art can select a proper catalyst, such as a selectable TS-1 titanium silicon analysis sieve catalyst, through non-creative labor.

It should be noted that the specific structure of each stage of reaction kettle in the oxidation process is not limited in the invention, in a further example of the invention, a jacket or a built-in coil pipe of the reaction kettle can be optionally configured to control the reaction temperature, the oxidation reaction can be optionally performed under the stirring condition, and other technical features for promoting temperature and pressure control can be set by a person skilled in the art through non-creative labor, so that the formed technical scheme is within the protection scope of the invention.

It should be noted that the production process of the invention is not limited to the distribution amount and the addition rate of the oxidant in the total N-1 reaction kettles, and the oxidant average amount can be selected and uniformly input into the total N-1 reaction kettles so as to be convenient for integral regulation and control, or the total N-1 reaction kettles are input in a mode that the addition amount is gradually reduced, so that the feeding amount of the raw material cycloolefin is matched with the continuous reduction working condition from the 1 st reaction kettle to the N-1 reaction kettle, or the hydrogen peroxide feeding condition of each kettle is regulated according to the actual working condition; the addition of the oxidizing agent can be monitored and regulated by a flow meter during the actual process.

In a further example of the invention, a catalyst filtration process is provided after the oxidation process, optionally with a membrane filtration device or other filtration device, to filter, separate and remove catalyst entrained in the first material to facilitate the efficiency of the subsequent polishing process.

In a further example of the invention, the concentration of the hydrogen peroxide is 25-70wt%, preferably 30-50wt%, and the reaction is ensured to be carried out along a specific path by optimizing the concentration of the hydrogen peroxide, so that the reaction rate and the efficiency are convenient to control, and the operability of the process is improved.

The epoxy cycloparaffin production process has wide universality and is suitable for preparing corresponding epoxy cycloparaffin by taking a plurality of cycloolefins with different carbon atoms as raw materials; in a further example of the present invention, the cyclic olefin may be selected from cyclic mono-olefins or cyclic poly-olefins having 8 to 16 carbon atoms, and further selected from cyclic mono-olefins or cyclic poly-olefins having 12 carbon atoms; the embodiment of the invention shows the technical process for preparing the corresponding epoxycycloalkane by taking cycloolefins with different carbon numbers as raw materials.

The production process of the invention is not limited to the types of the solvents, and in a further example of the invention, the solvents can be selected to be C5-C8 alcohols, so that the compatibility of raw material cycloolefins and hydrogen peroxide is promoted, the efficient reaction is promoted, and the production efficiency is improved.

In a further example of the invention, the amount of solvent is heuristically optimized. Optionally, the mass ratio of cycloolefin to solvent is 1 (2-4), and optimizing the solvent dosage of the reaction medium improves the process stability and controllability.

In a further example of the invention, the number of reaction vessels in the oxidation process is optimized. Optionally, the number N of the reaction kettles is a natural number of 2-8, preferably a natural number of 3-6, which is favorable for promoting the full utilization of hydrogen peroxide in the oxidation process, reducing the equipment investment cost of the production process and improving the economic benefit of the production process.

In a further example of the present invention, the amount of hydrogen added in the hydrogenation step is optimized. Optionally, the molar ratio of the second material to the hydrogen in the hydrogenation procedure is 1 (2-4), and the product yield of the whole process is improved by inputting excessive hydrogen.

In a further example of the invention, the control conditions of the hydrogenation process are explored to be optimized. Optionally, the reaction temperature of the hydrogenation procedure is 80-100 ℃, and the reaction pressure is 0.1-1MPa; optionally, the feeding space velocity of the second material in the hydrogenation process is 0.5-2h ^-1.

The type of catalyst used in the hydrogenation step in the production process of the present invention is not limited, and one skilled in the art can select a suitable type of hydrogenation catalyst in the actual process. In a further optional example of the present invention, the catalyst in the hydrogenation procedure may be a supported catalyst comprising an active component and a carrier, where the active component may include one or more of Pt, pd, and Ru, so as to improve hydrogenation efficiency; it should be noted that the specific preparation process of the catalyst used in the present invention may be selected from: loading the noble metal nitrate or chloride on a carrier, drying and calcining to form a catalyst finished product, wherein the noble metal exists in an oxidation state; the finished catalyst product is loaded into a reactor, and hydrogen is used for pre-reduction operation before use, so that the oxidation state is reduced to the metal state. Optionally, the carrier comprises one or more of alumina, silica and magnesia.

In a further example of the present invention, the solvent separated in the first refining step is rectified and purified and then returned to the oxidation step, and the solvent is circulated to reduce the process cost. In still further examples of the present invention, the temperature at the top of the solvent rectification purification column may be selected to be 30-60 ℃, the temperature at the bottom of the column may be selected to be 90-120 ℃, the pressure at the top of the column may be selected to be 0.5-1mpa, and the reflux ratio may be selected to be 20-30.

In a further example of the present invention, the hydrogen gas discharged from the gas-liquid separation in the second refining step is returned to the hydrogenation step, so that raw material waste is avoided, and the raw material utilization rate is improved.

In a further example of the present invention, the second heavy component separated in the second refining step is returned to the first refining step, and the target product in the second heavy component is recycled, thereby improving the product yield.

In a further example of the invention, control conditions of the first and second rectification operations are heuristically optimized. Optionally, the first rectification operation includes a primary rectification column rectification, a secondary rectification column rectification and a tertiary rectification column rectification; further alternatively, the temperature of the rectifying tower top of the primary rectifying tower is 50-90 ℃, the temperature of the tower kettle is 150-200 ℃, the pressure of the tower top is 0.5-1bar, and the reflux ratio is 0.5-1; further alternatively, the temperature of the top of the rectifying tower of the secondary rectifying tower is 100-140 ℃, the temperature of the tower kettle is 150-200 ℃, the pressure of the top of the tower is 0.1-0.5bar, and the reflux ratio is 1-5; further alternatively, the temperature of the top of the rectifying tower of the three-stage rectifying tower is 100-150 ℃, the temperature of the tower kettle is 160-210 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 5-20. Optionally, the second rectification operation comprises a four-stage rectification column rectification and a five-stage rectification column rectification; further alternatively, the temperature of the top of the rectifying tower of the four-stage rectifying tower is 90-120 ℃, the temperature of the tower kettle is 150-180 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 20-30; further alternatively, the temperature of the top of the rectifying tower of the five-stage rectifying tower is 120-140 ℃, the temperature of the tower kettle is 150-180 ℃, the pressure of the top of the tower is 0.01-0.1bar, the reflux ratio is 5-20, and the separation efficiency can be improved, the product loss is avoided, and the product purity is improved through optimizing the control conditions.

