CN115286611B - Method for simultaneously preparing epsilon-caprolactone and propionic acid - Google Patents
Method for simultaneously preparing epsilon-caprolactone and propionic acid Download PDFInfo
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- CN115286611B CN115286611B CN202211005048.2A CN202211005048A CN115286611B CN 115286611 B CN115286611 B CN 115286611B CN 202211005048 A CN202211005048 A CN 202211005048A CN 115286611 B CN115286611 B CN 115286611B
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 235000019260 propionic acid Nutrition 0.000 title claims abstract description 56
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 80
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 23
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000005711 Benzoic acid Substances 0.000 abstract description 3
- 235000010233 benzoic acid Nutrition 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 24
- 239000000706 filtrate Substances 0.000 description 24
- 238000004817 gas chromatography Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for simultaneously preparing epsilon-caprolactone and propionic acid, which comprises the following steps: adding cyclohexanone and nitrogen-doped carbon nanotubes encapsulating iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde with an organic solvent, and adding the mixture into the reaction kettle in a continuous feeding manner for oxidation reaction to obtain epsilon-caprolactone and propionic acid. According to the invention, fe@NCNTs are used as a catalyst, oxygen is used as an oxidant, propionaldehyde is used as an auxiliary oxidant, cyclohexanone is efficiently converted into epsilon-caprolactone under semi-batch operation conditions, propionic acid is combined, the highest conversion rate of cyclohexanone can reach more than 96%, and the selectivities of epsilon-caprolactone and propionic acid can reach 100%, so that the problems of difficult separation of benzoic acid, low total added value and the like in a benzaldehyde system are solved, the problems of unstable reaction conditions and low selectivity of byproduct acid under batch operation are also solved, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for simultaneously preparing epsilon-caprolactone and propionic acid.
Background
Epsilon-caprolactone is an important organic chemical intermediate, can be used as a strong polar solvent to dissolve a plurality of indissolvable substances, can be used for resin modification, synthesis of polycaprolactone and other polymers, and has wide application. At present, the supply of epsilon-caprolactone on the market is short, so the efficient synthesis of epsilon-caprolactone is always a hot spot for research at home and abroad.
The main method for industrially synthesizing epsilon-caprolactone is Baeyer-Villiger oxidation, which is to prepare epsilon-caprolactone by directly oxidizing cyclohexanone. The oxidizing agents adopted by the Baeyer-Villiger oxidation method mainly comprise peroxyacid, hydrogen peroxide and oxygen, the peroxyacid and the hydrogen peroxide have high safety requirements in the preparation, storage and use processes, the production cost of epsilon-caprolactone is high, the oxidizing capability of the oxygen is weak, and an auxiliary oxidizing agent is also needed to be added.
Yuta Nabae et al (ACS catalyst.2013, 3, 230-236) uses oxygen as an oxidant and benzaldehyde as an auxiliary oxidant, adopts various carbon materials to catalyze the Baeyer-Villiger oxidation reaction of cyclohexanone, and can enable the selectivity of epsilon-caprolactone to be close to 100% under certain reaction conditions. Ma Jiantai et al (ACS Sustainable chem. Eng.2018,6,5,5868-5876) at university of Lanzhou in oxygen/benzaldehyde oxidation systems in the form of a plurality of metal-free mesoporous SiOs 2 The nanorods catalyze the Baeyer-Villiger oxidation of cyclohexanone, and the selectivity of the product epsilon-caprolactone is similar to 100%. However, the use of benzaldehyde as a co-oxidant has the problems of low total industrial added value, easy blockage of pipelines and difficult separation of benzoic acid generated by oxidation of benzaldehyde, and the like, and is not beneficial to industrial application. In addition, the Baeyer-Villiger oxidation method is completed under intermittent operation condition, i.e. the reaction substrate is added into the reactor all at once, and the reaction is a strong exothermic reaction, after the reaction is started, obvious temperature runaway occurs in the reactor, thus leading to unstable operation condition and huge potential safety hazard in the actual production process.
Therefore, the development of the epsilon-caprolactone high-efficiency synthesis method with the advantages of mild and stable reaction conditions, easy separation of products, low production cost and the like has very important significance.
Disclosure of Invention
The invention aims to provide a method for simultaneously preparing epsilon-caprolactone and propionic acid.
