CN115286611A - Method for simultaneously preparing epsilon-caprolactone and propionic acid - Google Patents
Method for simultaneously preparing epsilon-caprolactone and propionic acid Download PDFInfo
- Publication number
- CN115286611A CN115286611A CN202211005048.2A CN202211005048A CN115286611A CN 115286611 A CN115286611 A CN 115286611A CN 202211005048 A CN202211005048 A CN 202211005048A CN 115286611 A CN115286611 A CN 115286611A
- Authority
- CN
- China
- Prior art keywords
- caprolactone
- epsilon
- propionic acid
- reaction
- cyclohexanone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 235000019260 propionic acid Nutrition 0.000 title claims abstract description 59
- 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 59
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- 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
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 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
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 28
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 14
- 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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 19
- 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 7
- 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 compound 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
- 238000001816 cooling Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000005086 pumping Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 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
- 238000001514 detection method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 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
Images
Classifications
-
- 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
Landscapes
- 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 nano tubes for packaging iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde and 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 is 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 a semi-batch operation condition, and propionic acid is co-produced, the conversion rate of cyclohexanone can reach more than 96%, and the selectivity of epsilon-caprolactone and propionic acid can reach 100%, so that the problems of difficult benzoic acid separation, low total added value and the like existing in a benzaldehyde system are solved, the problems of unstable reaction condition and low selectivity of by-product acid under batch operation are solved, and the industrial production is favorably realized.
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, not only can be used as a strong polar solvent to dissolve a plurality of insoluble substances, but also can be used for resin modification and synthesis of polymers such as polycaprolactone and the like, and has wide application. At present, the epsilon-caprolactone on the market is in short supply, so the high-efficiency synthesis of the epsilon-caprolactone is always a hot spot of research at home and abroad.
The main method for industrially synthesizing the epsilon-caprolactone is a Baeyer-Villiger oxidation method, which is to prepare the epsilon-caprolactone by directly oxidizing cyclohexanone. The Baeyer-Villiger oxidation method adopts oxidants mainly including peroxy acid, hydrogen peroxide and oxygen, wherein the peroxy acid and the hydrogen peroxide have high safety requirements in the preparation, storage and use processes, so that the production cost of epsilon-caprolactone is high, and the oxidation capacity of the oxygen is weak, and a co-oxidant needs to be added.
Yuta Nabae et al (ACS Catal.2013,3, 230-236) adopt oxygen as an oxidant, benzaldehyde as an auxiliary oxidant, and various carbon materials to catalyze the Baeyer-Villiger oxidation reaction of cyclohexanone, so that the selectivity of epsilon-caprolactone can approach 100% under certain reaction conditions. Majiantai et al (ACS Sustainable chem. Eng.2018,6,5, 5868-5876) of Lanzhou university use multiple metal-free mesoporous SiO in oxygen/benzaldehyde oxidation system 2 The nanorods catalyze the Baeyer-Villiger oxidation reaction of cyclohexanone, and the selectivity of the product epsilon-caprolactone is also close to 100%. However, the use of benzaldehyde as a co-oxidant has the problems of low total industrial added value, easy pipeline blockage and difficult separation of benzoic acid generated by benzaldehyde oxidation, and the like, and is not favorable for industrial application. Furthermore, the Baeyer-Villiger oxidation process is carried out in batch operation, i.e.the reaction substrates are introduced into the reactor all at once, andbecause the reaction is a strong exothermic reaction, obvious temperature runaway can occur in the reactor after the reaction is started, so that the operation condition is unstable, and huge potential safety hazards exist in the actual production process.
Therefore, the development of the efficient synthesis method of the epsilon-caprolactone, which has the advantages of mild and stable reaction conditions, easy product separation, 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 method for simultaneously preparing epsilon-caprolactone and propionic acid comprises the following steps: adding cyclohexanone and nitrogen-doped carbon nano tubes for packaging iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde and 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 nanotube encapsulating the iron particles is 1.
Further preferably, the mass ratio of the cyclohexanone to the nitrogen-doped carbon nanotube encapsulating the iron particles is 1.
