CN115353503A - Preparation method of epsilon-caprolactone - Google Patents
Preparation method of epsilon-caprolactone Download PDFInfo
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- CN115353503A CN115353503A CN202210783664.4A CN202210783664A CN115353503A CN 115353503 A CN115353503 A CN 115353503A CN 202210783664 A CN202210783664 A CN 202210783664A CN 115353503 A CN115353503 A CN 115353503A
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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
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Abstract
The invention provides a preparation method of epsilon-caprolactone. The preparation method comprises the following steps: reacting tetrahydropyran with carbon monoxide under the action of a catalyst to obtain epsilon-caprolactone; the catalyst comprises a molecular sieve and an active metal loaded in the molecular sieve, wherein the active metal comprises metallic copper. The method takes tetrahydropyran and carbon monoxide as raw materials, and prepares the epsilon-caprolactone with high added value by 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
The 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 high molecular polycaprolactone through ring-opening polymerization reaction. Polycaprolactone has good biocompatibility as polylactic acid, and cells can normally grow on the base frame of polycaprolactone and degrade to produce carbon dioxide and water, so that polycaprolactone can be used for drug slow-release carriers, cosmetic materials, vascular stents, surgical sutures, cell tissue culture base frames and the like. Compared with polylactic acid, polycaprolactone has better hydrophobicity and good chemical compatibility with high polymer materials such AS PE, PP, ABS, AS, PC, PVAC, PVB, PVE, PA, natural rubber and the like; the polycaprolactone also has good mechanical properties, and can be processed by injection molding, blow molding, die pressing, extrusion and other forming methods.
Currently, epsilon-caprolactone is prepared industrially mainly by the Baeyer-Villiger reaction of cyclohexane with peroxide. However, the method generates a plurality of three wastes, and the use of peroxide has greater potential safety hazard.
Therefore, the development of a novel safe and environment-friendly preparation method of the epsilon-caprolactone has important significance.
Disclosure of Invention
The invention provides a preparation method of epsilon-caprolactone, which uses cheap and easily obtained tetrahydropyran and carbon monoxide as raw materials and adopts a specific supported catalyst to prepare the chemical epsilon-caprolactone with high added value through a 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: reacting tetrahydropyran with carbon monoxide under the action of a catalyst to obtain epsilon-caprolactone;
the catalyst comprises a molecular sieve and an active metal loaded in the molecular sieve, wherein the active metal comprises metallic copper.
The preparation method as described above, wherein the loading amount of the active metal is 6 to 10wt%.
The preparation method as described above, wherein the active metal of the catalyst further comprises metallic cobalt.
The preparation method as described above, wherein the loading amount of the metal copper is 3-5wt%, and the loading amount of the metal cobalt is 2-6wt%.
The preparation method as described above, wherein the molecular sieve is ZSM-22 molecular sieve.
The preparation method as described above, wherein the SiO of the ZSM-22 molecular sieve 2 :Al 2 O 3 The molar ratio of (50-100): 1.
The preparation method as described above, wherein the reaction temperature is 150 to 300 ℃; and/or the pressure of the reaction is 1.5-3 MPa.
The preparation method as described above, wherein the catalyst is prepared by a method comprising the following steps: the method comprises the steps of dipping a salt solution of active metal on a molecular sieve carrier by an isometric dipping method, drying a dipping system to obtain a catalyst precursor, and roasting the catalyst precursor at 500-550 ℃ for 4-8 h to obtain the catalyst.
The preparation method as described above, wherein the preparation method comprises: passing a feed gas through a fixed bed reactor loaded with the catalyst to carry out the reaction;
the feed gas comprises tetrahydropyran and carbon monoxide;
the tetrahydropyran was fed through a saturation tube with nitrogen entrainment.
The production process as described above, wherein the flow rate of nitrogen when the tetrahydropyran is passed into the saturated tube by carrying with it the nitrogen is 3 to 5mL/min, and the feed flow rate of the carbon monoxide is 30 to 50mL/min.
The preparation method of the epsilon-caprolactone provided by the invention takes tetrahydropyran and carbon monoxide as raw materials, and obtains the chemical epsilon-caprolactone with high added value in one step through catalytic carbonylation ring-expanding reaction under the action of a specific supported catalyst. The method has the advantages of simple reaction process, cheap and easily-obtained raw materials, no adoption of a noble metal catalyst, less 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
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of epsilon-caprolactone, which comprises the following steps: reacting tetrahydropyran with carbon monoxide under the action of a catalyst 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 of the present invention can be represented by the following reaction formula:
the carbonylation ring-expanding reaction of epoxy compound makes one of the important methods for synthesizing lactone compounds. At present, the carbonylation ring expansion reaction of epoxy compounds with three-membered ring, four-membered ring and five-membered ring has been reported. But the tension of the three-membered ring and the four-membered ring is larger, the tension of the expanded ring can be relieved, and the tension of the five-membered ring and the six-membered ring is small, so that the tension of the expanded five-membered ring into the six-membered ring is relatively smaller. However, since the six-membered ring has a stable structure and the seven-membered ring has an unstable structure, it is difficult to expand the six-membered ring into the seven-membered ring, and it has not been reported until now that the tetrahydropyran having a six-membered ring is carbonylated and expanded into e-caprolactone having a seven-membered ring structure.
