CN114054083A - Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof - Google Patents
Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof Download PDFInfo
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 230000008707 rearrangement Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 23
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 3
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 23
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- RRXGIIMOBNNXDK-UHFFFAOYSA-N [Mg].[Sn] Chemical compound [Mg].[Sn] RRXGIIMOBNNXDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- BQCXRUZEFAZKMU-UHFFFAOYSA-N cyclohexanone;hydrogen peroxide Chemical compound OO.O=C1CCCCC1 BQCXRUZEFAZKMU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and a preparation method thereof. The catalyst SnO2MgO-TS-1 takes TS-1 as a carrier, SnO2MgO is an active component; SnO2SiO in MgO-TS-12/TiO2Molar ratio of 30-100, SnO2The mass ratio of MgO/TS-1 is 2:1, and MgO/SnO2The molar ratio is 3:1-1: 2. The preparation method comprises the following steps: (1) synthesizing Sn/Mg-TS-1 by a coprecipitation method by taking tin tetrachloride pentahydrate as a tin source, magnesium nitrate hexahydrate as a magnesium source and TS-1 as a carrier; (2) weighing stannic chloride pentahydrate, magnesium nitrate hexahydrate and TS-1, adding deionized water, and stirring for dissolving for 0.5 h; (3) preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the step (2) to generate white precipitate, stopping dropwise adding until the pH of the solution is =10, continuously stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours; (4) precipitation ofAnd (4) carrying out suction filtration and drying, grinding into fine powder, and then roasting to obtain the catalyst. The catalyst has better catalytic performance.
Description
Technical Field
The invention relates to a catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and a preparation method thereof.
Background
Epsilon-caprolactone is a monomer used to prepare biodegradable polymers that are widely used in tissue engineering, biocompatible coatings and drug delivery systems. In industry, peroxy acid is commonly used for oxidizing cyclohexanone to prepare epsilon-caprolactone, and due to the high cost of the peroxy acid, the generation of acid by-products causes a reaction system to further cause chemical reactions, such as caprolactone polymerization and the like, and causes negative influence on the environment. Therefore, the use of more environmentally friendly, safe peroxides instead of peroxyacid oxidants, such as H, has become an important research direction2O2The oxidative rearrangement of cyclohexanone in combination with a suitable catalyst under the action of a solvent has attracted considerable attention. Because the water in the hydrogen peroxide is easily decomposed by contacting with the product epsilon-caprolactone, the conversion rate of the cyclohexanone in the hydrogen peroxide system and the selectivity of the epsilon-caprolactone are low, which become technical difficulties at present.
TS-1 is a titanium silicon molecular sieve, belonging to Pentasil type heteroatom molecular sieve, orthorhombic system, having three-dimensional pore channel structure represented by ZSM-5, and composed of Z-shaped channel and oval straight channel intersecting with Z-shaped channel. The four-coordinated Ti in the framework of the titanium-silicon molecular sieve TS-1 is an active center of selective oxidation reaction, and besides the topological structure of the original MFI molecular sieve, the TS-1 forms a framework Si-O-Ti bond with special properties due to the uniform distribution of titanium atoms in the framework, so that the titanium-silicon molecular sieve TS-1 has catalytic oxidation activity and shape-selective catalytic performance. As strong acid Al ions do not exist in the skeleton structure, TS-1 has strong hydrophobicity and H2O2The participated shape-selective oxidation reaction of various organic compounds has unique catalytic performance, and the new generation of shape-selective oxidation catalytic material is regarded as a novel catalyst in the technical field of green chemistry.
Recently, the research on the catalytic reaction of applying a single metal oxide on a titanium silicalite molecular sieve (TS-1) as a catalyst to Bayer-Villeger attracts people's attention, but the application of a multi-metal oxide on the titanium silicalite molecular sieve as a catalyst to the oxidation rearrangement (B-V) reaction of cyclohexanone is not seen.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and a preparation method thereof.