The technical scheme adopted by the invention is as follows:
a process for the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of: adding cyclohexanone and nitrogen-doped carbon nanotubes encapsulating iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde with an organic solvent, and adding the mixture into the reaction kettle in a continuous feeding manner for oxidation reaction to obtain epsilon-caprolactone and propionic acid.
Preferably, the mass ratio of the cyclohexanone to the nitrogen-doped carbon nano tube of the encapsulated iron particles is 1:0.001-0.05.
Further preferably, the mass ratio of the cyclohexanone to the nitrogen-doped carbon nanotubes of the encapsulated iron particles is 1:0.01-0.05.
Preferably, the molar ratio of cyclohexanone to propionaldehyde is 0.1-10:1.
Further preferably, the molar ratio of cyclohexanone to propionaldehyde is 4-7:1.
Preferably, the atomic percentage of Fe in the nitrogen-doped carbon nano tube of the encapsulated iron particles is 1at% to 10at%.
Preferably, the nitrogen-doped carbon nanotubes encapsulating the iron particles are made by the following method: and dispersing ferric salt and melamine in a solvent for reaction, and then placing the obtained product in a protective atmosphere for calcination to obtain the nitrogen-doped carbon nano tube for encapsulating the iron particles.
Preferably, the preset reaction temperature is 30-80 ℃.
Further preferably, the preset reaction temperature is 40-60 ℃.
Preferably, the organic solvent is at least one of 1, 2-dichloroethane, acetonitrile and ethyl acetate.
Preferably, the time of the oxidation reaction is 0.5 to 10 hours.
More preferably, the time of the oxidation reaction is 5 to 8 hours.
Preferably, the oxidation reaction is carried out under the condition that the pressure in the reaction kettle is 0.1MPa to 2.0 MPa.
More preferably, the oxidation reaction is carried out under a pressure of 0.3MPa to 1.0MPa in the reaction vessel.
Preferably, the oxidation reaction is carried out at a stirring speed of 500rpm to 1200 rpm.
Further preferably, the oxidation reaction is carried out at a stirring speed of 800rpm to 1200 rpm.
The beneficial effects of the invention are as follows: according to the invention, fe@NCNTs are used as a catalyst, oxygen is used as an oxidant, propionaldehyde is used as an auxiliary oxidant, cyclohexanone is efficiently converted into epsilon-caprolactone under semi-batch operation conditions, propionic acid is combined, the highest conversion rate of cyclohexanone can reach more than 96%, and the selectivities of epsilon-caprolactone and propionic acid can reach 100%, so that the problems of difficult separation of benzoic acid, low total added value and the like in a benzaldehyde system are solved, the problems of unstable reaction conditions (extremely easy temperature flying) and low selectivity of byproduct acid under batch operation are also solved, and the industrial production is facilitated.
Drawings
FIG. 1 is a TEM image of the catalyst Fe@NCNTs.
FIG. 2 is an XRD pattern of the catalyst Fe@NCNTs.
FIG. 3 is a gas chromatogram of the reaction solution in example 1.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
The catalysts Fe@NCNTs in examples 1-11 were prepared by the following method: adding 2g of ferric trichloride hexahydrate and 2g of melamine into 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 1h, stirring at room temperature for 12h, filtering, drying the obtained solid in a drying oven at 100 ℃ for 10h, grinding, spreading in a porcelain boat, placing in a constant temperature section of a tubular furnace, and adding N into a reaction kettle 2 Heating to 800 ℃ in an atmosphere in a gradient heating mode (heating rate is 10 ℃/min), preserving heat for 1.5h, and naturally cooling to room temperature to obtain the nitrogen-doped carbon nanotube (marked as a catalyst Fe@NCNTs, wherein the atomic percentage of Fe is 4.3 at%) for encapsulating the iron particles.
The Transmission Electron Microscope (TEM) pattern of the catalyst fe@ncnts is shown in fig. 1, and the X-ray diffraction (XRD) pattern is shown in fig. 2.
As can be seen from fig. 1 and 2: the catalyst Fe@NCNTs is indeed a nitrogen-doped carbon nanotube encapsulating iron particles.
Example 1:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8125g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 6.3545g of 1, 2-dichloroethane into a reaction kettle, stirring and heating to 50 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 1MPa, uniformly mixing 2.9356g of propanal and 32.1066g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.1mL/min, stopping the reaction after 5h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was subjected to detection by Gas Chromatography (GC) (internal standard is o-dichlorobenzene) and the resulting gas chromatogram is shown in FIG. 3.