Preferably, the molar ratio of the cyclohexanone to the propionaldehyde is 0.1-10.
More preferably, the molar ratio of cyclohexanone to propionaldehyde is 4 to 7.
Preferably, the atomic percentage of Fe in the nitrogen-doped carbon nanotube encapsulating the iron particle is 1at% to 10at%.
Preferably, the nitrogen-doped carbon nanotube encapsulating the iron particles is prepared 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 packaging 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 0.5h to 10h.
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 0.3 to 1.0MPa in the reaction vessel.
Preferably, the oxidation reaction is carried out at a stirring speed of 500rpm to 1200 rpm.
More preferably, the oxidation reaction is carried out at a stirring speed of 800rpm to 1200 rpm.
The invention has the beneficial effects that: according to the invention, fe @ NCNTs is 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 a semi-batch operation condition, and propionic acid is co-produced, the conversion rate of cyclohexanone can reach more than 96%, and the selectivity of epsilon-caprolactone and propionic acid can reach 100%, so that the problems of difficult benzoic acid separation, low total added value and the like existing in a benzaldehyde system are solved, the problems of unstable reaction condition (easy temperature runaway) and low selectivity of by-product acid under batch operation are solved, and the industrial production is favorably realized.
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 will be further explained and illustrated with reference to specific examples.
The catalysts Fe @ NCNTs in examples 1 to 11 were prepared by the following method: 2g of ferric chloride hexahydrate and 2g of melamine were added to 100mL of absolute ethanolSounding for 1h, stirring at room temperature for 12h, filtering, drying the filtered solid in an oven at 100 deg.C for 10h, grinding, spreading in a porcelain boat, and placing in a constant temperature zone of a tube furnace under N 2 Heating to 800 ℃ in the atmosphere in a gradient heating mode (the heating rate is 10 ℃/min), then preserving heat for 1.5h, and naturally cooling to room temperature to obtain the nitrogen-doped carbon nano tube (marked as catalyst Fe @ NCNTs, the atomic percentage of Fe is 4.3 at%) for encapsulating the iron particles.
A Transmission Electron Microscope (TEM) image and an X-ray diffraction (XRD) image of the catalyst Fe @ NCNTs are shown in FIG. 1 and FIG. 2, respectively.
As can be seen from fig. 1 and 2: the catalyst Fe @ NCNTs is indeed nitrogen-doped carbon nanotubes encapsulating iron particles.
Example 1:
a process for the simultaneous preparation of 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 reaction kettle until the pressure of the reaction kettle is 1MPa, uniformly mixing 2.9356g of propionaldehyde and 32.1066g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at a flow rate of 0.1mL/min, stopping the reaction after 5 hours, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was subjected to detection by Gas Chromatography (GC) (the internal standard was o-dichlorobenzene), and the obtained gas chromatogram was 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 the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8179g of cyclohexanone, 20mg of catalyst Fe @ NCNTs and 6.3351g of 1, 2-dichloroethane into a reaction kettle, stirring and heating to 45 ℃, stirring at the speed of 800rpm, introducing oxygen to the reaction kettle until the pressure of the reaction kettle is 1MPa, uniformly mixing 2.9385g of propionaldehyde and 32.0942g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at the flow rate of 0.1mL/min, stopping the reaction after 5 hours, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: the conversion of cyclohexanone was 90.77%, the selectivity for epsilon-caprolactone was 100%, the conversion of propionaldehyde was 48.73%, and the selectivity for propionic acid was 97.38%.
Example 3:
a process for the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8124g of cyclohexanone, 20mg of catalyst Fe @ NCNTs and 6.3472g of 1, 2-dichloroethane into a reaction kettle, stirring and heating to 45 ℃, stirring at 800rpm, introducing oxygen to the reaction kettle until the pressure of the reaction kettle is 0.5MPa, uniformly mixing 2.9281g of propionaldehyde and 32.0997g of 1, 2-dichloroethane, pumping the mixture 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 a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: 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 the simultaneous preparation of 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 the speed of 1200rpm, introducing oxygen to the reaction kettle until the pressure of the reaction kettle is 0.3MPa, uniformly mixing 1.8201g of propionaldehyde and 18.7586g of acetonitrile, pumping the mixture into the reaction kettle at the flow rate of 0.06mL/min, stopping reaction after 8 hours, 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 tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: the conversion of cyclohexanone was 86.28%, the selectivity for epsilon-caprolactone was 98.69%, the conversion of propionaldehyde was 41.66%, and the selectivity for propionic acid was 99.53%.
