CN114426459A - Device and method for preparing KA oil through cyclohexane oxidation - Google Patents
Device and method for preparing KA oil through cyclohexane oxidation Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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Abstract
The invention provides a device for preparing KA oil by oxidizing cyclohexane, which comprises: a micro mixer; a micro-reactor connected with the micro-mixer; and optionally, a gas-liquid separator connected to the microreactor; wherein, the micro mixer is a lamination type micro mixer or a chaotic micro mixer. The invention adopts the lamination type micro-mixer or the chaotic micro-mixer, can fully ensure the uniform mixing of materials, and greatly enhances the mass transfer efficiency of gas phase and liquid phase, thereby shortening the reaction time, improving the safety performance of the reaction, improving the space-time yield of the reactor and the like.
Description
Technical Field
The invention relates to the technical field of preparation of KA oil, and particularly relates to a device and a method for preparing KA oil through cyclohexane oxidation.
Background
KA oil, which is a mixture of cyclohexanol and cyclohexanone, is an important organic chemical raw material. Cyclohexanone and cyclohexanol are widely used in industrial field, are main intermediates for preparing caprolactam and adipic acid, are important industrial solvents, can be used in the industries of medicine, paint, coating, rubber, pesticide and the like, and also have application in the aspects of printing and plastic recovery. At present, monomers of caprolactam and adipic acid for synthesizing fiber nylon-6 and nylon-66 are mainly produced by taking cyclohexanone as a raw material.
At present, more than 90 percent of cyclohexanone and cyclohexanol in industrial production are produced by adopting a cyclohexane oxidation method, and 70 percent of cyclohexanone and cyclohexanol in industrial production adopt a cyclohexane non-catalytic oxidation method. The cyclohexane oxidation process without catalyst was first developed by Rhone-Ponlene, France (US3510526), and is characterized by the fact that the reaction is divided into two steps, the first step is the direct oxidation of cyclohexane to cyclohexyl hydroperoxide by air, and the second step is the decomposition of cyclohexyl hydroperoxide to cyclohexanol and cyclohexanone under alkaline conditions and the action of catalyst. According to the method, the single-pass conversion rate of cyclohexane is 3-5%, the selectivity of cyclohexanol and cyclohexanone is about 80%, the retention time of reaction materials is about 1 hour, the reaction temperature is 120-200 ℃, and the reaction pressure is 1.3MPaG (US5406001, EP 0092867). The process has the advantages that the reaction is carried out step by step, no catalyst is adopted in the oxidation stage, the problem of slagging of an oxidation reactor is avoided, the device is continuously operated under the condition allowed by equipment, and the yield of the cyclohexyl hydrogen peroxide in the oxidation process can reach more than 95%. The disadvantages are that the selectivity of cyclohexanol and cyclohexanone in the decomposition process of cyclohexyl hydroperoxide is only below 88 percent, and a large amount of alkali is needed, and the process has long process flow and high energy consumption because the single-pass conversion rate of cyclohexane is low.
The cyclohexane oxidation reaction is considered to belong to a free radical reaction type, an induction period exists in the reaction, and the length of the induction period is related to conditions such as reaction temperature, raw material composition, existence of a catalyst and the like. In the absence of catalytic oxidation, an induction period of 60-70 minutes is typically required before significant oxygen uptake begins. In order to shorten the induction period, in the current industrial production, crude alcohol ketone (cyclohexanol and cyclohexanone) is added as an initiator at the start-up stage. And the cyclohexane oxidation reaction takes place partly or completely in the liquid film, at least at the end of the induction phase, the reaction taking place at the beginning of the acceleration of the reaction. Cyclohexane, cyclohexanol, cyclohexanone and the like involved in the production have wider explosion limit and low flash point, belong to flammable and explosive substances, the upper part of a reactor in the oxidation reaction process is mixed gas of cyclohexane, nitrogen, unreacted oxygen, carbon monoxide, carbon dioxide and the like generated by reaction, and explosion accidents can be caused if the concentration of tail oxygen is increased to be within the explosion limit under certain temperature and pressure.