The invention aims to solve the problem that a new catalyst is prepared by loading a bimetallic oxide on TS-1 in H2O2The oxidation rearrangement of cyclohexanone in the system for preparing epsilon-caprolactone improves the conversion rate of cyclohexanone and simultaneously improves the selectivity of epsilon-caprolactone.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement, and SnO (stannic oxide) serving as catalyst2MgO-TS-1 takes TS-1 as a carrier, SnO2MgO is an active component; SnO2SiO in MgO-TS-12/TiO2Molar ratio of 30-100, SnO2The mass ratio of MgO/TS-1 is 2:1, and MgO/SnO2The molar ratio is 3:1-1: 2.
The MgO/SnO2The molar ratio is 3: 1.
The preparation method of the catalyst comprises the following steps:
(1) synthesizing Sn/Mg-TS-1 by a coprecipitation method by taking tin tetrachloride pentahydrate as a tin source, magnesium nitrate hexahydrate as a magnesium source and TS-1 as a carrier;
(2) weighing stannic chloride pentahydrate, magnesium nitrate hexahydrate and TS-1, adding deionized water, and stirring for dissolving for 0.5 h;
(3) preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the step (2) to generate white precipitate, stopping dropwise adding until the pH of the solution is =10, continuously stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours;
(4) and (3) carrying out suction filtration on the precipitate, washing the precipitate with a large amount of deionized water to neutrality, drying a filter cake at 80 ℃, grinding the filter cake into fine powder, heating the fine powder to 600 ℃ at a speed of 5 ℃/min in a tubular furnace, and roasting the fine powder for 3 hours to obtain the catalyst.
The invention has the beneficial effects that:
the invention adopts the catalyst prepared by loading the magnesium-tin bimetallic oxide on the TS-1 molecular sieve to carry out the experiment of preparing the epsilon-caprolactone by oxidizing and rearranging the cyclohexanone in a hydrogen peroxide system, and the reaction result shows that the conversion rate of the cyclohexanone on the TS-1 loaded by the bimetallic oxide and the selectivity of the epsilon-caprolactone are obviously improved compared with the catalyst prepared by loading the TS-1 by the single metal oxide. The carrier of the catalyst improves the properties of TS-1 due to the addition of Sn, increases the active sites of Mg and Sn, obviously improves the conversion rate of the reaction, proves that a synergistic effect exists among Mg, Sn and TS-1, and is not reported at present.
Detailed Description
The catalyst of the present invention will be further illustrated by the following examples, but the present invention is not limited to these examples. Mg (magnesium)aSn1-athe-TS-1 is a representation mode for preparing epsilon-caprolactone by oxidizing and rearranging cyclohexanone in a hydrogen peroxide system, wherein a is the ratio of the feeding molar weight of magnesium.
Example 1 Mg0.5Sn0.5Preparation of (E) -TS-1
(1) 0.02 mol (7.01 g) of tin tetrachloride pentahydrate (SnCl) was weighed out separately4·5H2O), 0.02 mol (5.13 g) of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) and 1.51g TS-1 in a round bottom flask, 40 mL deionized water was added and dissolved at 35 ℃ for 0.5h with stirring.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) Filtering the precipitate with a funnel, washing the precipitate with deionized water until the mother liquor is neutral, drying the filter cake at 80 deg.C, grinding into fine powder, calcining at 5 deg.C/min in a tubular furnace to 600 deg.C for 3 h to obtain the catalyst designated as Mg0.5Sn0.5-TS-1。
Example 2 Mg0.75Sn0.25Preparation of (E) -TS-1
(1) 0.01 mol (3.51 g) of tin tetrachloride pentahydrate (SnCl) was weighed out separately4·5H2O), 0.03 mol (7.70 g) of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) and 0.75g TS-1 in a round bottom flask, adding 40 mL deionized water, at 35 degrees C stirring dissolved 0.5 h.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) Filtering the precipitate with a funnel, washing the precipitate with a large amount of deionized water to neutrality, drying the filter cake at 80 deg.C, grinding into fine powder, calcining at 5 deg.C/min in a tube furnace to 600 deg.C for 3 h to obtain the catalyst designated as Mg0.75Sn0.25-TS-1。
Example 3 Mg0.67Sn0.33Preparation of (E) -TS-1
(1) 0.01 mol (3.51 g) of tin tetrachloride pentahydrate (SnCl) was weighed out separately4·5H2O), 0.02 mol (5.13 g) of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) and 0.75g TS-1 in a round bottom flask, 40 mL deionized water was added and dissolved at 35 ℃ for 0.5h with stirring.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) Filtering the precipitate with a funnel, washing the precipitate with a large amount of deionized water to neutrality, drying the filter cake at 80 deg.C, grinding into fine powder, calcining at 5 deg.C/min in a tube furnace to 600 deg.C for 3 h to obtain the catalyst designated as Mg0.67Sn0.33-TS-1。
Example 4 Mg0.33Sn0.67Preparation of (E) -TS-1
(1) 0.02 mol (7.01 g) of tin tetrachloride pentahydrate (SnCl) was weighed out separately4·5H2O), 0.01 mol (2.56 g) of magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O) and 1.51g TS-1 in a round bottom flask, 40 mL deionized water was added and dissolved at 35 ℃ for 0.5h with stirring.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) Filtering the precipitate with a funnel, washing the precipitate with a large amount of deionized water to neutrality, drying the filter cake at 80 deg.C, grinding into fine powder, calcining at 5 deg.C/min in a tube furnace to 600 deg.C for 3 h to obtain the catalyst designated as Mg0.33Sn0.67-TS-1。
Comparative example 1 preparation of Sn-TS-1.