In another aspect, the present invention provides a system for producing epoxycycloalkanes, the system comprising the following units:

An oxidation unit: the device comprises N reaction kettles which are connected in series, wherein a discharge hole of the last reaction kettle is connected with a feed hole of the next reaction kettle, the 1 st reaction kettle is connected with a raw material cycloolefin input pipe and a solvent input pipe, the 1 st to N-1 st reaction kettles are connected with a hydrogen peroxide input pipe, and the N th reaction kettle is provided with a discharge hole for outputting materials after oxidation reaction;

A first refining unit: the device comprises at least one rectifying tower, wherein a discharge port of the Nth reaction kettle is connected with a feed port of a first rectifying tower of the first refining unit;

hydrogenation unit: the device comprises a hydrogenation reactor, wherein the top outlet of the last rectifying tower of the first refining unit is connected with the raw material inlet of the hydrogenation reactor, and the hydrogenation reactor is also connected with a hydrogen input pipe;

A second refining unit: the hydrogenation device comprises a gas-liquid separation device and at least one rectifying tower, wherein a discharge port of the hydrogenation reactor is connected with a feed port of the gas-liquid separation device, and a liquid phase outlet of the gas-liquid separation device is connected with a feed port of a first rectifying tower of the second refining unit; and the top outlet of the last rectifying tower of the second refining unit outputs a high-purity epoxy naphthene product. .

It should be noted that the type and structure of the reactors used in the hydrogenation process in the production process of the present invention are not limited, fixed bed reactors may be selected, tube-type fixed bed reactors may be further selected, and those skilled in the art may select a suitable hydrogenation reactor in the actual process, so that the technical solutions formed are all within the scope of the present invention. The invention also does not limit the specific structure of the gas-liquid separation device, and a person skilled in the art can select a proper device according to specific working conditions to carry out gas-liquid separation on the material after hydrogenation reaction, so that the formed technical scheme is within the protection scope of the invention. Further, it will be understood by those skilled in the art that the specific structure, number, etc. of the rectifying towers of the first refining unit and the second refining unit are not limited, and may be set according to practical situations.

Further, N is a natural number of 2 to 8, preferably a natural number of 3 to 6.

Further, a filter device is arranged on a pipeline connecting the Nth reaction kettle and the first rectifying tower and used for separating out the catalyst in the material after the oxidation reaction so as to facilitate the subsequent separation and purification. Furthermore, a filtering device is arranged on the pipeline connecting the two adjacent reaction kettles. It should be noted that the specific structure of the filtering device is not limited in the present invention, and a person skilled in the art may select a suitable device according to specific working conditions to filter and separate the catalyst entrained in the material input from the reaction kettle, for example, the filtering device may be a filtering membrane, and thus all the technical solutions formed are within the scope of the present invention.

Further, the solvent purifying and rectifying tower is further included, when the first refining unit comprises at least 2 rectifying towers, the tower top extraction port of the first rectifying tower is connected with the feed inlet of the solvent purifying and rectifying tower, and the tower bottom extraction port of the solvent purifying and rectifying tower is connected with the feed inlet of the 1 st reaction kettle, so that solvent recycling is realized.

Further, the device also comprises a solvent purifying and rectifying tower, when the first refining unit comprises at least 3 rectifying towers, the tower top extraction port of the first rectifying tower is connected with the feed inlet of the solvent purifying and rectifying tower, and the tower bottom extraction port of the solvent purifying and rectifying tower is connected with the feed inlet of the 1 st reaction kettle, so that the solvent can be recycled; the top extraction ports of the rectifying towers except the first rectifying tower and the last rectifying tower are connected with the feeding port of the 1 st reaction kettle, cyclic olefin is recycled, and the product yield is improved.

Further, a gas phase outlet of the gas-liquid separation device is connected with a hydrogen inlet of the hydrogenation reactor, raw material hydrogen is recycled, and the raw material utilization rate is improved.

Further, the tower kettle extraction outlet of the last rectifying tower of the second refining unit is connected with the feeding port of the third rectifying tower, products are recycled, and the product yield is improved.

Further, the first refining unit comprises a first rectifying tower, a second rectifying tower and a third rectifying tower which are sequentially connected, the discharge port of the N-th reaction kettle is connected with the feed inlet of the first rectifying tower, and the top extraction port of the third rectifying tower is connected with the raw material inlet of the hydrogenation reactor.

Further, the second refining unit comprises a fourth rectifying tower and a fifth rectifying tower which are connected in sequence.

Compared with the prior art, the invention has the beneficial effects that:

The production process of the invention takes cycloolefin as raw material and double oxidation as oxidant, and obtains high-purity epoxy cycloparaffin product through oxidation procedure, first refining procedure, hydrogenation procedure and second refining procedure, the invention sets a plurality of synergistic promotion hydrogen peroxide effective utilization rate, promotes product yield, the method has the technical characteristics of promoting the complete reaction of the hydrogen peroxide, and realizes the effective utilization and full utilization of the hydrogen peroxide by adding the cycloolefin which is excessive relative to the hydrogen peroxide and combining specific reaction equipment, a hydrogen peroxide adding mode and the cyclic utilization of raw materials, thereby being a process which is safe, high in yield and suitable for large-scale industrial production; the production system of the epoxy cycloalkane has low equipment investment, safety, high efficiency and strong operability, and is suitable for industrial production.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:

FIG. 1 shows a structure and a process flow diagram of a production system of an epoxycycloalkane of the present invention.

FIG. 2 shows a detailed block diagram of the oxidation unit of FIG. 1;

Wherein the above figures include the following reference numerals:

1-oxidation unit, 11-reaction kettle, 12-raw material cycloolefin input pipe, 13-hydrogen peroxide input pipe, 14-solvent input pipe, 15-first material mixer, 111-1 st reaction kettle, 112-N-1 st reaction kettle, 113-N reaction kettle; 2-a first rectifying unit, 21-a first rectifying tower, 22-a second rectifying tower and 23-a third rectifying tower; 3-hydrogenation unit, 31-hydrogenation reactor, 32-hydrogen input pipe, 33-second material mixer; 4-second refining unit, 41-gas-liquid separation device, 42-fourth rectifying tower and 43-fifth rectifying tower; 5-a filtration device; 6-a solvent purification column;

S1-1 raw material cycloolefin, S1-2 solvent, S1-3 hydrogen peroxide, S1-4 first material, S1-5 primary refined material flow S1-6 raw material and solvent mixture flow, and S1-7 reaction kettle gas phase product; the method comprises the steps of S2-1 crude solvent, a stream after S2-2 solvent separation, S2-3 unreacted cycloolefin, a material after S2-4 solvent separation and unreacted raw materials, S2-5 second material and S2-6 first heavy component; s3-1 third material, S3-2 gas phase, S3-3 new input process hydrogen and S3-4 mixed hydrogen; s4-1 liquid phase, S4-2 light component, S4-3 material after separating light component, S4-4 second heavy component and S4-5 high-quality epoxy cycloparaffin product.

Detailed Description

In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to preferred embodiments thereof. It should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the invention in any way, i.e., not intended to limit the scope of the invention.

Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

It should be noted that, in the description of the preferred embodiment, unless explicitly stated and defined otherwise, the terms "first", "second", "third", "fourth", "fifth", "sixth", "first stage", "second stage", "third stage" are used for descriptive purposes only, and the specific meanings of the above terms in the present invention are understood by those skilled in the art according to specific circumstances and thus are not to be construed as limiting the present invention.