Cyclohexane oxidation is currently carried out industrially in a series of stirred tank reactors or cascaded bubble columns using air or a mixture of nitrogen and oxygen (with an oxygen content of less than 21%). The cyclohexane oxidation process generally adopts a mode of connecting a plurality of bubble columns in series, the cyclohexane generally flows through each reactor in sequence, the cyclohexanol and cyclohexanone in the cyclohexane oxidation liquid are maintained in a lower concentration, and the conversion rate of the cyclohexane is generally controlled between 3% and 5%. At present, the domestic industrial device for preparing cyclohexanone by oxidizing cyclohexane with air, which is the first step of producing cyclohexanone by oxidizing cyclohexane, consists of a plurality of (generally 3-8) stirring bubbling reactors or airlift loop reactors connected in series, as described in CN 103804161A. In order to improve the gas-liquid two-phase mass transfer efficiency and the selectivity of a target product, internal components such as a guide cylinder and the like can be added in the reactor, and stirring or an optimized gas distributor can be added to improve the mass transfer. However, the space-time yield of the oxidation reactor is generally 25kg/m3·h。
CN1982273A discloses a high gravity reactor-rotating packed bed for preparing cyclohexanone by oxidizing cyclohexane, which can enhance the oxidation process of cyclohexane. The high-gravity reactor can greatly improve the mass transfer speed and the heat transfer speed, but has limited influence on the reaction result due to the improvement of the mass transfer speed in the slow reaction process of which the chemical reaction is a control step, such as the preparation of cyclohexanone by cyclohexane oxidation.
CN101293810B adopts a micro-channel reactor and/or a micro-tube reactor to carry out cyclohexane liquid-phase non-catalytic oxidation, alcohol and ketone initiators are added under the condition of maintaining the equivalent cyclohexane conversion rate of the existing industrial device, the reaction time can be reduced to several minutes from the original 1 hour, and the total selectivity of the target product can reach more than 95%.
CN1834078A discloses a cyclohexane liquid-phase oxidation process, in which liquid-phase cyclohexane is passed through a bubble reactor in a plug flow manner, so as to improve the yield of cyclohexane oxidation. However, unless the residence time of the liquid phase cyclohexane in the reactor is short, such that the upward flow velocity of cyclohexane is close to the rising velocity of bubbles, the rising bubbles will cause turbulence in the liquid, and the flow pattern of the liquid in the bubble column will be far from plug flow and closer to complete flow. In the existing industrial device, the total residence time of liquid materials during cyclohexane oxidation is generally 20-80 minutes, which is converted into 4-16 minutes in each stage of reactor, and the bubbles in the reactor only need to rise from the tower bottom to the tower top for a few seconds. Therefore, it is difficult to achieve a plug flow state of the liquid in the bubble column having a large diameter.
CN103055792A discloses an oscillating tubular reactor for cyclohexane liquid phase oxidation and a use method thereof, wherein a reaction section is formed by connecting a plurality of chambers in series, and one tubular reactor is equivalent to the series connection of a plurality of full mixing kettle reactors, so that the flow mode of the whole reaction fluid is closer to plug flow, and the selectivity of an oxidation intermediate product KA oil is higher. However, the reactor also adopts multi-stage gas inlet, when air oxidation is adopted, the gas content of the material at the upper part of the straight cylinder section is greatly increased due to a large amount of nitrogen contained in the gas, and the flowing state in the reactor is deteriorated; the gas exiting the gas distributor located in the upper part of the reactor shaft escapes from the liquid phase over a relatively short period of time, and the oxygen content of the offgas may exceed the safety limit due to a too short residence time.
US6008415 discloses a cyclohexane non-catalytic oxidation reactor. The oxidizing gas is oxygen-enriched air or pure oxygen with oxygen concentration lower than 30%. The design of a baffle, a guide cylinder and blades of a component in the reactor is changed, so that liquid in the reactor is divided into a main fluid part and a static liquid part, the main fluid circulates in the reactor, the gas-liquid mass transfer is enhanced, the size of bubbles is reduced, and the utilization rate of oxygen can reach 99%; injecting inert gas into the gas phase space at the top of the reactor to keep the oxygen concentration below the ignition point, and generally keeping the oxygen content in the gas phase below 2 percent, so as to ensure the safety of the oxidation reaction of pure oxygen or oxygen-enriched air cyclohexane; compared with the conventional air oxidation, the special design of the internal structure of the reactor improves the performance of the oxidation reaction, reduces the retention time and the reaction temperature, slightly improves the selectivity of the target product, but has more complex internal structure and precise control requirement on the content of residual oxygen.