As can be seen from fig. 3: the conversion of cyclohexanone was 95.62%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 53.25%, and the selectivity of propionic acid was 100%.
Example 2:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
0.8179g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 6.3351g of 1, 2-dichloroethane are added into a reaction kettle, the mixture is stirred and heated to 45 ℃, the stirring speed is 800rpm, oxygen is introduced into the reaction kettle until the pressure is 1MPa, 2.9385g of propanal and 32.0942g of 1, 2-dichloroethane are uniformly mixed, then the mixture is pumped into the reaction kettle at a flow rate of 0.1mL/min, the reaction is stopped after 5 hours, the mixture is naturally cooled to room temperature, and the filtrate is filtered to obtain a reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 90.77%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 48.73%, and the selectivity of propionic acid was 97.38%.
Example 3:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
0.8124g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 6.3472g of 1, 2-dichloroethane are added into a reaction kettle, then the mixture is stirred and heated to 45 ℃, the stirring speed is 800rpm, then oxygen is introduced into the reaction kettle until the pressure is 0.5MPa, 2.9281g of propanal and 32.0997g of 1, 2-dichloroethane are uniformly mixed, then the mixture is pumped into the reaction kettle at a flow rate of 0.1mL/min, after 5h, the reaction is stopped, the mixture is naturally cooled to room temperature, and the filtrate is filtered to obtain a reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 92.25%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 50.07%, and the selectivity of propionic acid was 100%.
Example 4:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.5113g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 7.0126g of acetonitrile into a reaction kettle, stirring and heating to 40 ℃, stirring at 1200rpm, introducing oxygen to the reaction kettle at 0.3MPa, uniformly mixing 1.8201g of propanal and 18.7586g of acetonitrile, pumping into the reaction kettle at a flow rate of 0.06mL/min, stopping reacting after 8h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 86.28%, the selectivity of epsilon-caprolactone was 98.69%, the conversion of propionaldehyde was 41.66%, and the selectivity of propionic acid was 99.53%.
Example 5:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
6.5477g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 11.2725g of 1, 2-dichloroethane are added into a reaction kettle, then the mixture is stirred and heated to 40 ℃, the stirring speed is 1200rpm, then oxygen is introduced into the reaction kettle until the pressure is 0.3MPa, then 4.133g of propanal and 30.6274g of 1, 2-dichloroethane are uniformly mixed, then the mixture is pumped into the reaction kettle at a flow rate of 0.06mL/min, after 8h, the pump is stopped, the reaction is stopped after the reaction is continued for 1h, the reaction is naturally cooled to room temperature, and the filtrate is the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 33.80%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 93.23%, and the selectivity of propionic acid was 100%.
Example 6:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
2.1826g of cyclohexanone, 20mg of catalyst Fe@NCNTs and 11.2802g of 1, 2-dichloroethane are added into a reaction kettle, then the mixture is stirred and heated to 40 ℃, the stirring speed is 1200rpm, then oxygen is introduced into the reaction kettle until the pressure is 0.3MPa, 4.1296g of propanal and 30.6425g of 1, 2-dichloroethane are uniformly mixed, then the mixture is pumped into the reaction kettle at a flow rate of 0.06mL/min, after 8h, the reaction is stopped, the mixture is naturally cooled to room temperature, and the filtrate is filtered to obtain a reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 61.79%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 60.14%, and the selectivity of propionic acid was 100%.
Example 7:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.5066g of cyclohexanone and 10mg of catalyst Fe@NCNTs into a reaction kettle, stirring and heating to 50 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 0.5MPa, uniformly mixing 1.9073g of propanal and 31.5507g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.07mL/min, stopping reacting after 7h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 94.46%, the selectivity of epsilon-caprolactone was 99.27%, the conversion of propionaldehyde was 54.51% and the selectivity of propionic acid was 100%.
Example 8:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8241g of cyclohexanone and 10mg of catalyst Fe@NCNTs into a reaction kettle, stirring and heating to 50 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 0.5MPa, uniformly mixing 0.9467g of propanal and 34.4144g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.07mL/min, stopping reacting after 7h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 46.77%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 65.37%, and the selectivity of propionic acid was 100%.