Example 5:
a process for the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of:
adding 6.5477g cyclohexanone, 20mg catalyst Fe @ NCNTs and 11.2725g 1, 2-dichloroethane into a reaction kettle, stirring and heating to 40 ℃, stirring at 1200rpm, introducing oxygen to the reaction kettle at 0.3MPa, uniformly mixing 4.133g propionaldehyde and 30.6274g 1, 2-dichloroethane, pumping into the reaction kettle at a flow of 0.06mL/min, stopping the pump after 8h, continuing to react for 1h, stopping the reaction, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: the conversion of cyclohexanone was 33.80%, the selectivity for epsilon-caprolactone was 100%, the conversion of propionaldehyde was 93.23%, and the selectivity for propionic acid was 100%.
Example 6:
a process for the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of:
adding 2.1826g of cyclohexanone, 20mg of catalyst Fe @ NCNTs and 11.2802g of 1, 2-dichloroethane into a reaction kettle, stirring and heating to 40 ℃, stirring at 1200rpm, introducing oxygen to the reaction kettle until the pressure of the reaction kettle is 0.3MPa, uniformly mixing 4.1296g of propionaldehyde and 30.6425g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at a flow rate of 0.06mL/min, stopping reaction after 8h, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: the conversion of cyclohexanone was 61.79%, the selectivity for epsilon-caprolactone was 100%, the conversion of propionaldehyde was 60.14%, and the selectivity for propionic acid was 100%.
Example 7:
a process for the simultaneous preparation of 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 the speed of 1200rpm, introducing oxygen to the reaction kettle at the pressure of 0.5MPa, uniformly mixing 1.9073g of propionaldehyde and 31.5507g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at the flow rate of 0.07mL/min, stopping reaction after 7h, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was taken for detection by Gas Chromatography (GC) (internal standard is o-dichlorobenzene), and the test results are as follows: the conversion of cyclohexanone was 94.46%, the selectivity for epsilon-caprolactone was 99.27%, the conversion of propionaldehyde was 54.51%, and the selectivity for propionic acid was 100%.
Example 8:
a process for the simultaneous preparation of 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 reaction kettle at 0.5MPa, uniformly mixing 0.9467g of propionaldehyde and 34.4144g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at a flow rate of 0.07mL/min, stopping reaction after 7h, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: 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 the simultaneous preparation of 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 reaction kettle at the pressure of 1.5MPa, uniformly mixing 7.8847g of propionaldehyde and 23.4339g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at the flow rate of 0.07mL/min, stopping reaction after 7h, naturally cooling to room temperature, and filtering to obtain a filtrate, namely the reaction liquid containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: 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 the simultaneous preparation of 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 the speed of 1200rpm, introducing oxygen to the pressure of the reaction kettle to be 0.5MPa, uniformly mixing 1.9069g of propionaldehyde and 31.5534g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at the flow rate of 0.07mL/min, stopping reaction after 7 hours, 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 tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: 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 the simultaneous preparation of 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 the speed of 1200rpm, introducing oxygen to the reaction kettle at the pressure of 0.5MPa, uniformly mixing 1.8889g of propionaldehyde and 31.1543g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at the flow rate of 0.07mL/min, heating to 65 ℃ after 3h, continuing pumping for 4h, stopping reaction, 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 for detection by Gas Chromatography (GC) (internal standard is o-dichlorobenzene), and the test results are 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 the simultaneous preparation of epsilon-caprolactone and propionic acid comprising the steps of:
adding 0.8116g of cyclohexanone and 6.318g of 1, 2-dichloroethane into a reaction kettle, stirring and heating to 50 ℃, stirring at 1200rpm, introducing oxygen to the reaction kettle at 1MPa, uniformly mixing 2.934g of propionaldehyde and 32.1078g of 1, 2-dichloroethane, pumping the mixture into the reaction kettle at a flow rate of 0.1mL/min, stopping reaction after 5 hours, naturally cooling to room temperature, and filtering to obtain a filtrate, namely a reaction solution containing epsilon-caprolactone and propionic acid.