In a word, the problems of long reaction time, low safety, large environmental pollution, low reactor efficiency and low space-time yield exist in the current industrial production. Therefore, in order to reduce the raw material cost of caprolactam, the reaction and reaction efficiency of KA prepared by cyclohexane oxidation must be improved, the safety of the device is improved, the environmental pollution is reduced, and the development direction of cyclohexane oxidation technology during clean, efficient and safe production is realized.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a device for preparing KA oil by oxidizing cyclohexane, which can sufficiently ensure uniform mixing of materials and greatly enhance the gas-liquid two-phase mass transfer efficiency by using a lamination type micro mixer or a chaotic micro mixer, thereby shortening the reaction time, improving the safety performance of the reaction, and improving the space-time yield of the reactor.
The second purpose of the invention is to provide a method for preparing KA oil by cyclohexane oxidation corresponding to the first purpose.
The third purpose of the invention is to provide the KA oil prepared by the device or the method corresponding to the purpose.
The fourth purpose of the present invention is to provide an application of the KA oil prepared by the device or the method of the present invention corresponding to the above purpose.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
an apparatus for preparing KA oil by cyclohexane oxidation, comprising:
a micro mixer;
a micro-reactor connected with the micro-mixer; and
optionally, a gas-liquid separator connected to the microreactor;
wherein, the micro mixer is a lamination type micro mixer or a chaotic micro mixer.
According to the invention, the number of the microreactors can be single or multiple. When the number of the reactors is plural, the reactors may be connected in series or in parallel.
According to the invention, the micromixer can be adjusted on the basis of the micromixers of the prior art, the adjustment comprising the adjustment of the microchannel equivalent diameter and/or the microchannel volume.
According to the present invention, the specific type of the micro mixer (i.e., the lamination type micro mixer or the chaotic micro mixer) that can be applied to the present invention is not limited as long as the equivalent diameter of the micro channel can be regulated within the range required by the present invention.
In some preferred embodiments of the present invention, the micro-channel equivalent diameter of the micro-mixer is 50 μm to 500 μm, preferably 60 μm to 150 μm.
According to the invention, the micro-channel volume can be adjusted according to the actual production requirements.
In some preferred embodiments of the present invention, the microreactor is selected from one or more of a microchannel reactor and a microreactor reactor.
In some preferred embodiments of the invention, the micro-channel equivalent diameter of the microreactor is from 100 μm to 2000 μm, preferably from 200 μm to 1000 μm.
According to the present invention, the specific type of the microreactor is not limited as long as the microchannel equivalent diameter is within the range defined in the present invention. Exemplary types of microreactors that may be employed in the present invention include: ERHFELD, CHEMTRx, etc.
In some preferred embodiments of the present invention, the included angle between the micromixer and the microreactor is from 45 ° to 75 °, preferably from 50 ° to 70 °.
In some preferred embodiments of the invention, the micromixer and the microreactor are located within a heating chamber.
In some preferred embodiments of the invention, the micromixer and the microreactor are located in the same heating chamber.
In some preferred embodiments of the present invention, the micromixer is further provided with an oxygen-containing gas feed line and a cyclohexane feed line.
In some preferred embodiments of the present invention, the oxygen-containing gas feed line is provided with a gas preheater; and/or a liquid preheater is arranged on the cyclohexane feeding pipeline.
The inventors of the present application have found, through research, that under the above-mentioned specific apparatus, the oxidation of cyclohexane to KA oil can be achieved without adding an initiator, and the ratio of cyclohexanone to cyclohexanol in the obtained KA oil can reach about 3:1, which is not achieved by the prior art (the ratio of cyclohexanol to cyclohexanone in the KA oil obtained by the prior art is about 2: 1). Because the produced cyclohexanone is used for synthesizing caprolactone in the subsequent process of cyclohexane industrial production without catalytic oxidation at present, the quantity of the produced cyclohexanone is expected to be larger than that of cyclohexanol, so that a working section for cyclohexanol dehydrogenation can be omitted, and the device disclosed by the invention can well meet the requirement.
