CN115353503B - Preparation method of epsilon-caprolactone - Google Patents
Preparation method of epsilon-caprolactone Download PDFInfo
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- CN115353503B CN115353503B CN202210783664.4A CN202210783664A CN115353503B CN 115353503 B CN115353503 B CN 115353503B CN 202210783664 A CN202210783664 A CN 202210783664A CN 115353503 B CN115353503 B CN 115353503B
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- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7684—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention provides a preparation method of epsilon-caprolactone. The preparation method comprises the following steps: under the action of a catalyst, tetrahydropyran reacts with carbon monoxide to obtain epsilon-caprolactone; the catalyst comprises a molecular sieve and an active metal supported in the molecular sieve, wherein the active metal comprises metallic copper. The invention takes the tetrahydropyran and the carbon monoxide as raw materials, and prepares the epsilon-caprolactone with high added value through one-step carbonylation ring expansion.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a preparation method of epsilon-caprolactone.
Background
Epsilon-caprolactone is an important organic intermediate raw material and is mainly applied to the production of synthetic rubber, synthetic fiber, synthetic resin and the like. The epsilon-caprolactone can generate ring-opening polymerization reaction to generate high molecular polycaprolactone. As with polylactic acid, polycaprolactone has good biocompatibility, cells can grow normally on the basal frame, and degrade and produce carbon dioxide and water, so that the polycaprolactone can be used for drug slow release carriers, cosmetic materials, vascular stents, surgical sutures, cell tissue culture basal frames and the like. Compared with polylactic acid, the polycaprolactone has better hydrophobicity and good chemical compatibility with high polymer materials such as PE, PP, ABS, ABS, AS, PC, PVAC, PVB, PVE, PA, natural rubber and the like; polycaprolactone also has good mechanical properties and can be processed by molding methods such as injection molding, blow molding, mould pressing, extrusion and the like.
Currently epsilon-caprolactone is produced industrially mainly by the reaction of cyclohexane with peroxides by Baeyer-Villiger. However, the method generates more three wastes, and the peroxide has a great potential safety hazard.
Therefore, the development of a novel safe and environment-friendly preparation method of epsilon-caprolactone has important significance.
Disclosure of Invention
The invention provides a preparation method of epsilon-caprolactone, which takes cheap and easily available tetrahydropyran and carbon monoxide as raw materials and adopts a specific supported catalyst to prepare the chemical epsilon-caprolactone with high value added value through one-step catalytic carbonylation ring-expanding reaction. The method has the advantages of safety, environmental protection and low cost.
The invention provides a preparation method of epsilon-caprolactone, which comprises the following steps: under the action of a catalyst, tetrahydropyran reacts with carbon monoxide to obtain epsilon-caprolactone;
the catalyst comprises a molecular sieve and an active metal supported in the molecular sieve, wherein the active metal comprises metallic copper.
The preparation method comprises the step of loading the active metal into the catalyst, wherein the loading amount of the active metal is 6-10wt%.
The preparation method as described above, wherein the active metal of the catalyst further comprises metallic cobalt.
The preparation method comprises the steps of loading 3-5wt% of metal copper and loading 2-6wt% of metal cobalt.
The preparation method comprises the step of preparing the molecular sieve, wherein the molecular sieve is ZSM-22 molecular sieve.
The preparation method comprises the steps of, wherein, siO of the ZSM-22 molecular sieve 2 :Al 2 O 3 The molar ratio of (2) is (50-100): 1.
The preparation method comprises the steps of reacting at 150-300 ℃; and/or the pressure of the reaction is 1.5-3 MPa.
The preparation method comprises the following steps of: and (3) impregnating the salt solution of the active metal on the molecular sieve carrier by adopting an isovolumetric impregnation method, drying the impregnation system to obtain a catalyst precursor, and roasting the catalyst precursor at 500-550 ℃ for 4-8 hours to obtain the catalyst.
The preparation method as described above, wherein the preparation method comprises the following steps: passing a feed gas through a fixed bed reactor loaded with the catalyst to effect the reaction;
the feed gas comprises tetrahydropyran and carbon monoxide;
the tetrahydropyran was fed through a saturated tube with nitrogen.
The preparation method comprises the steps of carrying the tetrahydropyran into a saturated pipe through nitrogen, wherein the flow rate of the nitrogen is 3-5mL/min, and the feeding flow rate of the carbon monoxide is 30-50mL/min.