The filtrate in this example was tested by Gas Chromatography (GC) (internal standard o-dichlorobenzene) with the following test results: 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 embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for simultaneously preparing epsilon-caprolactone and propionic acid is characterized by comprising the following steps: adding cyclohexanone and nitrogen-doped carbon nano tubes for packaging iron particles into a reaction kettle, heating to a preset reaction temperature, introducing oxygen, mixing propionaldehyde and 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.
2. The process of claim 1 for the simultaneous production of epsilon-caprolactone and propionic acid, wherein: the mass ratio of the cyclohexanone to the nitrogen-doped carbon nano tube for encapsulating the iron particles is 1.
3. The process for the simultaneous preparation of epsilon-caprolactone and propionic acid as claimed in claim 1, wherein: the molar ratio of the cyclohexanone to the propionaldehyde is 0.1-10.
4. The process for simultaneous production of epsilon-caprolactone and propionic acid as claimed in any one of claims 1 to 3, wherein: the atomic percentage of Fe in the nitrogen-doped carbon nano tube for packaging the iron particles is 1at% -10 at%.
5. The process of claim 4 for the simultaneous production of epsilon-caprolactone and propionic acid, wherein: the nitrogen-doped carbon nanotube for encapsulating the iron particles is prepared by the following method: and dispersing ferric salt and melamine in a solvent for reaction, and calcining the obtained product in a protective atmosphere to obtain the nitrogen-doped carbon nano tube for packaging iron particles.
6. The method for simultaneously producing epsilon-caprolactone and propionic acid according to any one of claims 1 to 3, wherein: the preset reaction temperature is 30-80 ℃.
7. The method for simultaneously producing epsilon-caprolactone and propionic acid according to any one of claims 1 to 3, wherein: the organic solvent is at least one of 1, 2-dichloroethane, acetonitrile and ethyl acetate.
8. The process for 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.
9. The method for simultaneously producing epsilon-caprolactone and propionic acid according to 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 MPa-2.0 MPa.
10. The method for simultaneously producing epsilon-caprolactone and propionic acid according to any one of claims 1 to 3, wherein: the oxidation reaction is carried out at a stirring speed of 500rpm to 1200 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211005048.2A CN115286611B (en) | 2022-08-22 | 2022-08-22 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211005048.2A CN115286611B (en) | 2022-08-22 | 2022-08-22 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115286611A true CN115286611A (en) | 2022-11-04 |
| CN115286611B CN115286611B (en) | 2023-08-22 |
Family
ID=83830516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211005048.2A Active CN115286611B (en) | 2022-08-22 | 2022-08-22 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115286611B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592192A (en) * | 2015-01-26 | 2015-05-06 | 上海应用技术学院 | Method for preparing epsilon-caprolactone |
| CN105367537A (en) * | 2014-08-18 | 2016-03-02 | 江苏扬农化工集团有限公司 | Method for preparing caprolactone by catalyzing cyclohexanone through MgO-supported and modified H beta |
| CN106397386A (en) * | 2016-09-13 | 2017-02-15 | 华南理工大学 | Method used for preparing epsilon-hexanolactone |
| CN108558819A (en) * | 2018-04-24 | 2018-09-21 | 华南理工大学 | A method of preparing 6-caprolactone using carbon nanotube |
| CN110922385A (en) * | 2019-12-23 | 2020-03-27 | 华南理工大学 | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
| CN111100105A (en) * | 2019-12-31 | 2020-05-05 | 广州昊科生物科技有限公司 | Method for preparing epsilon-caprolactone from solvent-free cyclohexanone |