The inventor researches and discovers that when a supported catalyst is adopted and a carrier is selected from a molecular sieve, and an active metal loaded on the molecular sieve comprises metallic copper, the carbonylation ring-expanding reaction of tetrahydropyran can be realized, and a chemical epsilon-caprolactone with high added value can be obtained through a one-step method.
The raw materials of tetrahydropyran and carbon monoxide used in the preparation method are cheap and easy to obtain, noble metal elements are not used in the catalyst, the reaction condition is simple and mild, three wastes are hardly generated, and the preparation method has the advantages of safety, environmental protection and low cost.
Further, when the supported amount of the active metal is 6 to 10wt%, the catalyst has more excellent catalytic effect. Wherein the loading amount of the active metal can be calculated by the mass of the active metal component/(mass of the active metal component + mass of the carrier).
In a particular embodiment, the active metal of the catalyst comprises metallic cobalt in addition to metallic copper. The metal cobalt and the metal copper can play a catalytic synergistic role, so that the reaction has higher tetrahydropyrane 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 in the catalyst is ZSM-22 molecular sieve. Besides a pore channel structure which is more matched with tetrahydropyran, the surface of the ZSM-22 molecular sieve has a certain acidic site, so that the ZSM-22 molecular sieve can assist active metal to enhance the catalytic activity of the catalyst.
As is well known to those skilled in the art, the catalyst can be prepared by subjecting ZSM-22 molecular sieve SiO 2 :Al 2 O 3 The regulation and control of the molar ratio of (a) and (b) realizes the condition of the acid density of the molecular sieve. Specifically, siO 2 :Al 2 O 3 The higher the molar ratio of (a), the lower the acid density of the molecular sieve; siO 2 2 :Al 2 O 3 The lower the molar ratio of (a), the higher the acid density of the molecular sieve. The inventor finds that when the SiO of the ZSM-22 molecular sieve is used as the SiO 2 :Al 2 O 3 The molar ratio of (50-100): 1, and the molecular sieve has a relatively proper acid density, thereby ensuring that the catalyst has good catalytic performance.
Further, the above reaction can 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 adopting the preparation method of the supported catalyst which is conventional in the field. For example, the catalyst can be prepared by an isometric impregnation method, for example, a salt solution of an active metal is impregnated on a molecular sieve carrier by the isometric impregnation method, then the impregnation system is dried to obtain a catalyst precursor, and finally the catalyst precursor is calcined at 500-550 ℃ for 4-8 h to obtain the supported metal catalyst of the invention.
The preparation reaction of the invention can be carried out in a fixed bed reactor, and specifically comprises the step of enabling a raw material gas to pass through the fixed bed reactor loaded with the catalyst for reaction, wherein the raw material gas comprises tetrahydropyran and carbon monoxide. Since tetrahydropyran is liquid at room temperature, tetrahydropyran may be fed through a saturated tube with nitrogen entrainment.
Before the reaction, the method also comprises a process of pretreating the catalyst, wherein the pretreatment comprises the following steps: the catalyst was pretreated at 300 ℃ for 1h under nitrogen atmosphere.
The gases produced after the reaction in the fixed bed reactor can be introduced into an on-line chromatograph for analysis through a heated line.
In a specific embodiment, the reaction can be carried out using a reaction tube having an inner diameter of 10mm and a length of 40cm, and the reaction tube is filled with 0.5g of the catalyst to obtain a good reaction effect.
According to the comprehensive consideration of the volume of the reactor selected by the invention, the activity of the catalyst and other factors, 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 by the nitrogen and is introduced into the saturation tube.
The preparation process of epsilon-caprolactone provided by the present invention will be further described with reference to specific examples.
In the following examples, all starting materials and reagents were prepared by either commercially available or conventional methods, unless otherwise specified.
Example 1
The preparation of epsilon-caprolactone of this example is as follows:
1) 123g of Co (NO) 3 ) 2 ·6H 2 O and 95g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 100g water, stirring to dissolve completely, adding 500g ZSM-22 molecular Sieve (SiO) 2 :Al 2 O 3 The molar ratio of (1) is 70);
wherein the supported bimetallic catalyst has a cobalt loading of 5wt% and a copper loading of 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 200 ℃, introducing reaction raw material gas for reaction, wherein the tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 3mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) The collected product was analyzed by gas chromatography, and fig. 1 is a gas chromatogram of the product collected in example 1, from which fig. 1 it was calculated that the conversion of tetrahydropyran was 25.6% and the selectivity of epsilon-caprolactone was 93.9%.