According to the preparation method of epsilon-caprolactone, provided by the invention, the chemical epsilon-caprolactone with high added value is obtained by taking the tetrahydropyran and the carbon monoxide as raw materials through catalyzing carbonylation ring-expanding reaction in one step under the action of a specific supported catalyst. The method has the advantages of simple reaction process, low cost and easy obtainment of raw materials, no adoption of noble metal catalyst, less amount of three wastes, safety, environmental protection and low cost, and has good industrial application prospect.
Drawings
FIG. 1 is a gas chromatogram of the product collected in example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of epsilon-caprolactone, which comprises the following steps: under the action of a catalyst, tetrahydropyran reacts with carbon monoxide to obtain epsilon-caprolactone;
wherein the catalyst comprises a molecular sieve and an active metal loaded in the molecular sieve, and the active metal comprises metallic copper.
The preparation process of epsilon-caprolactone can be represented by the following reaction formula:
the carbonylation ring-expanding reaction of epoxy compounds is one of the important methods for synthesizing lactone compounds. Currently, carbonylation ring-expanding reactions of three-membered, four-membered and five-membered epoxy compounds have been reported. However, the tension of the three-membered ring and the four-membered ring is larger, the tension of the ring can be relieved by expanding the ring, and the tension of the five-membered ring and the six-membered ring is small, so that the tension of expanding the ring from the five-membered ring to the six-membered ring is relatively smaller. However, the six-membered ring has a stable structure, while the seven-membered ring is not stable, so that the difficulty of expanding the six-membered ring into the seven-membered ring is great, and it has not been reported yet that the tetrahydropyran with the six-membered ring is carbonylated to expand the ring into epsilon-caprolactone with the seven-membered ring structure.
The inventor researches and discovers that when a supported catalyst is adopted and the carrier is selected from molecular sieves, and the active metal supported on the molecular sieves comprises metallic copper, carbonylation ring-expanding reaction of tetrahydropyran can be realized, and the chemical epsilon-caprolactone with high added value is obtained through a one-step method.
The preparation method has the advantages that the raw materials of the tetrahydropyran and the carbon monoxide are low in cost and easy to obtain, noble metal elements are not used in the catalyst, the reaction conditions are simple and mild, three wastes are hardly generated, safety and environmental protection are realized, and the cost is low.
Further, when the loading amount of the active metal is 6 to 10wt%, the catalyst has more excellent catalytic effect. Wherein, the loading of the active metal can be calculated by the mass of the active metal component/(the mass of the active metal component+the mass of the carrier).
In a specific embodiment, the active metal of the catalyst comprises, in addition to metallic copper, metallic cobalt. The cobalt and the copper can play a catalytic synergistic role, so that the reaction has higher tetrahydropyran conversion rate and epsilon-caprolactone selectivity.
When the active metal component comprises both metallic copper and metallic cobalt, the loading of metallic copper in the catalyst is 3-5wt% and the loading of metallic cobalt is 3-5wt%.
Further, the carrier molecular sieve used for the catalyst is a ZSM-22 molecular sieve. Besides the pore canal structure which is more matched with the tetrahydropyran, the ZSM-22 molecular sieve also has a certain acid position on the surface, and can assist the active metal to enhance the catalytic activity of the catalyst.
As is well known to those skilled in the art, the molecular sieve may be prepared by reacting a ZSM-22 molecular sieve SiO 2 :Al 2 O 3 The regulation of the molar ratio of the molecular sieve realizes the condition of acid density of the molecular sieve. Specifically, siO 2 :Al 2 O 3 The higher the molar ratio of (2), the lower the acid density of the molecular sieve; siO (SiO) 2 :Al 2 O 3 The lower the molar ratio of (c) the higher the acid density of the molecular sieve. The inventor finds that when ZSM-22 molecular sieve is SiO through experimental study 2 :Al 2 O 3 The molar ratio of (50-100): 1, the molecular sieve has a proper acid density, thereby ensuring that the catalyst has good catalytic performance.
Further, the above reaction may be carried out under mild reaction conditions at a temperature of 150 to 300℃and a pressure of 1.5 to 3MPa.
The catalyst of the invention can be prepared by a preparation method of a conventional supported catalyst in the field. For example, the catalyst may be prepared by an isovolumetric impregnation method, for example, an isovolumetric impregnation method is first used to impregnate a salt solution of an active metal onto a molecular sieve support, then the impregnation system is dried to obtain a catalyst precursor, and finally the catalyst precursor is calcined at 500 to 550 ℃ for 4 to 8 hours to obtain the supported metal catalyst of the present invention.