(1) 0.02 mol (7.01 g) of tin tetrachloride pentahydrate (SnCl) was weighed out separately5·5H2O) and 1.51g TS-1 in a round bottom flask, 40 mL deionized water was added and dissolved at 35 ℃ for 0.5h with stirring.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) And (3) carrying out suction filtration on the precipitate by using a funnel, washing the precipitate by using a large amount of deionized water until the precipitate is neutral, drying a filter cake at the temperature of 80 ℃, grinding the filter cake into fine powder, heating the fine powder to the temperature of 600 ℃ at the speed of 5 ℃/min in a tubular furnace, and roasting the fine powder for 3 hours to obtain the catalyst, wherein the obtained catalyst is marked as Sn-TS-1.
Comparative example 2 preparation of Mg-TS-1.
(1) 0.02 mol (5.13 g) of magnesium nitrate hexahydrate (Mg (NO) was weighed out separately3)2·6H2O) and 0.4g TS-1 in a round bottom flask, 40 mL deionized water was added and dissolved at 35 ℃ for 0.5h with stirring.
(2) And preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the solution to generate white precipitate, stopping dropwise adding until the pH =10 of the solution is about, continuing stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours.
(3) Filtering the precipitate with a funnel, washing the precipitate with deionized water to neutrality, drying the filter cake at 80 deg.C, grinding into fine powder, and placing in a tubular container
The temperature in the furnace is raised to 600 ℃ at the rate of 5 ℃/min and the catalyst is roasted for 3 h, and the obtained catalyst is marked as Mg-TS-1.
Application example
Cyclohexanone hydrogen peroxide oxidation evaluation reaction of the catalyst is carried out in a three-neck flask. A catalyst (0.235 g) accounting for 20% of the mass of cyclohexanone, 12 mmol (1.1777 g) of cyclohexanone, 10 mL (7.9 g) of acetonitrile, 72 mmol (8.16 g) of 30wt% hydrogen peroxide are taken, the reaction temperature is 75 ℃, and the reaction time is 6 h.
The catalysts prepared in examples 1-4 and the catalysts prepared in the comparative examples are applied to the activity and selectivity of oxidizing cyclohexanone by a hydrogen peroxide system, and the reaction results are data after the reaction reaches a stable state.
TABLE 1 catalytic performance of TS-1 loaded catalysts with different magnesium-tin molar ratios in oxidation reaction of cyclohexanone and hydrogen peroxide
| Catalyst and process for preparing same | Conversion rate/% | Selectivity/%) | Yield/% | |
| 1 | SnO2- TS-1 | 83.0 | 16.6 | 13.8 |
| 2 | Mg0.33Sn0.67- TS-1 | 95.7 | 21.1 | 20.0 |
| 3 | Mg0.5Sn0.5- TS-1 | 90.8 | 35.6 | 32.3 |
| 4 | Mg0.67Sn0.33- TS-1 | 89.9 | 57.2 | 51.4 |
| 5 | Mg0.75Sn0.25- TS-1 | 94.5 | 73.2 | 69.1 |
| 6 | MgO- TS-1 | 81.5 | 39.5 | 32.2 |
As can be seen from Table 1, the catalyst of the invention can obviously improve the conversion rate of cyclohexanone, and the selectivity of the catalyst containing magnesium to cyclohexanone is kept at a higher level, so that the catalyst is a high-efficiency catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone in a hydrogen peroxide system.