In addition, the device provided by the invention can reduce or basically eliminate the generation of intermediate product cyclohexyl peroxidation, and omits the need of adding a catalyst to decompose the intermediate product into cyclohexanol in the subsequent industrial production, thereby avoiding the use of additional equipment.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a method for preparing KA oil by cyclohexane oxidation is carried out in the device.
In some preferred embodiments of the invention, the method comprises the steps of:
s1, introducing oxygen-containing gas and cyclohexane into the micro mixer for mixing to obtain a first reaction material flow;
s2, introducing the first reactant flow into the microreactor to perform oxidation reaction to obtain a second reactant flow containing KA oil; and
optionally, S3, introducing the second reaction material flow into the gas-liquid separator to obtain KA oil;
in step S1, the mixing conditions include: the temperature is 140-220 ℃; the pressure is 0.5MPaG to 4 MPaG; the mixing time is 10 s-120 s; and/or in step S2, the conditions of the oxidation reaction include: the temperature is 140-220 ℃; the pressure is 0.5MPaG to 4 MPaG; the reaction time is 0.5 min-30 min.
In some preferred embodiments of the present invention, in step S1, the mixing conditions include: the temperature is 150-200 ℃; the pressure is 1 MPaG-2.5 MPaG; the mixing time is 10 s-120 s; and/or in step S2, the conditions of the oxidation reaction include: the temperature is 150-200 ℃; the pressure is 1 MPaG-2.5 MPaG; the reaction time is 1 min-10 min.
In some preferred embodiments of the present invention, the mixing in step S1 and the oxidation reaction in step S2 are at the same temperature and pressure.
In some preferred embodiments of the present invention, in step S1, the molar ratio of the oxygen-containing gas to the cyclohexane is (0.1-10): 1, preferably (0.2-5): 1.
In some preferred embodiments of the present invention, in step S1, the oxygen concentration in the oxygen-containing gas is 10% to 100%, preferably 50% to 100%.
According to the invention, the oxygen concentration refers to the volume concentration.
In some preferred embodiments of the present invention, the oxygen-containing gas is passed through the gas preheater to perform a first preheating process on the oxygen-containing gas in step S1.
In some preferred embodiments of the present invention, the cyclohexane is passed through the liquid preheater in step S1, thereby subjecting the cyclohexane to a second preheating treatment.
In some preferred embodiments of the present invention, the conditions of the first and second pre-heat treatments are the same or different, and each independently comprises: the preheating temperature is 80-150 ℃.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
the KA oil prepared by the device or the method is characterized in that the molar ratio of cyclohexanone to cyclohexanol in the KA oil is (2-4): 1, preferably (2.5-3.5): 1.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
the KA oil is used as a raw material for synthesizing caprolactone.
The invention has the advantages that at least the following aspects are achieved:
firstly, the use of the micro-mixer greatly enhances the mass transfer efficiency of gas phase and liquid phase, thereby shortening the reaction time, improving the safety performance of the reaction and improving the space-time yield of the reactor.
Secondly, when the reaction temperature and the pressure of the micro mixer and the micro reactor are consistent, the micro mixer can also be used as a pre-reactor, and the oxidation reaction of cyclohexane can be carried out under the condition of not adding an initiator.
Thirdly, the cyclohexane adopted by the existing industry has no catalytic oxidation mode, and the invention provides a new oxidation mode.
Fourthly, the micro-reactor is large in specific surface area compared with a traditional reactor, and mass transfer on the transverse dimension is strengthened, so that the multiphase reaction is strengthened, hot spots and chain type explosion can be effectively avoided, and pressure and temperature are prevented from flying. Therefore, when oxygen-enriched or pure oxygen is used for oxidation, the safety of the oxidation reaction can be ensured. And the restriction effect of the micro-scale structure realizes that the reaction fluid in the device flows in a plug flow mode, thereby greatly reducing the back mixing of the reaction product and the product, and improving the selectivity of the target product while improving the reaction rate.
Fifthly, the device and the method provided by the invention can reduce or basically eliminate the generation of intermediate product cyclohexyl peroxidation, and omit the subsequent catalyst addition in the current industrial production to decompose the intermediate product into cyclohexanol, thereby avoiding the use of additional equipment.
Sixthly, the ratio of cyclohexanone to cyclohexanol in the KA oil prepared by the present invention can reach about 3:1, which cannot be achieved by the prior art (the ratio of cyclohexanol to cyclohexanone in the KA oil prepared by the prior art is about 2: 1). Because the produced cyclohexanone is used for synthesizing caprolactone in the subsequent process of cyclohexane industrial production without catalytic oxidation at present, the quantity of the produced cyclohexanone is expected to be larger than that of cyclohexanol, so that a working section for cyclohexanol dehydrogenation can be omitted, and the device disclosed by the invention can well meet the requirement.
Seventhly, under the reaction conditions of the temperature of 140-220 ℃ and the pressure of 0.5-4 MPaG, the molar ratio is 0.1-10: 1, respectively preheating oxygen-containing gas and cyclohexane to 80-150 ℃, mixing the oxygen-containing gas and the cyclohexane in a gas-liquid micro-mixer, and then reacting in a microreactor, wherein the reaction residence time is 0.5-30 min, so that the cyclohexane conversion rate and the KA oil selectivity on the current industrial device can be ensured to be equivalent to the current level, and the space-time yield of the reactor can be 25kg/m3H is increased to 6000kg/m3H or so.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Description of reference numerals: in FIG. 1, 1 is cyclohexane; 2 is a liquid feed pump; 3 is a liquid preheater; 4 is an oxygen-containing gas; 5 is a gas flowmeter; 6 is a gas preheater; 7 is a micro mixer; 8 is a micro-reactor; 9 is a heating box; 10 is a gas-liquid separator; 11 is a cooler; 12 is a product; 13 is reaction tail gas.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
In the following embodiments, unless otherwise specified, pure oxygen is used as the oxygen-containing gas; the micro-reactor is a single micro-reactor, and the equivalent diameter of a micro-pipe of the micro-reactor is 500 mu m; the micro mixer is a chaotic micro mixer, and the equivalent diameter of a micro channel is 100 mu m.
In the following embodiment, the formula for calculating the conversion of cyclohexane is formula (1):
cyclohexane conversion (mol%) × 100% for moles of product/moles of cyclohexane charge formula (1).
In the following embodiment, the formula for calculating the selectivity for cyclohexanone is given by formula (2):
cyclohexanone selectivity (mol%) ═ cyclohexanone formation moles/cyclohexane conversion × 100% formula (2).
In the following embodiment, the formula for calculating the selectivity for cyclohexanol is formula (3):
cyclohexanol selectivity (mol%): cyclohexanol formation mole/cyclohexane conversion × 100% formula (3).
In the following embodiment, the formula for calculating the selectivity of cyclohexyl hydroperoxide is formula (4):
selectivity (mol%) to cyclohexyl hydroperoxide is the number of moles of cyclohexyl hydroperoxide formed per cyclohexane conversion x 100% formula (4).
In the following embodiments, the overall selectivity of cyclohexanone, cyclohexanol, cyclohexyl hydroperoxide is calculated by formula (5):
total selectivity (mol%)/cyclohexane conversion × 100% formula (5) (moles of cyclohexanone + moles of cyclohexanol + moles of cyclohexyl hydroperoxide).
Example 1
The apparatus used in example 1 comprises: a liquid feed pump 2; a liquid preheater 3; a gas flow meter 5; a gas preheater 6; a micro mixer 7; a microreactor 8; a heating box 9; a gas-liquid separator 10; a cooler 11; the connection of the various components is shown in figure 1.