The preparation reaction of the present invention can be carried out in a fixed bed reactor, and specifically comprises passing a feed gas through a fixed bed reactor loaded with a catalyst to carry out the reaction, wherein the feed gas comprises tetrahydropyran and carbon monoxide. Since tetrahydropyran is liquid at room temperature, tetrahydropyran can be fed through a saturated tube with nitrogen.
Before the reaction, the method also comprises a catalyst pretreatment process, wherein the pretreatment steps are as follows: the catalyst was pretreated under nitrogen at 300 ℃ for 1h.
The gases produced after the reaction in the fixed bed reactor can be introduced into an in-line chromatograph through a heated line for analysis.
In a specific embodiment, a reaction tube having an inner diameter of 10mm and a length of 40cm may be used for the reaction, and a good reaction effect can be obtained by filling 0.5g of the catalyst in the reaction tube.
According to the volume of the reactor selected by the invention, the comprehensive consideration of factors such as the activity of the catalyst and the like can determine that the flow rate of nitrogen is 3-5mL/min and the feeding flow rate of carbon monoxide is 30-50mL/min when the tetrahydropyran is carried into a saturated pipe through nitrogen.
The method for preparing epsilon-caprolactone provided by the invention will be further described with reference to specific examples.
In the examples which follow, all starting materials and reagents are prepared by commercial or conventional methods, unless otherwise specified.
Example 1
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) 123g of Co (NO) 3 ) 2 ·6H 2 O and 95g of Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 100g of water and stirred to dissolve completely, and 500g of ZSM-22 molecular sieve (SiO 2 :Al 2 O 3 The molar ratio of (1) is 70:1) is immersed for 2 hours by ultrasonic, filtered, washed, dried at 120 ℃, and baked at 550 ℃ for 5 hours to obtain the supported bimetallic catalyst loaded with metallic cobalt and copper;
wherein the loading of cobalt in the supported bimetallic catalyst is 5wt% and the loading of copper is 5wt%.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 200 ℃, and reaction raw material gas is introduced to react, wherein, tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 3mL/min when the tetrahydropyran is carried into the saturated pipe by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph, FIG. 1 is a gas chromatogram of the product collected in example 1, and it can be calculated from FIG. 1 that the conversion of tetrahydropyran is 25.6% and the selectivity of ε -caprolactone is 93.9%.
Example 2
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of ZSM-22 molecular sieve is 100:1, the loading of cobalt in the catalyst is 3 weight percent, and the loading of copper is 3 weight percent.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 250 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 1.5MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 5mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 20.1% and an epsilon-caprolactone selectivity of 90.4%.
Example 3
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of ZSM-22 molecular sieve is 60:1, the loading of cobalt in the catalyst is 6 weight percent, and the loading of copper is 3 weight percent.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 250 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 1.5MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 16.8% and an epsilon-caprolactone selectivity of 96.7%.
Example 4
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (2) to (4) of ZSM-22 molecular sieve is 80:1, the cobalt loading in the catalyst is 2wt% and the copper loading is 4wt%.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 150 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 3MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 5mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 40mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 9.6% and an epsilon-caprolactone selectivity of 90.1%.
Example 5
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of ZSM-22 molecular sieve is 90:1, the loading of cobalt in the catalyst is 4 weight percent, and the loading of copper is 4 weight percent.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 180 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 3mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 21.7% and an epsilon-caprolactone selectivity of 95.5%.
Example 6
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) 95g of Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 100g of water and stirred to dissolve completely, and 500g of ZSM-22 molecular sieve (SiO 2 :Al 2 O 3 The molar ratio of (2) is 70: 1) Ultrasonic dipping for 2h, filtering, washing, drying at 120 ℃, and roasting at 550 ℃ for 5h to obtain a supported catalyst loaded with metallic copper;
wherein the copper loading in the supported catalyst was 5wt%.
2) Weighing 0.5g of the supported metal catalyst prepared in the step 1), filling the supported metal catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm, the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under a nitrogen atmosphere;
the temperature of the reactor is regulated to 200 ℃, and reaction raw material gas is introduced to react, wherein, tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 10.3% and an epsilon-caprolactone selectivity of 99.7%.
Example 7
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of ZSM-22 molecular sieve is 60:1, the loading of cobalt in the catalyst is 2wt percent, and the loading of copper is 1wt percent.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 250 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 1.5MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 4.2% and an epsilon-caprolactone selectivity of 85.3%.
Example 8
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of ZSM-22 molecular sieve is 60:1, the loading of cobalt in the catalyst is 8 weight percent, and the loading of copper is 8 weight percent.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 250 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 1.5MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 30.7% and an epsilon-caprolactone selectivity of 62.0%.