Example 2
The preparation of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 100, and a catalyst, wherein the molar ratio of the ZSM-22 molecular sieve to the catalyst is 100The loading of medium cobalt was 3wt% and the loading of copper was 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 250 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 5mL/min, and the feed 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 of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (1) is 60, the loading of cobalt in the catalyst is 6wt%, and the loading of copper 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 250 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when tetrahydropyran is passed into the saturation tube by nitrogen entrainment is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a tetrahydropyran conversion of 16.8% and an epsilon-caprolactone selectivity of 96.7%.
Example 4
The preparation of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (1) is 80, the loading of cobalt in the catalyst is 2wt%, and the loading of copper 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 150 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, the reaction pressure is controlled at 3MPa, and the reacted gas is introduced into a gas chromatograph through a heated pipeline;
wherein the flow rate of nitrogen when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 5mL/min, and the feed flow rate of carbon monoxide is 40mL/min.
3) Analysis of the collected product by gas chromatography gave a tetrahydropyran conversion of 9.6% and an epsilon-caprolactone selectivity of 90.1%.
Example 5
The preparation of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 In a molar ratio of90, the catalyst has a cobalt loading of 4wt% and a copper loading of 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 180 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when tetrahydropyran is passed into the saturation tube by nitrogen entrainment is 3mL/min, and the feed flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product by gas chromatography gave a tetrahydropyran conversion of 21.7% and an epsilon-caprolactone selectivity of 95.5%.
Example 6
The preparation of epsilon-caprolactone of this example is as follows:
1) 95g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 100g water, stirring to dissolve completely, adding 500g ZSM-22 molecular Sieve (SiO) 2 :Al 2 O 3 In a molar ratio of 70: 1) Ultrasonically dipping for 2h, filtering, washing, drying at 120 ℃, and then roasting for 5h at 550 ℃ to obtain a supported catalyst loaded with metal copper;
wherein the loading of copper in the supported catalyst is 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, and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 200 ℃, introducing reaction raw material gas for reaction, wherein the tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of tetrahydropyran of 10.3% and a selectivity of epsilon-caprolactone of 99.7%.
Example 7
The preparation of epsilon-caprolactone in this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (1) to (2%) is 60, and the loading amount of cobalt in the catalyst is 2wt% and the loading amount of copper is 1wt%.
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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 250 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of tetrahydropyran of 4.2% and a selectivity of epsilon-caprolactone of 85.3%.
Example 8
The preparation of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (1) is 60, the loading of cobalt in the catalyst is 8wt%, and the loading of copper is 8wt%.
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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 250 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a tetrahydropyran conversion of 30.7% and an epsilon-caprolactone selectivity of 62.0%.
Example 9
The preparation of epsilon-caprolactone of this example is as follows:
1) Preparing a supported bimetallic catalyst loaded with metal cobalt and copper by referring to the same method as the step 1) of the example;
wherein the catalyst carrier is SiO 2 :Al 2 O 3 The molar ratio of (1) is 60, the loading of cobalt in the catalyst is 6wt%, and the loading of copper 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 pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 250 ℃, starting to introduce reaction raw material gas for reaction, wherein tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of tetrahydropyran of 5.8% and a selectivity of epsilon-caprolactone of < 1%.
Comparative example 1
1) 0.5g of ZSM-22 molecular Sieve (SiO) was weighed 2 :Al 2 O 3 At a molar ratio of 70).
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, and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pretreating the filled catalyst for 1 hour at 300 ℃ in a nitrogen atmosphere;
adjusting the temperature of the reactor to 200 ℃, introducing reaction raw material gas for reaction, wherein the tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when tetrahydropyran is passed into the saturation tube by nitrogen entrainment is 5mL/min, and the feed flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of < 1% tetrahydropyran, with no detectable production of epsilon-caprolactone.
Comparative example 2
1) 0.5g of ZSM-5 molecular Sieve (SiO) was weighed 2 :Al 2 O 3 At a molar ratio of 70).
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, and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 200 ℃, introducing reaction raw material gas for reaction, wherein the tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when tetrahydropyran is passed into the saturation tube by nitrogen entrainment is 5mL/min, and the feed flow rate of carbon monoxide is 50mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of < 1% tetrahydropyran, with no detectable production of epsilon-caprolactone.