Example 9:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 6.5913g of cyclohexanone and 10mg of catalyst Fe@NCNTs into a reaction kettle, stirring and heating to 60 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 1.5MPa, uniformly mixing 7.8847g of propanal and 23.4339g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.07mL/min, stopping reacting after 7h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 53.67%, the selectivity of epsilon-caprolactone was 98.64%, the conversion of propionaldehyde was 95.62%, and the selectivity of propionic acid was 97.90%.
Example 10:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8227g of cyclohexanone and 10mg of catalyst Fe@NCNTs into a reaction kettle, stirring and heating to 60 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 0.5MPa, uniformly mixing 1.9069g of propanal and 31.5534g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.07mL/min, stopping reacting after 7h, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 76.17%, the selectivity of epsilon-caprolactone was 98.33%, the conversion of propionaldehyde was 57.06%, and the selectivity of propionic acid was 98.07%.
Example 11:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.5044g of cyclohexanone and 10mg of catalyst Fe@NCNTs into a reaction kettle, stirring and heating to 45 ℃, stirring at 1200rpm, introducing oxygen to the pressure of the reaction kettle of 0.5MPa, uniformly mixing 1.8889g of propanal and 31.1543g of 1, 2-dichloroethane, pumping into the reaction kettle at a flow rate of 0.07mL/min, heating to 65 ℃ after 3 hours, continuing pumping for 4 hours, stopping reacting, naturally cooling to room temperature, and filtering to obtain filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 96.60%, the selectivity of epsilon-caprolactone was 100%, the conversion of propionaldehyde was 47.23%, and the selectivity of propionic acid was 100%.
Comparative example:
a process for simultaneously preparing epsilon-caprolactone and propionic acid comprising the steps of:
0.8116g of cyclohexanone and 6.318g of 1, 2-dichloroethane are added into a reaction kettle, stirred and heated to 50 ℃, the stirring speed is 1200rpm, oxygen is introduced until the pressure of the reaction kettle is 1MPa, 2.934g of propanal and 32.1078g of 1, 2-dichloroethane are uniformly mixed, then the mixture is pumped into the reaction kettle at a flow rate of 0.1mL/min, the reaction is stopped after 5h, the mixture is naturally cooled to room temperature, and the filtrate is filtered, thus obtaining the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken and tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) and the test results were as follows: the conversion of cyclohexanone was 27.88%, the selectivity of epsilon-caprolactone was 88.70%, the conversion of propionaldehyde was 16.35%, and the selectivity of propionic acid was 98.67%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A process for the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of: adding cyclohexanone and nitrogen-doped carbon nanotubes encapsulating iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde with an organic solvent, and adding the mixture into the reaction kettle in a continuous feeding manner for oxidation reaction to obtain epsilon-caprolactone and propionic acid; the atomic percentage of Fe in the nitrogen-doped carbon nano tube of the encapsulated iron particles is 1at% -10 at%; the nitrogen-doped carbon nano tube for encapsulating the iron particles is prepared by the following method: dispersing ferric salt and melamine in a solvent for reaction, and then placing the obtained product in a protective atmosphere for calcination to obtain the nitrogen-doped carbon nano tube for encapsulating the iron particles; the preset reaction temperature is 30-80 ℃.
2. The method for simultaneously preparing epsilon-caprolactone and propionic acid as claimed in claim 1, wherein: the mass ratio of the cyclohexanone to the nitrogen-doped carbon nano tube of the encapsulated iron particles is 1:0.001-0.05.
3. The method for simultaneously preparing epsilon-caprolactone and propionic acid as claimed in claim 1, wherein: the molar ratio of the cyclohexanone to the propionaldehyde is 0.1-10:1.
4. A process for the simultaneous production of epsilon-caprolactone and propionic acid as claimed in any one of claims 1 to 3, wherein: the organic solvent is at least one of 1, 2-dichloroethane, acetonitrile and ethyl acetate.
5. A process for the simultaneous production of epsilon-caprolactone and propionic acid as claimed in any one of claims 1 to 3, wherein: the time of the oxidation reaction is 0.5 h-10 h.
6. A process for the simultaneous production of epsilon-caprolactone and propionic acid as claimed in any one of claims 1 to 3, wherein: the oxidation reaction is carried out under the condition that the pressure in the reaction kettle is 0.1-2.0 MPa.
7. A process for the simultaneous production of epsilon-caprolactone and propionic acid as claimed in any one of claims 1 to 3, wherein: the oxidation reaction is carried out under the condition that the stirring speed is 500 rpm-1200 rpm.
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