Example 9
The preparation method of epsilon-caprolactone of the embodiment is as follows:
1) Preparing a supported bimetallic catalyst loaded with metallic cobalt and copper by referring to the same method as in the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (3) is 60:1, the cobalt loading in the catalyst is 6wt% and the copper loading is 3wt%.
2) Weighing 0.5g of the supported bimetallic catalyst prepared in the step 1), filling the supported bimetallic catalyst into a reaction tube (the inner diameter of the reaction tube is 10mm and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 250 ℃, and reaction raw material gas is introduced to react, wherein the tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 1.5MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph gave a tetrahydropyran conversion of 5.8% with epsilon-caprolactone selectivity of < 1%.
Comparative example 1
1) 0.5g of ZSM-22 molecular sieve (SiO 2 :Al 2 O 3 70:1) and roasting at 550 ℃ for 5 hours to obtain the fractionAnd (3) sub-sieving the catalyst.
2) Filling 0.5g of the molecular sieve catalyst prepared in the step 1) into a reaction tube (the inner diameter of the reaction tube is 10mm, the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 200 ℃, and reaction raw material gas is introduced to react, wherein, tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 5mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product using a gas chromatograph showed that the conversion of tetrahydropyran was < 1% and that no epsilon-caprolactone formation was detected.
Comparative example 2
1) 0.5g of ZSM-5 molecular sieve (SiO 2 :Al 2 O 3 The molar ratio of (2) is 70:1), and roasting for 5 hours at 550 ℃ to obtain the molecular sieve catalyst.
2) Filling 0.5g of the molecular sieve catalyst prepared in the step 1) into a reaction tube (the inner diameter of the reaction tube is 10mm, the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 200 ℃, and reaction raw material gas is introduced to react, wherein, tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 5mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product using a gas chromatograph showed that the conversion of tetrahydropyran was < 1% and that no epsilon-caprolactone formation was detected.
Comparative example 3
1) 123gCo (NO) 3 ) 2 ·6H 2 O was dissolved in 100g of water and stirred to dissolve completely, and 500g of ZSM-22 (SiO 2 :Al 2 O 3 The molar ratio of (2) is 70: 1) Ultrasonic dipping for 2h, filtering, washing, drying at 120 ℃ and roasting at 550 ℃ for 5h to obtain a supported catalyst loaded with metallic cobalt;
wherein the loading of cobalt in the supported catalyst is 5wt%.
2) Filling 0.5g of the molecular sieve catalyst prepared in the step 1) into a reaction tube (the inner diameter of the reaction tube is 10mm, the length of the reaction tube is 40 cm) of a fixed bed reactor, and pre-treating the filled catalyst for 1h at 300 ℃ under the nitrogen atmosphere;
the temperature of the reactor is regulated to 200 ℃, and reaction raw material gas is introduced to react, wherein, tetrahydropyran is fed through a saturated pipe by adopting nitrogen, the reaction pressure is controlled to be 2MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein, the flow rate of nitrogen is 4mL/min when the tetrahydropyran is carried into the saturated tube by nitrogen, and the feeding flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product using a gas chromatograph showed that the conversion of tetrahydropyran was < 1% and that no epsilon-caprolactone formation was detected.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. A method for preparing epsilon-caprolactone, which is characterized by comprising the following steps: under the action of a catalyst, tetrahydropyran reacts with carbon monoxide to obtain epsilon-caprolactone;
the catalyst is a molecular sieve and active metal loaded in the molecular sieve, wherein the active metal comprises metallic copper;
the loading amount of the active metal is 6-10wt%;
the molecular sieve is a ZSM-22 molecular sieve, and the SiO of the ZSM-22 molecular sieve 2 :Al 2 O 3 The molar ratio of (2) is (50-100): 1.
2. The method of claim 1, wherein the active metal of the catalyst further comprises metallic cobalt.
3. The method according to claim 2, wherein the metal copper is supported in an amount of 3 to 5wt% and the metal cobalt is supported in an amount of 2 to 6wt%.
4. A process according to any one of claims 1 to 3, wherein the temperature of the reaction is 150 to 300 ℃ and the pressure of the reaction is 1.5 to 3MPa.
5. A process according to any one of claims 1 to 3, wherein the catalyst is prepared by a process comprising: and (3) impregnating the salt solution of the active metal on the molecular sieve carrier by adopting an isovolumetric impregnation method, drying the impregnation system to obtain a catalyst precursor, and roasting the catalyst precursor at 500-550 ℃ for 4-8 hours to obtain the catalyst.