The molecular sieve loaded single metal oxide has a certain promotion effect on the reaction effect. The MgO-TS-1 catalyst shows better catalytic activity, the experimental yield reaches 32.2 percent, and the MgO alkaline oxide is presumed to beThe activated hydrogen peroxide and acetonitrile form a new intermediate, which has an accelerating effect on the activation of cyclohexanone and the oxidation process of the reaction. SnO2The catalytic activity of the-TS-1 catalyst is poor, the yield is only 13.8 percent, the hydrogen peroxide is presumed to be acidic, and simultaneously Sn (C)
) Has Lewis acidity, and the product is easily over-oxidized into adipic acid and other byproducts under the acidic condition. Catalyst MgaSn1-aThe selectivity and yield of the reaction are obviously improved when the feeding molar ratio a of the magnesium salt in the TS-1 is 0.67 and 0.75, and the Mg (C) is presumed to be
) Activating hydrogen peroxide and acetonitrile, and simultaneously Sn: (
) Effectively activate the carbonyl of the cyclohexanone, and the synergistic effect of the two promotes the improvement of the selectivity of the reaction. When a is 0.75, the yield of the reaction reaches 69.1%, and the synergy is optimal, and the selectivity of the reaction is obviously reduced when a is less than 0.75, which is presumed to be caused by SnO2The increase of (a) is that the acidic enhanced by-product of the reaction is easy to proceed, and when the a is 0.2, the selectivity is still higher than SnO2TS-1, description of Mg (
) Has the promotion effect on high reaction selectivity.
For the catalyst prepared by loading the single metal oxide on the existing TS-1 molecular sieve, the bimetallic oxide loaded on the TS-1 molecular sieve has better catalytic performance, and for the existing system for oxidizing cyclohexanone by hydrogen peroxide, the application of TS-1 in the system is preliminarily explored, and the catalyst has a leading effect on the subsequent TS-1 series catalyst in the preparation of epsilon-caprolactone from cyclohexanone.
Claims (3)
1. A catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement is characterized in that: the catalyst SnO2MgO-TS-1 takes TS-1 as a carrier, SnO2MgO is an active component; SnO2SiO in MgO-TS-12/TiO2Molar ratio of 30-100, SnO2The mass ratio of MgO/TS-1 is 2:1, and MgO/SnO2The molar ratio is 3:1-1: 2.
2. The catalyst of claim 1, wherein: the MgO/SnO2The molar ratio is 3: 1.
3. The method for preparing a catalyst according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) synthesizing Sn/Mg-TS-1 by a coprecipitation method by taking tin tetrachloride pentahydrate as a tin source, magnesium nitrate hexahydrate as a magnesium source and TS-1 as a carrier;
(2) weighing stannic chloride pentahydrate, magnesium nitrate hexahydrate and TS-1, adding deionized water, and stirring for dissolving for 0.5 h;
(3) preparing 2 mol/L ammonia water solution, slowly dropwise adding the ammonia water solution into the step (2) to generate white precipitate, stopping dropwise adding until the pH of the solution is =10, continuously stirring for 2 hours, and then standing the reaction solution at room temperature for 48 hours;
(4) and (3) carrying out suction filtration on the precipitate, washing the precipitate with deionized water to be neutral, drying a filter cake at 80 ℃, grinding the filter cake into fine powder, heating the fine powder to 600 ℃ at a speed of 5 ℃/min, and roasting the fine powder for 3 h to obtain the catalyst.
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| CN202111235261.8A CN114054083A (en) | 2021-10-22 | 2021-10-22 | Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof |
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| CN115445601A (en) * | 2022-08-15 | 2022-12-09 | 南京工业大学 | Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof |
| CN116116410A (en) * | 2023-02-24 | 2023-05-16 | 湘潭大学 | Copper-based catalyst and preparation method and application thereof |
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| CN116116410A (en) * | 2023-02-24 | 2023-05-16 | 湘潭大学 | Copper-based catalyst and preparation method and application thereof |
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