Search example

The exploring example takes the reaction of preparing epoxy cyclododecadiene (OCDT) by oxidizing Cyclododecatriene (CDT) with hydrogen peroxide as an example, and explores the influence of cycloolefin and hydrogen peroxide addition on the hydrogen peroxide utilization rate. The specific reaction is as follows:

After the reaction is finished, detecting the CDT and OCDT content in the reacted material by gas chromatography to obtain the raw material conversion rate, and further obtaining the amount of hydrogen peroxide actually participating in the cycloolefin oxidation reaction; the residual amount of hydrogen peroxide is measured by adopting an iodometric method, and then the total consumption of hydrogen peroxide is calculated by combining with the addition amount of hydrogen peroxide. The effective utilization rate of hydrogen peroxide is defined as the ratio of the amount of hydrogen peroxide participating in the oxidation of olefin to the total consumption of hydrogen peroxide.

Search example 1

300G of t-butanol solvent and 20g of TS molecular sieve were added to the reactor and stirred well. 50gCDT and 21g hydrogen peroxide (50%) were slowly added dropwise to the reactor with two peristaltic pumps, respectively, wherein the molar ratio of CDT to hydrogen peroxide was 1:1. The feeding time of the two peristaltic pumps is controlled to be 5 hours, and the reaction is finished after stirring for 1 hour after the feeding is finished. Stirring is kept all the time in the reaction process, and the temperature is controlled at 80 ℃ and the pressure is controlled at 6000pa. And filtering and separating the catalyst after the reaction to obtain a final reaction solution. The reaction solution was analyzed: the CDT conversion rate was analyzed by gas chromatography, the residual amount of hydrogen peroxide in the reaction liquid was determined to be 0.59% by iodometry, and the final hydrogen peroxide effective utilization rate was calculated. The final CDT conversion rate is 70.5%, and the effective utilization rate of hydrogen peroxide is 78.8%.

Search example 2

300G of t-butanol solvent and 20g of TS molecular sieve were added to the reactor and stirred well. 50gCDT g and 15.8g hydrogen peroxide (50%) were slowly added dropwise to the above reactor with two peristaltic pumps, respectively, wherein the molar ratio of CDT to hydrogen peroxide was 1.3:1. The feeding time of the two peristaltic pumps is controlled to be 5 hours, and the reaction is finished after stirring for 1 hour after the feeding is finished. Stirring is kept all the time in the reaction process, and the temperature is controlled at 80 ℃ and the pressure is controlled at 6000pa. And filtering and separating the catalyst after the reaction to obtain a final reaction solution. The reaction solution was analyzed: the CDT conversion rate was analyzed by gas chromatography, the residual amount of hydrogen peroxide in the reaction liquid was measured by an iodometry to be 0.22%, and the final hydrogen peroxide effective utilization rate was calculated. The final CDT conversion rate is 61.5%, and the effective utilization rate of hydrogen peroxide is 86.1%.

Search example 3

300G of t-butanol solvent and 20g of TS molecular sieve were added to the reactor and stirred well. 50gCDT g hydrogen peroxide and 10.5g hydrogen peroxide (50%) were slowly added dropwise to the reactor with two peristaltic pumps, respectively, wherein the molar ratio of CDT to hydrogen peroxide was 2:1. The feeding time of the two peristaltic pumps is controlled to be 5 hours, and the reaction is finished after stirring for 1 hour after the feeding is finished. And filtering and separating the catalyst after the reaction to obtain a final reaction solution. The reaction solution was analyzed. The CDT conversion rate was analyzed by gas chromatography, the residual amount of hydrogen peroxide in the reaction liquid was measured by an iodometry to be 0.02%, and the final hydrogen peroxide effective utilization rate was calculated. Stirring is kept all the time in the reaction process, and the temperature is controlled at 80 ℃ and the pressure is controlled at 6000pa. The final CDT conversion rate is 48.7%, and the effective utilization rate of hydrogen peroxide is 98.2%.

Search example 4

300G of t-butanol solvent and 20g of TS molecular sieve were added to the reactor and stirred well. 50gCDT g of hydrogen peroxide and 7g of hydrogen peroxide (50%) are slowly added dropwise into the reactor by two peristaltic pumps respectively, wherein the molar ratio of CDT to hydrogen peroxide is 3:1. The feeding time of the two peristaltic pumps is controlled to be 5 hours, and the reaction is finished after stirring for 1 hour after the feeding is finished. Stirring is kept all the time in the reaction process, and the temperature is controlled at 80 ℃ and the pressure is controlled at 6000pa. And filtering and separating the catalyst after the reaction to obtain a final reaction solution. The reaction solution was analyzed: and (3) analyzing the CDT conversion rate by using gas chromatography, measuring the residual quantity of hydrogen peroxide in the reaction liquid by using an iodometry, and calculating the effective utilization rate of the final hydrogen peroxide. The final CDT conversion rate is 32%, and the effective utilization rate of hydrogen peroxide is 99.3%.

As known in the field, the hydrogen peroxide is generally required to be fully involved in the reaction when the effective utilization rate of the hydrogen peroxide is more than 95%, namely, the hydrogen peroxide is reacted completely. The comparative analysis and exploration examples 1-4 prove that the effective utilization rate of hydrogen peroxide can be effectively improved by more than 98% by controlling the ratio of olefin to hydrogen peroxide to be not less than 2.

Example 1

A system for producing an epoxycycloalkane, as shown in FIG. 1, which comprises an oxidation unit 1, a first purification unit 2, a hydrogenation unit 3 and a second purification unit 4, wherein,

Oxidation unit 1: referring to fig. 2, the oxidation unit 1 includes N reaction kettles 11 connected in series, and a discharge port of a previous reaction kettle 11 is connected to a feed port of a next reaction kettle 11, wherein a1 st reaction kettle 111 is connected to a raw material cycloolefin input pipe 12 and a solvent input pipe 14, 1 st to N-1 st reaction kettles 112 are connected to a hydrogen peroxide input pipe 13, and an nth reaction kettle 113 is provided with a discharge port for outputting a material after oxidation reaction.

Alternatively, N is a natural number from 2 to 8, further alternatively a natural number from 3 to 6.

The first refining unit 2: the device comprises a first rectifying tower 21, a second rectifying tower 22 and a third rectifying tower 23, wherein a discharge port of an Nth reaction kettle 113 is connected with a feed inlet of the first rectifying tower 21 through a pipe; the first rectifying tower 21 is provided with a tower top extraction port and a tower bottom extraction port, and the tower bottom extraction port is connected with a feed inlet of the second rectifying tower 22 through a pipeline; the second rectifying tower 22 is provided with a collecting outlet and a tower kettle collecting outlet, and the tower kettle collecting outlet is connected with a feeding port of the third rectifying tower 23 through a pipeline; the third rectifying tower 23 is provided with a tower top outlet and a tower bottom outlet.