| CN112479860A (en) * | 2019-09-12 | 2021-03-12 | 浙江大学 | Novel method for co-production of carboxylic acid and epsilon-caprolactone based on oxygen oxidation |
-
2022
- 2022-08-22 CN CN202211005048.2A patent/CN115286611B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367537A (en) * | 2014-08-18 | 2016-03-02 | 江苏扬农化工集团有限公司 | Method for preparing caprolactone by catalyzing cyclohexanone through MgO-supported and modified H beta |
| CN104592192A (en) * | 2015-01-26 | 2015-05-06 | 上海应用技术学院 | Method for preparing epsilon-caprolactone |
| CN106397386A (en) * | 2016-09-13 | 2017-02-15 | 华南理工大学 | Method used for preparing epsilon-hexanolactone |
| CN108558819A (en) * | 2018-04-24 | 2018-09-21 | 华南理工大学 | A method of preparing 6-caprolactone using carbon nanotube |
| CN112479860A (en) * | 2019-09-12 | 2021-03-12 | 浙江大学 | Novel method for co-production of carboxylic acid and epsilon-caprolactone based on oxygen oxidation |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
| CN110922385A (en) * | 2019-12-23 | 2020-03-27 | 华南理工大学 | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde |
| CN111100105A (en) * | 2019-12-31 | 2020-05-05 | 广州昊科生物科技有限公司 | Method for preparing epsilon-caprolactone from solvent-free cyclohexanone |
Non-Patent Citations (1)
| Title |
|---|
| JIANGNAN HUANG ET AL.: "Catalytic Synthesis of Lactones from Alkanes in the Presence of Aldehydes and Carbon Nanotubes", 《ACS SUSTAINABLE CHEM. ENG.》, vol. 10, pages 6713 - 6723 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115286611B (en) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1993000166A1 (en) | Process for the transformation of vanadium/phosphorus mixed oxide catalyst precursors into active catalysts for the production of maleic anhydride | |
| JP2014518759A (en) | Catalyst for producing acrylic acid and acrylate | |
| CN113443964B (en) | Method for synthesizing higher alcohol by catalytic conversion of ethanol | |
| CN103201031A (en) | Novel glycerol dehydration catalyst and production method therefor | |
| CN107649155A (en) | A kind of doping Nb vpo catalyst, preparation method and its application in acrylic acid is produced | |
| TWI383971B (en) | Process for preparing at least one organic target compound by heterogeneously catalyzed gas phase partial oxidation | |
| JP2000079344A (en) | Gas phase synthesis of pyromellitic anhydride | |
| CN109574834A (en) | The production method of glyoxylic ester | |
| JP4442317B2 (en) | Method for producing composite oxide catalyst | |
| CN115286611B (en) | Method for simultaneously preparing epsilon-caprolactone and propionic acid | |
| CN110922385A (en) | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde | |
| CN110038609B (en) | Dehydration catalyst and application thereof in preparation of organic carboxylic anhydride | |
| JP5831329B2 (en) | Composite oxide catalyst | |
| JP2017176932A (en) | catalyst | |
| CN111018823B (en) | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone | |
| CN109574844A (en) | The manufacturing method of glyoxylic ester | |
| CN111100105A (en) | Method for preparing epsilon-caprolactone from solvent-free cyclohexanone | |
| JP2008238098A (en) | Method for preparing composite oxide catalyst | |
| JP6136436B2 (en) | Catalyst production method | |
| CN111974393A (en) | Preparation method of catalyst for preparing methanol by low-temperature plasma-optical coupling of methane and method for preparing methanol | |
| US4740614A (en) | Process for preparation of p-hydroxybenzoic acid from p-methoxytoluene | |
| CN115518630B (en) | Application of zinc silicate material as styrene catalyst prepared by ethylbenzene dehydrogenation | |
| CN102649082B (en) | Method for enhancing activity of catalyst for preparing oxalic ester from CO | |
| CN114433155B (en) | Catalyst for synthesizing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof | |
| CN102219678B (en) | Starting-up method for producing oxalic acid ester with CO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |