CN112517021B - Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof - Google Patents
Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof Download PDFInfo
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- CN112517021B CN112517021B CN202011430737.9A CN202011430737A CN112517021B CN 112517021 B CN112517021 B CN 112517021B CN 202011430737 A CN202011430737 A CN 202011430737A CN 112517021 B CN112517021 B CN 112517021B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention discloses cobalt-doped modified dioxygenA tin-dissolving catalyst, a preparation method and application thereof. The catalyst is used for modifying pure-phase tin dioxide by doping cobalt, the mass fraction of Co is 1.0-5.0 wt.%, and SnO is added 2 Dispersing the powder in an ethanol-water solution containing cobalt nitrate hexahydrate and polyvinylpyrrolidone, continuously stirring under a heating condition until the solution is completely evaporated to dryness, and finally putting the sample in a crucible and calcining at 400-600 ℃ to obtain the catalyst. The invention applies the cobalt-doped modified stannic oxide catalyst to the epoxidation of styrene for the first time, and has excellent catalytic reaction effect.
Description
Technical Field
The invention relates to a cobalt-doped modified tin dioxide catalyst, a preparation method and application thereof, belonging to the technical field of preparation of organic reaction catalysts.
Background
Styrene oxide is an important fine chemical and is widely applied. At present, the traditional halohydrin method and peroxy acid direct oxidation method are mainly adopted for preparing epoxyphenylethane industrially, but the problems of high material cost, serious equipment corrosion, environmental pollution and the like exist. In order to solve the problems of the conventional methods, in recent years, attention has been paid to a method for producing styrene oxide by performing styrene epoxidation reaction by using an environmentally-friendly, economically-reasonable catalytic system. For example, The literature (The Journal of Physical Chemistry C,2020,124, 10530-10540) discloses The deposition of TiO by atomic layer 2 Coated on SBA-15/Au catalyst and used in styrene epoxidation reaction using tert-butyl hydroperoxide as oxidant in a series of different TiO 2 In the catalyst, after 6 hours of reaction, although the conversion rate of styrene can be close to 100% at most, the selectivity of the styrene oxide is lower than 50%. Literature (Nanoscale Advances,2020,2,1437) confines to mesoporous SiO 2 The Au catalyst is used in the styrene epoxidation reaction taking tert-butyl hydroperoxide as an oxidant, and after the reaction is carried out for 12 hours under the optimal reaction condition, the conversion rate of styrene reaches 88.0%, the selectivity of styrene oxide is 74.0%, and the yield is 65.1%. The literature (Materials Chemistry Frontiers,2019,3, 1580-1585) prepares Cu-porphyrin MOF nanosheetsWhen the catalyst is used in the styrene epoxidation reaction with tert-butyl hydroperoxide as an oxidant, the conversion rate of styrene reaches 94.0%, the selectivity of styrene oxide is 49.2%, and the yield is 46.2%. Literature (ACS Sustainable Chemistry)&Engineering 2019,7,17008-17019) prepared a series of three-dimensional/two-dimensional MnO 2 /g-C 3 N 4 The nano composite catalyst is used in the epoxidation reaction of styrene with tert-butyl hydroperoxide as oxidant, and 8MnO is found through screening 2 The NP/UCN catalyst has the best catalytic performance, the conversion rate of styrene is 78.3%, the selectivity of epoxyphenylethane is 77.6%, and the yield is 60.8%. Although many catalysts have been reported and have been developed obviously, the system still has the problems of complex catalyst preparation process, high preparation cost, low reaction activity, poor product selectivity and the like. Therefore, it is very important to find a catalyst which is simple and inexpensive to prepare and which can be used in the highly efficient selective epoxidation of styrene.
The stannic oxide has the characteristics of low price, environmental friendliness, good chemical stability and the like. Tin dioxide-based catalysts have been widely used in carbon dioxide electroreduction (Applied Catalysis B: Environmental,2020,261,118243), photocatalytic reduction of carbon dioxide (Catalysis Science)&Technology,2019,9,6566–6569)，NO x The selective catalytic reduction (Chinese Journal of Catalysis,2020,41, 877-3192) and the photocatalytic hydrogen production (Inorganic Chemistry,2020,59, 3181-3192). At present, the application of tin dioxide to the selective oxidation reaction of styrene is not studied.
Disclosure of Invention
The invention aims to provide a cobalt-doped modified tin dioxide catalyst which is simple to prepare, low in price and excellent in performance, a preparation method and application thereof in efficient selective catalytic epoxidation of styrene.
In order to achieve the purpose, the invention adopts the following scheme:
the preparation method of the cobalt-doped modified tin dioxide catalyst comprises the following steps:
(1) dissolving cobalt nitrate hexahydrate and polyvinylpyrrolidone (PVP, K30) in a mixed solution of water and ethanol;
(2) SnO 2 Dispersing the powder in the solution obtained in the step (1), and continuously stirring under a heating condition until the solution is completely evaporated to dryness;
(3) and (3) calcining the sample obtained in the step (2) in a crucible at 400-600 ℃ for 2h to obtain the cobalt-doped modified tin dioxide catalyst, wherein the mass fraction of Co is 1.0-5.0 wt.%.
Preferably, in step (1), the volume ratio of water to ethanol is 1: 1.
Preferably, in step (2), SnO 2 The mass ratio of the polyvinyl pyrrolidone to the polyvinyl pyrrolidone is 1: 1.
Preferably, in the step (2), the heating temperature is 60-80 ℃.
Preferably, in the step (3), the calcining temperature is 500 ℃ and the calcining time is 2 h.
Preferably, in the step (3), the mass fraction of Co is 2.0-3.0 wt.%.
The invention also provides a cobalt-doped modified tin dioxide catalyst prepared by the preparation method.
Further, the invention provides an application of the cobalt-doped modified tin dioxide catalyst in preparation of styrene oxide through selective oxidation of styrene.
Specifically, the application method comprises the following steps: uniformly mixing styrene, acetonitrile and tert-butyl hydroperoxide, adding a cobalt-doped modified tin dioxide catalyst, and reacting at 70-90 ℃ to obtain a product styrene oxide.
Preferably, in the application method, urea is also added into the catalytic system to improve the selectivity. In a specific embodiment of the invention, the mass ratio of urea to cobalt-doped modified tin dioxide catalyst is 4: 1.
Preferably, the amount of the cobalt-doped modified tin dioxide catalyst is 3.2-9.6 wt.% of styrene.
Preferably, the reaction time is 6-12 h.
Compared with the prior art, the invention has the following advantages:
(1) the cobalt-doped modified tin dioxide catalyst disclosed by the invention is simple in preparation method and low in preparation cost.
(2) The cobalt-doped modified tin dioxide catalyst is applied to the preparation of styrene oxide by selective oxidation of styrene for the first time, has good catalytic effect and can be recycled for multiple times; compared with the prior catalytic reaction system, the catalyst has remarkable advantages in comprehensive performance and good industrial application prospect.
Drawings
FIG. 1 shows cobalt-doped modified tin dioxide catalysts (Co-doped SnO) prepared in examples 1-5 2 ) And pure-phase SnO as in comparative example 1 2 XRD pattern of (a).
FIG. 2 is Co-doped SnO prepared in example 1 2 SEM picture of catalyst 2.
FIG. 3 is Co-doped SnO prepared in example 1 2 -2 TEM image of the catalyst.
FIG. 4 is Co-doped SnO prepared in example 1 2 HRTEM image of catalyst-2.
Detailed Description
The invention is further described in detail below with reference to the figures and examples.
Example 1
Weigh 0.0494gCo (NO) 3 ) 2 ·6H 2 O and 0.5g polyvinylpyrrolidone (PVP, K30) were dissolved in a mixed solvent (20ml deionized water and 20ml ethanol), and then 0.5g SnO was added 2 Powder is evenly stirred, the mixture is continuously stirred at 60 ℃ until the solution is completely evaporated to dryness, and then the mixture is placed in a crucible and calcined for 2 hours at 500 ℃ to obtain the cobalt-doped stannic oxide catalyst (the mass fraction of cobalt is 2 wt.%), and the catalyst is marked as Co-doped SnO 2 -2。
The prepared catalyst is used for the selective epoxidation reaction of styrene. First, 15mmol of styrene, 45mmol of t-butyl hydroperoxide and 0.7mol of acetonitrile were mixed, and then 0.1g of a catalyst was added to react in a constant temperature water bath at 80 ℃ for 8 hours, and the product was analyzed by gas chromatography, whereby it was found that the conversion of styrene reached 96.7% in the 8 th hour and the selectivity of ethylene oxide reached 75.5%. In addition, in order to test the recycling performance of the catalyst, the reacted catalyst was filtered, washed thoroughly with hot water and acetone, and then dried in vacuum at 120 ℃ for 24 hours for recycling test, and it was found that the activity and selectivity of the catalyst did not decrease significantly in five cycles.
FIG. 1 contains Co-doped SnO prepared in example 1 2 -2 XRD pattern of the catalyst.
FIG. 2 is Co-doped SnO prepared in example 1 2 -2 SEM picture of catalyst.
FIG. 3 is Co-doped SnO prepared in example 1 2 -2 TEM image of the catalyst.
FIG. 4 shows Co-doped SnO prepared in example 1 2 HRTEM image of the catalyst-2.