Optionally, a filtering device 5 is disposed on a pipeline connecting the nth reaction kettle 113 and the first rectifying tower 21. Still further alternatively, a filtering device 5 is arranged on the pipeline connecting the two adjacent reaction kettles.

Alternatively, the top outlet of the first rectifying column 21 is connected to the feed port of the solvent purifying column 6 via a pipe, and the bottom of the solvent purifying column 6 is connected to the solvent input pipe 14 and further to the oxidation unit 1. Further optionally, a pipeline connecting the oxidation unit and the feed inlet of the solvent purification tower is also provided for inputting the gas phase generated by each reaction kettle in the reaction process into the solvent purification tower for rectification.

Alternatively, the top take-off port of the second rectifying column 22 is connected to the 1 st reaction vessel 111 via a pipe.

Further alternatively, the oxidation unit 1 further comprises a first material mixer 15, and the solvent input pipe 14 is connected with the feed inlet of the 1 st reaction kettle 111 through the first material mixer 15; the top of the second rectifying tower 22 is connected with the feed inlet of the 1 st reaction kettle 111 through the first material mixer 15; the raw material cycloolefin input pipe 12 is connected to the feed inlet of the 1 st reaction vessel 111 via the first material mixer 15.

Hydrogenation unit 3: the hydrogenation device comprises a hydrogenation reactor 31, wherein the top extraction outlet of the third rectifying tower 23 is connected with the raw material inlet of the hydrogenation reactor 31 through a pipeline, and the hydrogenation reactor 31 is also connected with a hydrogen input pipe 32.

The second refining unit 4: the device comprises a gas-liquid separation device 41, a fourth rectifying tower 42 and a fifth rectifying tower 43, wherein a discharge port of the hydrogenation reactor 31 is connected with a feed port of the gas-liquid separation device 41 through a pipeline, and a liquid phase outlet of the hydrogenation reactor is connected with the feed port of the fourth rectifying tower 42; the fourth rectifying tower 42 is provided with a tower top outlet and a tower bottom outlet, and the tower bottom outlet is connected with a feed inlet of the fifth rectifying tower 43 through a pipeline; and outputting a high-purity epoxy cycloparaffin product from a top outlet of the rectifying tower.

Alternatively, the gas phase outlet of the gas-liquid separation device 41 is connected to the hydrogen inlet of the hydrogenation reactor 31 via a pipe.

Further alternatively, the gas phase outlet of the gas-liquid separation device 41 is connected to the hydrogen inlet of the hydrogenation reactor 31 via the second material mixer 33; the hydrogen inlet 32 of the system is connected to a second material mixer 33.

Optionally, the bottom outlet of the fifth rectifying column 43 is connected to the feed inlet of the third rectifying column 23 via a pipe.

Example 2

The present example describes the production process of an epoxycycloalkane based on the epoxycycloalkane production system shown in example 1, and specifically, the production process comprises:

Oxidation procedure: the oxidation process is carried out in N reaction kettles 11 which are connected in series, and a discharge port of the last reaction kettle 11 is connected with a feed port of the next reaction kettle 11; the raw material cycloolefin S1-1 and the solvent S1-2 are input into a feed inlet of the 1 st reaction kettle 111, and the oxidant hydrogen peroxide S1-3 is divided into N-1 parts and respectively added into the 1 st to N-1 st reaction kettles 112; and outputting the first material S1-4 after the oxidation reaction from the discharge hole of the last 1 reaction kettle.

Optionally, the molar ratio of the raw material cycloolefin S1-1 to the hydrogen peroxide S1-3 in the oxidation process is (3-2): 1.

Optionally, the reaction temperature of the oxidation procedure is 80-110 ℃ and the pressure is 3000-6000Pa; in the oxidation step, the residence time of the reaction materials in each reaction kettle 11 is 1-3h.

Optionally, the oxidant is an aqueous solution of hydrogen peroxide, the concentration of which is 25-70wt%, preferably 30-50wt%.

Alternatively, the cyclic olefin is a cyclic mono-or poly-olefin having 8 to 16 carbon atoms; further optionally a cyclic mono-or poly-olefin of 12 carbon atoms.

Alternatively, the solvent S1-2 is a C5-C8 alcohol.

Alternatively, the mass ratio of the starting cycloolefin S1-1 to the solvent S1-2 is 1 (2-4).

The first material S1-4 prepared in the oxidation step comprises unreacted cycloolefin S2-3, solvent, primary epoxy product, heavy component and the like, and in this example, the first material S1-4 is separated and purified in the subsequent first refining step.

Optionally, after the first material S1-4 is filtered by the filtering device 5, the catalyst entrained in the first material S1-4 is filtered and separated to obtain a primary refined stream S1-5, and the primary refined stream S1-5 is input into the efficiency of the subsequent refining process.

A first refining procedure: the first material S1-4 is subjected to a first rectification operation to separate a solvent, unreacted cycloolefin S2-3 and a first heavy component S2-6, and a second material S2-5 is obtained.

Optionally, the first rectification operation comprises a primary rectification column rectification, a secondary rectification column rectification and a tertiary rectification column rectification;

Further alternatively, the first rectifying column rectification is performed in the first rectifying column 21, the column top temperature is 50-90 ℃, the column bottom temperature is 150-200 ℃, the column top pressure is 0.5-1bar, and the reflux ratio is 0.5-1. After the first material S1-4 is rectified by a first rectifying tower, crude solvent S2-1 is extracted from the top of the first rectifying tower 21, a material flow S2-2 after solvent separation is extracted from the tower bottom, and the material flow is input into a second rectifying tower 22 for rectifying by a second rectifying tower. Further alternatively, the temperature of the rectifying tower top of the primary rectifying tower is 50-90 ℃, the temperature of the tower bottom is 150-200 ℃, the pressure of the tower top is 0.5-1bar, and the reflux ratio is 0.5-1.

Further alternatively, the crude solvent S2-1 separated in the first refining step is purified in the solvent purifying column 6, and the solvent S1-2 is recovered from the bottom of the solvent purifying column 6 and returned to the oxidation step. Further alternatively, the temperature of the tower top for solvent rectification and purification can be 30-60 ℃, the temperature of the tower bottom can be 90-120 ℃, the pressure of the tower top can be 0.5-1bar, and the reflux ratio can be 20-30; water is extracted from the top of the solvent purification column 6 and fed to a subsequent wastewater treatment step. Still further alternatively, the reaction vessel vapor phase product S1-7 produced by the reaction vessel in the oxidation unit is fed to a solvent purification column for rectification to recover the solvent therein.

Further alternatively, the second rectifying column rectification is performed in the second rectifying column 22, the top temperature of the second rectifying column 22 is 100-140 ℃, the bottom temperature of the column is 150-200 ℃, the top pressure is 0.1-0.5bar, and the reflux ratio is 1-5. Unreacted cycloolefin S2-3 is extracted from the top of the second rectifying tower 22, and part of the material is returned to the oxidation process for recycling; and the materials S2-4 after separating the solvent and unreacted raw materials are extracted from the tower bottom of the second rectifying tower 22 are input into a third rectifying tower 23 for three-stage rectifying tower rectification.