6. A method of preparation according to any one of claims 1 to 3, wherein the method of preparation comprises: passing a feed gas through a fixed bed reactor loaded with the catalyst to effect the reaction;
the feed gas comprises tetrahydropyran and carbon monoxide;
the tetrahydropyran was fed through a saturated tube with nitrogen.
7. The method according to claim 6, wherein the flow rate of nitrogen is 3-5mL/min and the flow rate of carbon monoxide is 30-50mL/min when the tetrahydropyran is carried through a saturated pipe by nitrogen.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5883265A (en) * | 1997-04-15 | 1999-03-16 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof |
| CN102702152A (en) * | 2012-06-04 | 2012-10-03 | 湖南大学 | Method for preparing organic lactone |
| CN104529950A (en) * | 2009-04-08 | 2015-04-22 | 诺沃梅尔公司 | Process for beta-lactone production |
| WO2020033248A1 (en) * | 2018-08-07 | 2020-02-13 | Novomer, Inc. | Processes for producing beta-lactone and beta-lactone derivatives with heterogenous catalysts |
| CN111393394A (en) * | 2020-05-12 | 2020-07-10 | 上海朴颐化学科技有限公司 | Synthesis method of butyrolactone compound |
| CN111484464A (en) * | 2020-05-28 | 2020-08-04 | 陕西延长石油（集团）有限责任公司 | Method for preparing valerolactone by catalyzing carbonylation of tetrahydrofuran |
| CN111548333A (en) * | 2020-05-28 | 2020-08-18 | 陕西延长石油（集团）有限责任公司 | New method for preparing valerolactone |
| CN112209913A (en) * | 2020-10-30 | 2021-01-12 | 陕西延长石油（集团）有限责任公司 | Method for preparing adipic anhydride by catalyzing carbonylation of tetrahydrofuran |
| CN112707883A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of epsilon-caprolactone |
| CN113441175A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Molecular sieve supported metal catalyst and preparation method thereof |
| CN114289060A (en) * | 2021-12-30 | 2022-04-08 | 美思德(吉林)新材料有限公司 | Supported bimetallic catalyst and preparation method and application thereof |
| CN114602539A (en) * | 2020-12-08 | 2022-06-10 | 中国石油天然气股份有限公司 | Copper-based-molecular sieve composite catalyst and preparation method and application thereof |
| CN114656426A (en) * | 2021-12-13 | 2022-06-24 | 上海中化科技有限公司 | Method for preparing beta-lactone by continuously carbonylating epoxy compound |
-
2022
- 2022-07-05 CN CN202210783664.4A patent/CN115353503B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5883265A (en) * | 1997-04-15 | 1999-03-16 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof |
| CN104529950A (en) * | 2009-04-08 | 2015-04-22 | 诺沃梅尔公司 | Process for beta-lactone production |
| CN102702152A (en) * | 2012-06-04 | 2012-10-03 | 湖南大学 | Method for preparing organic lactone |
| WO2020033248A1 (en) * | 2018-08-07 | 2020-02-13 | Novomer, Inc. | Processes for producing beta-lactone and beta-lactone derivatives with heterogenous catalysts |
| CN112707883A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of epsilon-caprolactone |
| CN113441175A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Molecular sieve supported metal catalyst and preparation method thereof |
| CN111393394A (en) * | 2020-05-12 | 2020-07-10 | 上海朴颐化学科技有限公司 | Synthesis method of butyrolactone compound |
| CN111548333A (en) * | 2020-05-28 | 2020-08-18 | 陕西延长石油（集团）有限责任公司 | New method for preparing valerolactone |
| CN111484464A (en) * | 2020-05-28 | 2020-08-04 | 陕西延长石油（集团）有限责任公司 | Method for preparing valerolactone by catalyzing carbonylation of tetrahydrofuran |
| CN112209913A (en) * | 2020-10-30 | 2021-01-12 | 陕西延长石油（集团）有限责任公司 | Method for preparing adipic anhydride by catalyzing carbonylation of tetrahydrofuran |
| CN114602539A (en) * | 2020-12-08 | 2022-06-10 | 中国石油天然气股份有限公司 | Copper-based-molecular sieve composite catalyst and preparation method and application thereof |
| CN114656426A (en) * | 2021-12-13 | 2022-06-24 | 上海中化科技有限公司 | Method for preparing beta-lactone by continuously carbonylating epoxy compound |
| CN114289060A (en) * | 2021-12-30 | 2022-04-08 | 美思德(吉林)新材料有限公司 | Supported bimetallic catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱龙观，主编.《高等配位化学》.华东理工大学出版社,2009,(第01版),第179-180页. * |
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