Comparative example 3
1) 123gCo (NO) 3 ) 2 ·6H 2 Dissolving O in 100g water, stirring to dissolve completely, adding 500g ZSM-22 (SiO) 2 :Al 2 O 3 In a molar ratio of 70: 1) Ultrasonic dipping for 2h, filtering, washing, drying at 120 ℃, and roasting at 550 ℃ for 5h to obtain a supported catalyst loaded with metal cobalt;
wherein the supported amount of cobalt in the supported catalyst was 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, and the length of the reaction tube is 40 cm) of a fixed bed reactor, and pretreating the filled catalyst for 1h in a nitrogen atmosphere at 300 ℃;
adjusting the temperature of the reactor to 200 ℃, introducing reaction raw material gas for reaction, wherein the tetrahydropyran is carried by nitrogen and fed through a saturation tube, 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 when the tetrahydropyran is introduced into the saturation tube by carrying the tetrahydropyran by nitrogen is 4mL/min, and the feed flow rate of carbon monoxide is 30mL/min.
3) Analysis of the collected product by gas chromatography gave a conversion of < 1% tetrahydropyran, with no detectable production of epsilon-caprolactone.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for producing epsilon-caprolactone, comprising: reacting tetrahydropyran with carbon monoxide under the action of a catalyst to obtain epsilon-caprolactone;
the catalyst comprises a molecular sieve and an active metal loaded in the molecular sieve, wherein the active metal comprises metallic copper.
2. The method according to claim 1, wherein the loading amount of the active metal is 6 to 10wt%.
3. The method of claim 1 or 2, wherein the active metal of the catalyst further comprises metallic cobalt.
4. The method according to claim 3, wherein the loading amount of the metallic copper is 3 to 5wt% and the loading amount of the metallic cobalt is 2 to 6wt%.
5. The method of any one of claims 1-4, wherein the molecular sieve is a ZSM-22 molecular sieve.
6. The method of claim 5, wherein the ZSM-22 molecular sieve is SiO 2 :Al 2 O 3 The molar ratio of (50-100): 1.
7. The method according to any one of claims 1 to 6, wherein the reaction temperature is 150 to 300 ℃; and/or the pressure of the reaction is 1.5-3 MPa.
8. The method according to any one of claims 1 to 7, wherein the catalyst is prepared by a method comprising: the method comprises the steps of dipping a salt solution of active metal on a molecular sieve carrier by an isometric dipping method, drying a dipping system to obtain a catalyst precursor, and roasting the catalyst precursor at 500-550 ℃ for 4-8 h to obtain the catalyst.
9. The production method according to any one of claims 1 to 7, characterized by comprising: passing a feed gas through a fixed bed reactor loaded with the catalyst to carry out the reaction;
the feed gas comprises tetrahydropyran and carbon monoxide;
the tetrahydropyran was fed through a saturation tube with nitrogen entrainment.
10. The method according to claim 9, wherein the flow rate of nitrogen when the tetrahydropyran is introduced into the saturation tube by carrying the nitrogen is 3 to 5mL/min, and the feed flow rate of the carbon monoxide is 30 to 50mL/min.
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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 (10)
| Title |
|---|
| GARY D.ANNIS, 等: "Preparation of lactones via tricarbonyliron-lactone complexes", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1: ORGANIC AND BIO-ORGANIC CHEMISTRY, no. 01, pages 270 - 277 * |
| JUAN ALMENA, 等: "Lithium 2-(2-lithiomethylphenyl)ethanolate from isochroman: easy preparation of substituted benzoxepines and functionalized arenes", TETRAHEDRON, vol. 51, no. 11, pages 3365 - 3374, XP004104770, DOI: 10.1016/0040-4020(95)00065-G * |
| YUTAN D. Y. L. GETZLER, 等: "Synthesis of β-Lactones: A Highly Active and Selective Catalyst for Epoxide Carbonylation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 124, no. 07, pages 1174 - 180 * |
| 刘建华, 等: "杂环化合物的羰基化反应", 化学进展, no. 06, pages 989 - 999 * |
| 吉定豪;等: "Cu/ZSM-5催化剂的表征及其环己醇脱氢性能", 石油化工, no. 06, pages 570 - 574 * |
| 张光旭;等: "固体酸催化合成ε-己内酯的研究 Ⅰ.催化剂的表征及其催化性能", 石油化工, vol. 40, no. 05, pages 486 - 491 * |
| 徐文涛;等: "环己酮催化氧化合成ε-己内酯催化剂的研究――介孔分子筛超强酸催化剂的研制及表征", 山东化工, vol. 37, no. 10, pages 1 - 4 * |
| 李相呈, 等: "SCM-14分子筛高效催化环己酮氧化制备ε-己内酯", 化学反应工程与工艺, vol. 35, no. 05, pages 385 - 392 * |
| 樊启佳, 等: "环氧化合物羰基化反应研究新进展", 催化学报, vol. 33, no. 09, pages 1435 - 1447 * |
| 程丹;等: "δ-环戊内酯的合成及应用", 安徽化工, no. 04, pages 6 - 9 * |
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