Further alternatively, the raw material cycloolefin S1-1, the solvent S1-2 and the unreacted cycloolefin S2-3 are mixed by the first material mixer 15 to obtain a raw material and solvent mixture stream S1-6, which is fed to the oxidation process.

Further alternatively, the three-stage rectifying tower rectification is performed in the third rectifying tower 23, the tower top temperature of the third rectifying tower 23 is 100-150 ℃, the tower bottom temperature is 160-210 ℃, the tower top pressure is 0.01-0.1bar, and the reflux ratio is 5-20. A second material S2-5 containing an epoxy primary product is extracted from the top of the third rectifying tower 23, and the second material S2-5 is input into a subsequent hydrogenation process; the first heavy component S2-6 extracted from the third rectifying tower 23 tower kettle is input into the subsequent waste liquid treatment process.

Hydrogenation procedure: the second material S2-5 reacts in the hydrogenation reactor 31 under the action of a hydrogenation catalyst to obtain a third material S3-1.

Optionally, the molar ratio of the second material S2-5 to the hydrogen in the hydrogenation procedure is 1 (2-4).

Optionally, the reaction temperature of the hydrogenation process is 80-100 ℃ and the reaction pressure is 0.1-1MPa.

Optionally, the feeding space velocity of the second material S2-5 in the hydrogenation process is 0.5-2h ^-1.

Optionally, the catalyst of the hydrogenation procedure is a supported catalyst comprising an active component and a carrier, wherein the active component comprises one or more of Pt, pd and Ru. Further alternatively, the carrier comprises one or more of alumina, silica, and magnesia.

The third material S3-1 obtained after the hydrogenation reaction comprises unreacted hydrogen, light components, heavy components and target products, and the partial material is input into a second refining process for separation and purification.

And a second refining procedure: and the third material S3-1 is sequentially subjected to gas-liquid separation to discharge unreacted hydrogen, and a second rectification operation to separate a light component and a second heavy component S4-4, so that a high-purity epoxy cycloparaffin product is obtained.

Optionally, in the second refining step, gas-liquid separation is performed to obtain a gas phase S3-2, wherein the gas phase S3-2 is unreacted hydrogen, and the gas-liquid separation is performed to obtain a liquid phase S4-1, which is fed back to the hydrogenation step, and the liquid phase S4-1 is fed into the second rectifying operation. Further alternatively, unreacted hydrogen separated in the second refining process and hydrogen S3-3 newly input into the process are mixed to obtain mixed hydrogen S3-4, and the mixed hydrogen is input into the hydrogenation process.

Optionally, the second rectification operation comprises a four-stage rectification column rectification and a five-stage rectification column rectification.

Further alternatively, the four-stage rectifying column rectification is performed in the fourth rectifying column 42, the column top temperature is 90-120 ℃, the column bottom temperature is 150-180 ℃, the column top pressure is 0.01-0.1bar, and the reflux ratio is 20-30. Separating and purifying the liquid phase S4-1 after gas-liquid separation by a fourth rectifying tower 42, and extracting a light component S4-2 from the top of the fourth rectifying tower 42, wherein the light component is discharged out of the boundary region; the material S4-3 after light component separation is extracted from the tower bottom of the fourth rectifying tower 42 and is input into a fifth rectifying tower 43 for rectifying in the fifth rectifying tower.

Further alternatively, the temperature of the top of the rectifying tower of the five-stage rectifying tower is 120-140 ℃, the temperature of the tower kettle is 150-180 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 5-20. The top of the fifth rectifying column 43 is taken out of the high-quality epoxycycloalkane product S4-5, and the second component S4-4 containing the target product is taken out of the bottom of the rectifying column 43. Optionally, the second fraction S4-4 separated in the second refining step is returned to the first refining step; still further alternatively, the second fraction S4-4 is returned to the three-stage rectification column for rectification.

Example 3

Based on the production process of epoxycycloalkane shown in example 2, this example shows a production process of epoxycycloalkane under specific conditions. It should be noted that the present embodiment is only a demonstration of the preferred working condition, and the protection scope of the present invention is not limited thereby.

A process for producing epoxycycloalkanes, for example, a 1200 ton/year epoxycyclododecane production system, comprises

Oxidation procedure: the reactor is formed by connecting 4 reaction kettles 11 in series, the raw materials are cyclododecatriene 1000kg/h and solvent octanol 2000kg/h, and the cyclododecatriene and the solvent octanol are added from the inlet of the 1 st reaction kettle 111 after being mixed; 50wt% hydrogen peroxide solution 60kg/h is divided into 3 equal parts and is respectively added into the first three reactors; the temperature of the oxidation reaction is 90 ℃, the pressure is 6000pa, the retention time of single kettle materials is 1.5h, the catalyst is TS-1 catalyst, and the solid content of the titanium-silicon molecular sieve catalyst in each kettle reactor is controlled at 20%; after the reaction is finished, the water content in the first material S1-4 is 1.49%, the solvent octanol 65.18%, cyclododecatriene 27.94%, epoxy primary products (including epoxy cyclododecamono/diene and the like) 5.25%, and the other materials are 0.14%; the effective utilization rate of the hydrogen peroxide in the reaction is 99.5%, and the hydrogen peroxide in the material after detection reaction basically reacts (the hydrogen peroxide content is lower than 0.05 wt%). The first material S1-4 flows out from the bottom of the 4 th-stage reaction kettle, is filtered by a membrane filter device 5 and enters a subsequent first refining process.

A first refining procedure: the first material S1-4 enters a first rectifying tower 21 at normal temperature for separation, the top temperature of the first rectifying tower 21 is 50 ℃, the tower kettle temperature is 150 ℃, the tower top pressure is 0.5bar, and the reflux ratio is 1; crude solvent S2-1 containing water, light components and organic solvent is separated from the top of the first rectifying column 21, and the material enters a solvent purifying column 6 for separation. The temperature of the top of the solvent purification tower 6 is 30 ℃, the temperature of the tower bottom is 90 ℃, the pressure of the top of the tower is 0.5bar, the reflux ratio is 20, 89.4kg/h of wastewater separated from the top of the solvent purification tower 6 is sent out of the boundary, the concentration of octanol is 99.95%, and the solvent octanol 1955kg/h obtained by rectification in the tower bottom is recycled to the oxidation process to continue to participate in the reaction. The tower bottom material flow of the first rectifying tower 21 continuously enters a second rectifying tower 22 for separation and purification, wherein the tower top temperature of the second rectifying tower 22 is 102 ℃, the tower bottom temperature is 154 ℃, the tower top pressure is 0.5bar, and the reflux ratio is 5; unreacted cyclododecatriene with purity of 99.88% is separated from the top of the second rectifying tower 22, and returned to the reaction kettle 11 for continuous reaction; the tower bottom material of the second rectifying tower 22 enters a third rectifying tower 23 for continuous separation and purification, wherein the tower top temperature of the third rectifying tower 23 is 110 ℃, the tower bottom temperature is 161 ℃, the tower top pressure is 0.1bar, and the reflux ratio is 20; the second material S2-5 mainly containing the primary epoxy product is separated from the top of the third rectifying tower 23, the flow is 159.7kg/h, the second material S2-5 is input into the hydrogenation process for reaction, the first heavy component S2-6 extracted from the bottom of the third rectifying tower 23 is a heavy component impurity, the heavy component impurity is mainly tar, and the heavy component impurity is discharged out of the world.

Hydrogenation procedure: the second material S2-5 and 60 m ²/h hydrogen enter a hydrogenation reactor 31 to carry out hydrogenation reaction to obtain a third material S3-1, wherein the third material S3-1 mainly comprises cyclododecane oxide obtained after cyclododecadiene oxide hydrogenation; the hydrogenation reaction reactor is a fixed bed, the hydrogenation catalyst is a platinum supported catalyst, the loading amount is 1%, and the carrier is a mixture of alumina and zirconia according to the mass ratio of 1:1. The hydrogenation reaction temperature is 100 ℃, the pressure in the tower is 0.1mpa, and the space velocity is 1h ^-1.

And a second refining procedure: the third material S3-1 is input into a gas-liquid separation device 41 to obtain a gas phase S3-2 and a liquid phase S4-1, wherein the gas phase S3-2 is basically unreacted hydrogen, and the unreacted hydrogen returns to a hydrogen inlet of the hydrogenation reactor 31 to continue the reaction; the liquid phase S4-1 enters the fourth rectifying tower 42 for separation. The fourth rectifying column 42 has a column top temperature of 91 ℃, a column bottom temperature of 153 ℃, a column top pressure of 0.05bar and a reflux ratio of 30. The top effluent of the fourth rectifying column 42 is mainly light component impurities, the flow rate is 1.89kg/h, wherein cyclododecane is 56%, and the epoxycyclododecane is 43.4%. And the tower bottom extract of the fourth rectifying tower 42 enters a fifth rectifying tower 43 for rectifying separation, wherein the tower top temperature of the fifth rectifying tower 43 is 140 ℃, the tower bottom temperature is 150 ℃, the tower top pressure is 0.05bar, and the reflux ratio is 20. 155kg/h of cyclododecane product with a purity of 99.9% and a product yield of 96.4% were obtained from the top of the fifth rectifying column 43. The bottom of the fifth rectifying column 43 produced 0.98kg/h of a second heavy component S4-4 mainly comprising tar and about 43% by weight of cyclododecane, and this partial stream was returned to the third rectifying column 23 for further recovery.

Example 4

A production process of epoxy cycloalkane, taking 10000 tons/year epoxy cyclooctane production device as an example, comprising:

Oxidation procedure: the reactor is formed by connecting a 6-level reaction kettle 11 in series, the raw material is cyclooctadiene 2.2t/h and the solvent is amyl alcohol 8.8t/h, and the cyclooctadiene and the amyl alcohol are added from the inlet of the 1-level reaction kettle after being mixed; 1130kg/h of 30wt% hydrogen peroxide is divided into 5 equal parts and respectively added into the previous 5-stage reactor; the reaction temperature is 110 ℃, the reaction pressure is 5000pa, the retention time of single kettle materials is 2h, and the solid content of the titanium-silicon molecular sieve catalyst in each kettle reactor is controlled at 20%. And the first material S1-4 obtained after the reaction is finished flows out from the bottom of the 6 th-stage reaction kettle. The water content of the first material S1-4 is 8%, the solvent octanol is 72.4%, the cyclooctadiene is 9.2%, the epoxy primary product (comprising epoxy cyclooctene and the like) is 10.12%, and the other is 0.28%. The effective utilization rate of the hydrogen peroxide in the reaction is 98.9%, and the hydrogen peroxide in the material after detection reaction basically reacts (the hydrogen peroxide content is lower than 0.05 wt%). The first material S1-4 flows out from the bottom of the 5 th-stage reaction kettle 11, is filtered by the membrane filter device 5 and enters the subsequent first refining process.

A first refining procedure: the first material S1-4 enters the first rectifying tower 21 at normal temperature for separation, the temperature of the top of the first rectifying tower 21 is 59 ℃, the temperature of the tower kettle is 118 ℃, the pressure of the top of the tower is 0.9bar, and the reflux ratio is 0.5. Crude solvent S2-1 is separated from the top of the first rectifying tower 21, the organic solvent enters a solvent purifying tower 6 for separation, the temperature of the top of the tower is 90 ℃, the temperature of the tower kettle is 180 ℃, the pressure of the top of the tower is 0.5, and the reflux ratio is 0.5. 1565kg/h of organic wastewater is separated from the top of the solvent purification tower 6 and sent out of the tank, 8201kg/h of solvent amyl alcohol obtained by rectifying the tower kettle of the solvent purification tower 6, wherein the concentration of amyl alcohol is 99.95%, and the amyl alcohol is circulated back to the reaction kettle 11 to continuously participate in the reaction. The bottom stream of the first rectifying tower 21 enters a second rectifying tower 22 for separation. The second rectifying column 22 had a column top temperature of 119 ℃, a column bottom temperature of 158 ℃, a column top pressure of 0.1bar and a reflux ratio of 2; unreacted cyclooctadiene was separated from the top of the second rectifying column 22 to a purity of 99.9%, and returned to the reaction vessel 11 for further reaction. The tower bottom material of the second rectifying tower 22 enters a third rectifying tower 23 for continuous rectification separation, the temperature of the tower top of the third rectifying tower 23 is 140 ℃, the temperature of the tower bottom is 200 ℃, the pressure of the tower top is 0.01bar, the reflux ratio is 5, a second material S2-5 mainly containing cyclooctene is separated from the tower top of the third rectifying tower 23, the flow is 1214kg/h, and the second material S2-5 enters a hydrogenation process for hydrogenation reaction. The first heavy component S2-6 is extracted from the tower bottom of the third rectifying tower 23 as heavy component impurities, and the heavy component impurities are mainly tar and are discharged outside the boundary.

Hydrogenation procedure: the second material S2-5 and hydrogen with the standard m ²/h of 450 enter a hydrogenation reactor 31 to carry out hydrogenation reaction to obtain a third material S3-1, wherein the third material S3-1 mainly comprises epoxy cyclooctane; the hydrogenation reaction reactor is a fixed bed reactor, the hydrogenation catalyst is a palladium and ruthenium supported catalyst, the loading capacity is 2%, and the carrier is a mixture of magnesium oxide and aluminum oxide according to the mass ratio of 1:1. The hydrogenation reaction temperature is 80 ℃, the pressure is 0.05mpa, and the space velocity is 0.5h ^-1.