As shown in fig. 1, the process flow of example 1 is:
the method comprises the steps of metering oxygen-containing gas by a gas flowmeter, then preheating the oxygen-containing gas to 120 ℃ in a gas preheater, metering cyclohexane by a metering pump, then preheating the cyclohexane in a liquid preheater to 120 ℃, wherein the molar ratio of the oxygen-containing gas to the cyclohexane is 0.3:1, simultaneously mixing the oxygen-containing gas and the cyclohexane in a micro mixer (the reaction temperature is 180 ℃, the pressure is 2.0MPaG, and the residence time is 60s) to form a uniform gas-liquid mixture, reacting the gas-liquid mixture in a microreactor (the reaction temperature is 180 ℃, the pressure is 2.0MPaG, and the residence time is 2min) to obtain a reaction mixture, separating the reaction mixture by a gas-liquid separation tank, removing reaction tail gas to a gas separation unit, and feeding the liquid into a subsequent rectification unit by a cooler.
And analyzing the liquid cooled by the cooler, wherein the conversion rate of the cyclohexane is 5 percent, and the total selectivity of the cyclohexanone, the cyclohexanol and the cyclohexyl hydroperoxide is 95 percent, wherein the selectivity of the cyclohexanone is 71 percent, and the selectivity of the cyclohexanol is 23.5 percent.
Example 2
Example 2 was set up substantially the same as example 1 except that a lamination type micromixer having a microchannel equivalent diameter of 100 μm was used instead of the chaotic micromixer in example 1.
Analysis of the liquid obtained in example 2 after cooling by the cooler revealed a cyclohexane conversion of 5% and a total selectivity of cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide of 95%, wherein the selectivity for cyclohexanone was 71.5% and the selectivity for cyclohexanol was 23%.
Example 3
Example 3 was set to be substantially the same as example 1, except that the conditions at the time of mixing in the micromixer in example 3 were: the temperature was 220 ℃ and the pressure was 4.0 MPaG.
Analysis of the liquid obtained in example 3 after cooling by the cooler revealed a cyclohexane conversion of 6% and a total selectivity for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide of 96%, wherein the selectivity for cyclohexanone was 72% and the selectivity for cyclohexanol was 24%.
Example 4
Example 4 was set to be substantially the same as example 1 except that the chaotic micromixer used in example 4 had a microchannel equivalent diameter of 50 μm.
Analysis of the liquid obtained in example 4 after cooling by the cooler revealed a cyclohexane conversion of 5% and a total selectivity of cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide of 96%, wherein the selectivity for cyclohexanone was 72.5% and the selectivity for cyclohexanol was 23.5%.
Example 5
Example 5 was set to be substantially the same as example 1 except that the chaotic micromixer used in example 5 had a microchannel equivalent diameter of 200 μm.
Analysis of the liquid obtained in example 5 after cooling by the cooler revealed a cyclohexane conversion of 5% and a total selectivity of cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide of 93%, wherein the selectivity for cyclohexanone was 69.55% and the selectivity for cyclohexanol was 23.25%.
Example 6
Example 6 was set to be substantially the same as example 1 except that the chaotic micromixer used in example 6 had a microchannel equivalent diameter of 350 μm.
Analysis of the liquid obtained in example 6 after cooling by the cooler revealed a cyclohexane conversion of 5% and a total selectivity for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide of 92%, wherein the selectivity for cyclohexanone was 68.8% and the selectivity for cyclohexanol was 23%.
Example 7
Example 7 was set to be substantially the same as example 1 except that the chaotic micromixer used in example 7 had a microchannel equivalent diameter of 500 μm.
Analysis of the liquid obtained in example 7 after cooling by the cooler revealed a cyclohexane conversion of 5% and a total selectivity of 91% for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, wherein the selectivity for cyclohexanone was 68% and the selectivity for cyclohexanol was 22.5%.
Comparative example 1
Comparative example 1 was set up substantially the same as example 1, except that a T-type mixer was used instead of the chaotic micromixer in example 1.
Analysis of the liquid obtained in comparative example 1 after cooling by the cooler revealed 4% conversion of cyclohexane and 90% total selectivity for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, wherein the selectivity for cyclohexanone was 40% and the selectivity for cyclohexanol was 43%.
Comparative example 2
Comparative example 2 was set up substantially the same as example 1, except that a Y-type mixer was used instead of the chaotic micromixer in example 1.