And a second refining procedure: the third material S3-1 enters a gas-liquid separation device 41 to obtain a gas phase S3-2 and a liquid phase S4-1, wherein the gas phase S3-2 is basically unreacted hydrogen, and the unreacted hydrogen returns to a hydrogen inlet of the hydrogenation reactor 31 to continue the reaction; the liquid phase S4-1 enters a fourth rectifying tower 42 for separation, wherein the temperature of the top of the fourth rectifying tower 42 is 110 ℃, the temperature of the tower kettle is 177 ℃, the pressure of the top of the tower is 0.01bar, and the reflux ratio is 20. The overhead of the fourth rectifying column 42 is mainly light-component impurities, and the flow rate is 2.24kg/h, including 53% of cyclooctane and 47% of cyclooctane. And the tower bottom product of the fourth rectifying tower 42 enters a fifth rectifying tower 43 for rectifying separation, wherein the tower top temperature of the fourth rectifying tower 42 is 120 ℃, the tower bottom temperature is 160 ℃, the tower top pressure is 0.01bar, and the reflux ratio is 5. The top of the fourth rectifying tower 42 obtains 1250kg/h of epoxy cyclooctane product, wherein the purity is 99.9%, and the product yield is 97.6%; the second component S4-4 with the flow rate of 2.13kg/h extracted from the bottom of the fourth rectifying tower 42 mainly comprises about 46wt% of cyclooctene oxide, about 54wt% of tar, and the second component S4-4 returns to the third rectifying tower 23 for further product recovery.

Example 5

Based on the production process of the epoxycycloalkane shown in example 2, this example shows a production process of epoxycyclohexane under specific conditions. It should be noted that the present embodiment is only a demonstration of the preferred working condition, and the protection scope of the present invention is not limited thereby.

A production process of epoxy ring hexadecane, taking 500 tons/year epoxy ring hexadecane production system as an example, comprises the following steps:

Oxidation procedure: the reactor is formed by connecting 3-level reaction kettles 11 in series, the raw materials are 417kg/h of hexa-hexadecatriene and 840kg/h of hexanol as a solvent, and the raw materials are added from the inlet of the 1-level reaction kettle after being mixed; 25wt% hydrogen peroxide 50kg/h is divided into 2 equal parts and respectively added into the previous two-stage reactor; the reaction temperature is 80 ℃, the pressure is 3000pa, the retention time of single kettle materials is 3h, and the solid content of the titanium-silicon molecular sieve catalyst in each kettle reactor is controlled at 20%. After the reaction is completed, the water content in the first material S1-4 is 2.87%, the solvent hexanol is 64.3%, the cyclohexanetricane is 25.7%, the epoxy primary product (including epoxy cyclohexanetricane mono/diene and the like) is 6.48%, and the other is 0.65%. The effective utilization rate of the hydrogen peroxide is 99.1%, and the hydrogen peroxide in the material is detected to be basically reacted. The first material S1-4 flows out from the bottom of the 3 rd-stage reaction kettle 11, and enters a first refining process after being filtered by the membrane filter device 5.

A first refining procedure: the first material S1-4 enters a first rectifying tower 21 at normal temperature for separation, the temperature of the top of the first rectifying tower 21 is 80 ℃, the temperature of a tower kettle is 190 ℃, the pressure of the top of the tower is 1bar, and the reflux ratio is 0.5; crude solvent S2-1 is separated from the top of the tower, the crude solvent S2-1 enters a solvent purification tower 6 for separation, the purpose is to separate the solvent from water, wherein the temperature of the top of the solvent purification tower 6 is 60 ℃, the temperature of the tower kettle is 120 ℃, the pressure of the top of the tower is 1bar, the reflux ratio is 30, 74.3kg/h of wastewater separated from the top of the solvent purification tower 6 is sent out of the boundary, 834kg/h of hexanol is obtained by rectifying the tower kettle, the concentration of hexanol is 99.95%, and the hexanol is recycled to the reaction kettle 11 to continuously participate in the reaction. The tower bottom material flow of the first rectifying tower 21 continuously enters a second rectifying tower 22 for separation, wherein the tower top temperature of the second rectifying tower 22 is 136 ℃, the tower bottom temperature is 187 ℃, the tower top pressure is 0.5bar, the reflux ratio is 3, unreacted hexahexadecatriene is separated from the tower top of the second rectifying tower 22, the purity is 99.9%, the mixture returns to the reaction kettle 11 for continuous reaction, and the tower bottom material of the second rectifying tower 22 enters a third rectifying tower 23 for rectification separation; wherein the temperature of the top of the third rectifying tower 23 is 150 ℃, the temperature of the tower bottom is 205 ℃, the pressure of the top of the tower is 0.05bar, the reflux ratio is 10, the second material S2-5 containing the primary epoxy product is separated from the top of the tower, the flow is 86kg/h, the second material S2-5 enters the hydrogenation process for reaction, the first heavy component S2-6 containing heavy component impurities is extracted from the tower bottom of the third rectifying tower 23, the first heavy component S2-6 mainly contains tar, and the first heavy component S2-5 is removed from the tower bottom.

Hydrogenation procedure: the second material S2-5 and hydrogen with the standard m ²/h of 25 enter a hydrogenation reactor 31 to carry out hydrogenation reaction to obtain a third material S3-1; the hydrogenation reactor 31 is a fixed bed reactor, the hydrogenation catalyst is a palladium supported catalyst, the load is 1%, and the carrier is a mixture of alumina and zirconia according to the mass ratio of 1:1. The hydrogenation reaction temperature is 80 ℃, the tower pressure is 1mpa, and the space velocity is 1h ^-1.

And a second refining procedure: the third material S3-1 enters a gas-liquid separation device 41 to obtain a gas phase S3-2 product and a liquid phase S4-1 product, wherein the gas phase S3-2 is basically unreacted hydrogen, the hydrogen returns to the inlet of the hydrogenation reactor 31 to continue the reaction, and the liquid phase S4-1 enters a fourth rectifying tower 42 to be separated; the top temperature of the fourth rectifying tower 42 is 190 ℃, the bottom temperature of the tower is 175 ℃, the top pressure of the tower is 0.04bar, the reflux ratio is 30, the tower top effluent mainly contains light component impurities, the flow is 1.89kg/h, wherein the ring hexadecane is 56%, the ring hexadecane is 43.4%, and the bottom product of the fourth rectifying tower 42 enters the fifth rectifying tower 43 for rectification separation; the temperature of the top of the fifth rectifying tower 43 is 140 ℃, the temperature of the tower bottom is 150 ℃, the pressure of the top of the tower is 0.02bar, the reflux ratio is 20, 85kg/h of epoxy cyclododecane product is obtained at the top of the tower, the purity is 99.9%, the product yield is 98%, the tower bottom of the fifth rectifying tower 43 is used for extracting 0.67kg/h of second heavy component S4-4, the content of epoxy cyclohexadecane in the second heavy component S4-4 is 41%, the balance is tar, and the second heavy component S4-4 is discharged from the tower bottom of the fifth rectifying tower 43 and returned to the third rectifying tower 23 for further recovery.

The above examples prove that the purity of the epoxy cycloalkane prepared by the epoxy cycloalkane production process is more than 99.8%, the product yield is more than 96%, and the hydrogen peroxide in the material is basically reacted after the oxidation process is finished (the content is less than 0.05 wt%), so that the effective utilization rate of the hydrogen peroxide is more than 98%, and the epoxy cycloalkane production process is a green and safe epoxy cycloalkane preparation process.

It should be noted that the above description of the present invention is further detailed in connection with specific embodiments, and it should not be construed that the present invention is limited to the specific embodiments; the size data of the embodiment is not limited to the technical scheme, but only shows one specific working condition. It will be apparent to those skilled in the art that several simple modifications and adaptations of the invention can be made without departing from the spirit of the invention and are intended to be within the scope of the invention.

Claims

1. A process for producing an epoxycycloalkane, characterized by comprising the steps of

and a second refining procedure: the third material is subjected to gas-liquid separation in sequence to discharge unreacted hydrogen, and light components and second heavy components are separated through second rectification operation, so that a high-quality epoxy cycloparaffin product is obtained;

2. The process for producing epoxycycloalkane according to claim 1, wherein the molar ratio of cycloolefin to hydrogen peroxide in hydrogen peroxide is (2-3): 1, a step of;

Preferably, the reaction temperature of the oxidation process is 80-110 ℃ and the pressure is 3000-6000Pa; in the oxidation process, the residence time of the reaction materials in each reaction kettle is 1-3h.

3. The process for producing epoxycycloalkanes as claimed in claim 1, wherein the concentration of hydrogen peroxide is 25-70wt%, preferably 30-50wt%.

4. The process for producing epoxycycloalkane according to claim 1, wherein the cycloolefin is a cyclic mono-olefin or a cyclic poly-olefin having 8 to 16 carbon atoms; preferably, the cycloolefin is a cyclic mono-olefin or a cyclic poly-olefin having 12 carbon atoms;

Preferably, the solvent is a C5-C8 alcohol;

Preferably, the mass ratio of cycloolefin to solvent is 1 (2-4).

5. The process for producing epoxycycloalkanes as claimed in claim 1, wherein N is a natural number of 2 to 8, preferably a natural number of 3 to 6.

6. The process for producing epoxycycloalkane according to claim 1, wherein the molar ratio of the second material to hydrogen in the hydrogenation step is 1 (2-4);

preferably, the reaction temperature of the hydrogenation process is 80-100 ℃, and the reaction pressure is 0.1-1MPa;

preferably, the feeding space velocity of the second material in the hydrogenation process is 0.5-2h ^-1.

7. The process for producing epoxycycloalkane according to claim 1, wherein the catalyst of the hydrogenation step is a supported catalyst comprising an active component and a carrier, the active component comprising one or more of Pt, pd, ru;

preferably, the carrier comprises one or more of alumina, silica and magnesia.

8. The process for producing epoxycycloalkanes according to claim 1, wherein the crude solvent separated in the first refining step is returned to the oxidation step after being purified by distillation;

Preferably, the temperature of the tower top of the solvent rectification purification is 30-60 ℃, the temperature of the tower bottom is 90-120 ℃, the pressure of the tower top is 0.5-1bar, and the reflux ratio is 20-30;

Preferably, the hydrogen gas discharged from the gas-liquid separation in the second refining step is returned to the hydrogenation step;

preferably, the second fraction separated in the second purification step is returned to the first purification step;

Preferably, the first material is filtered and then input into the first refining process.

9. The process for producing epoxycycloalkane according to claim 1, wherein the first rectification operation comprises primary rectification column rectification, secondary rectification column rectification and tertiary rectification column rectification;

Preferably, the temperature of the rectifying tower top of the primary rectifying tower is 50-90 ℃, the temperature of the tower bottom is 150-200 ℃, the pressure of the tower top is 0.5-1bar, and the reflux ratio is 0.5-1;

Preferably, the temperature of the top of the rectifying tower of the secondary rectifying tower is 100-140 ℃, the temperature of the tower kettle is 150-200 ℃, the pressure of the top of the tower is 0.1-0.5bar, and the reflux ratio is 1-5;

Preferably, the temperature of the top of the rectifying tower of the three-stage rectifying tower is 100-150 ℃, the temperature of the tower kettle is 160-210 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 5-20;

preferably, the second rectification operation comprises a four-stage rectification column rectification and a five-stage rectification column rectification;

Preferably, the temperature of the top of the rectifying tower of the four-stage rectifying tower is 90-120 ℃, the temperature of the tower kettle is 150-180 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 20-30;

preferably, the temperature of the top of the rectifying tower of the five-stage rectifying tower is 120-140 ℃, the temperature of the tower kettle is 150-180 ℃, the pressure of the top of the tower is 0.01-0.1bar, and the reflux ratio is 5-20.

10. A system for producing epoxycycloalkane, comprising the following units

An oxidation unit: the device comprises N reaction kettles which are connected in series, wherein a discharge hole of the last reaction kettle is connected with a feed hole of the next reaction kettle, the 1 st reaction kettle is connected with a raw material cycloolefin input pipe and a solvent input pipe, the 1 st to N-1 st reaction kettles are connected with a hydrogen peroxide input pipe, and the N th reaction kettle is provided with a discharge hole for outputting materials after oxidation reaction; wherein N is at least 2;

A second refining unit: the hydrogenation device comprises a gas-liquid separation device and at least one rectifying tower, wherein a discharge port of the hydrogenation reactor is connected with a feed port of the gas-liquid separation device, and a liquid phase outlet of the gas-liquid separation device is connected with a feed port of a first rectifying tower of the second refining unit; and the top outlet of the last rectifying tower of the second refining unit outputs a high-purity epoxy naphthene product.

11. The system for producing epoxycycloalkane according to claim 10, wherein N is a natural number of 2-8, preferably a natural number of 3-6;

preferably, a filtering device is arranged on a pipeline connecting the Nth reaction kettle and the first refining unit.

12. The epoxycycloalkane production system according to claim 10, further comprising a solvent purification rectifying column, wherein when said first refining unit comprises at least 2 rectifying columns, the top outlet of the first rectifying column is connected to the feed inlet of said solvent purification rectifying column, and the bottom outlet of said solvent purification rectifying column is connected to the feed inlet of said 1 st reaction vessel;

Preferably, the first refining unit comprises at least 3 rectifying towers, the top extraction port of the first rectifying tower is connected with the feed inlet of the solvent purifying rectifying tower, and the bottom extraction port of the solvent purifying rectifying tower is connected with the feed inlet of the 1 st reaction kettle; the top extraction ports of the rectifying towers except the first rectifying tower and the last rectifying tower are connected with the feed inlet of the 1 st reaction kettle;

preferably, the gas phase outlet of the gas-liquid separation device is connected with the hydrogen inlet of the hydrogenation reactor;

Preferably, the bottom outlet of the last rectifying tower of the second refining unit is connected with the feed inlet of the third rectifying tower.

13. The production system of epoxy cycloalkane according to claim 10, wherein the first refining unit comprises a first rectifying tower, a second rectifying tower and a third rectifying tower which are sequentially connected, a discharge port of the nth reaction kettle is connected with a feed port of the first rectifying tower, and a top outlet of the third rectifying tower is connected with a raw material inlet of the hydrogenation reactor;

preferably, the second refining unit comprises a fourth rectifying tower and a fifth rectifying tower which are connected in sequence.