Analysis of the liquid obtained in comparative example 2 after cooling by the cooler revealed 4% conversion of cyclohexane and 80% total selectivity for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, wherein the selectivity for cyclohexanone was 35% and the selectivity for cyclohexanol was 43%.
Comparative example 3
Comparative example 3 was set up to be substantially the same as example 1 except that a three-way mixer was used instead of the chaotic micromixer in example 1.
Analysis of the liquid obtained in comparative example 3 after cooling by the cooler revealed 4% conversion of cyclohexane and 70% total selectivity for cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, wherein the selectivity for cyclohexanone was 30% and the selectivity for cyclohexanol was 38%.
Comparative example 4
Comparative example 4 was set up substantially the same as example 1, except that a batch tank was used instead of the microreactor in example 1.
When the liquid obtained by the comparative example 4 and cooled by the cooler is analyzed, the conversion rate of cyclohexane is 1%, and the total selectivity of cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide is 90%, wherein the selectivity of cyclohexanone is 35% and the selectivity of cyclohexanol is 50%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An apparatus for preparing KA oil by cyclohexane oxidation, comprising:
a micro mixer;
a micro-reactor connected with the micro-mixer; and
optionally, a gas-liquid separator connected to the microreactor;
the micro mixer is a lamination type micro mixer or a chaotic micro mixer, preferably, the equivalent diameter of a micro channel of the micro mixer is 50-500 μm, preferably 60-150 μm.
2. The apparatus of claim 1, wherein the microreactor is selected from one or more of a microchannel reactor and a microreactor reactor; preferably, the micro-channels of the microreactor have an equivalent diameter of 100 to 2000. mu.m, preferably 200 to 1000. mu.m.
3. The apparatus according to claim 1 or 2, wherein the micromixer and the microreactor are located in a heating chamber, preferably in the same heating chamber.
4. The apparatus according to any of claims 1 to 3, wherein the micromixer is further provided with an oxygen-containing gas feed line and a cyclohexane feed line; preferably, a gas preheater is provided on the oxygen-containing gas feed line; and/or a liquid preheater is arranged on the cyclohexane feeding pipeline.
5. A process for oxidation of cyclohexane to KA oil, the process being carried out in the apparatus of any of claims 1-4.
6. The method of claim 5, comprising the steps of:
s1, introducing oxygen-containing gas and cyclohexane into the micro mixer for mixing to obtain a first reaction material flow;
s2, introducing the first reactant flow into the microreactor to perform oxidation reaction to obtain a second reactant flow containing KA oil; and
optionally, S3, introducing the second reaction material flow into the gas-liquid separator to obtain KA oil;
in step S1, the mixing conditions include: the temperature is 140-220 ℃, and the preferable temperature is 150-200 ℃; the pressure is 0.5MPaG to 4MPaG, preferably 1MPaG to 2.5 MPaG; the mixing time is 10 s-120 s; and/or in step S2, the conditions of the oxidation reaction include: the temperature is 140-220 ℃, and the preferable temperature is 150-200 ℃; the pressure is 0.5MPaG to 4MPaG, preferably 1MPaG to 2.5 MPaG; the reaction time is 0.5min to 30min, preferably 1min to 10 min.
7. The method according to claim 5 or 6, wherein in step S1, the molar ratio of the oxygen-containing gas to the cyclohexane is (0.1-10): 1, preferably (0.2-5): 1; preferably, the oxygen concentration in the oxygen-containing gas is 10% to 100%, preferably 50% to 100%.
8. The method of any of claims 5 to 7, wherein in step S1, the oxygen-containing gas is passed through the gas preheater to thereby subject the oxygen-containing gas to a first preheating treatment; and/or passing the cyclohexane through the liquid preheater, thereby subjecting the cyclohexane to a second preheating treatment; preferably, the conditions of the first preheating treatment and the second preheating treatment are the same or different, and each independently comprise: the preheating temperature is 80-150 ℃.
9. KA oil produced by the device according to any one of claims 1 to 4 or produced by the method according to any one of claims 5 to 8, wherein the molar ratio of cyclohexanone to cyclohexanol in the KA oil is (2-4): 1, preferably (2.5-3.5): 1.
10. Use of the KA oil of claim 9 as a feedstock for the synthesis of caprolactone.
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