Example 2
Example 1 was repeated, except that 0.0247g Co (NO) was added to the catalyst preparation process 3 ) 2 ·6H 2 O to obtain Co-doped SnO 2 1 catalyst (mass fraction of cobalt 1 wt.%). Under otherwise identical reaction conditions, the conversion of styrene was 60.9% and the selectivity to styrene oxide was 71.3%.
FIG. 1 contains Co-doped SnO prepared in example 2 2 -1 XRD pattern of the catalyst.
Example 3
Example 1 was repeated, except that in the catalyst preparation method, 0.0741g of Co (NO) was added 3 ) 2 ·6H 2 O to obtain Co-doped SnO 2 -3 catalyst (mass fraction of cobalt 3 wt.%). Under otherwise identical reaction conditions, the conversion of styrene was 97.4% and the selectivity to styrene oxide was 70.8%.
FIG. 1 contains Co-doped SnO prepared in example 3 2 -3 XRD pattern of the catalyst.
Example 4
Example 1 was repeated, except that 0.0988g of Co (NO) were added in the catalyst preparation process 3 ) 2 ·6H 2 O to obtain Co-doped SnO 2 4 catalyst (mass fraction of cobalt 4 wt.%). Under otherwise identical reaction conditions, the conversion of styrene was 94.3% and the selectivity to styrene oxide was 43.8%.
FIG. 1 contains Co-doped SnO prepared in example 4 2 -XRD pattern of catalyst 4.
Example 5
Example 1 was repeated, except that 0.1235g of Co (NO) were added in the catalyst preparation process 3 ) 2 ·6H 2 O to obtain Co-doped SnO 2 -5 catalyst (mass fraction of cobalt 5 wt.%). Under otherwise identical reaction conditions, the conversion of styrene was 94.4% and the selectivity to styrene oxide was 62.8%.
Example 6
Example 1 was repeated, except that 0.05g of Co-doped SnO was added 2 -2 catalyst to the catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 75.2% and the selectivity to styrene oxide was 71.5%.
Example 7
Example 1 was repeated, except that 0.15g of Co-doped SnO was added 2 -2 catalyst to the catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 99.6% and the selectivity to styrene oxide was 62.6%.
Example 8
Example 1 was repeated except that the calcination temperature used for the catalyst preparation was 400 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 81.3% and the selectivity to styrene oxide was 78.7%.
Example 9
Example 1 was repeated except that the calcination temperature used for the catalyst preparation was 600 ℃. Under otherwise identical reaction conditions, the conversion of styrene at 8h was 95.4% and the selectivity to styrene oxide was 71.5%.
Example 10
Example 1 was repeated except that the catalytic reaction temperature was 70 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 54.3% and the selectivity to styrene oxide was 68.3%.
Comparative example 1
The catalytic performance test was carried out using pure tin dioxide powder as a catalyst under otherwise the same reaction conditions as in example 1, and the results showed that: the styrene conversion was 18.8% and the selectivity to styrene oxide was 47.1%.
FIG. 1 contains tin dioxide (SnO) used in comparative example 1 2 ) XRD pattern of catalyst.
Comparative example 2
Example 1 was repeated, except that 0.02g of Co-doped SnO was added 2 -2 catalyst to the catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 38.6% and the selectivity to styrene oxide was 79.6%.
Comparative example 3
Example 1 was repeated, except that 0.2g of Co-doped SnO was added 2 -2 catalyst to the catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 97.6% and the selectivity to styrene oxide was 59.5%.
Example 11
Example 1 was repeated except that the catalytic reaction temperature was 90 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 86.7% and the selectivity to styrene oxide was 60.7%.
Comparative example 4
Example 1 was repeated except that the catalytic reaction temperature was 60 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 32.1% and the selectivity to styrene oxide was 44.8%.
Comparative example 5
Example 1 was repeated except that the catalytic reaction temperature was 95 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 69.4% and the selectivity to styrene oxide was 48.8%.
Example 12
Example 1 was repeated, except that the catalytic reaction time was 6 h. Under otherwise identical reaction conditions, the conversion of styrene was 85.3% and the selectivity to styrene oxide was 77.0%.
Example 13
Example 1 was repeated, except that the catalytic reaction time was 7 h. Under otherwise identical reaction conditions, the conversion of styrene was 92.2% and the selectivity to styrene oxide was 77.7%.
Example 14
Example 1 was repeated, except that the catalytic reaction time was 9 h. Under otherwise identical reaction conditions, the conversion of styrene was 98.1% and the selectivity to styrene oxide was 73.9%.
Example 15
Example 1 was repeated, except that the catalytic reaction time was 10 h. Under otherwise identical reaction conditions, the conversion of styrene was 99.9% and the selectivity to styrene oxide was 70.2%.
Example 16
Example 1 was repeated, except that the catalytic reaction time was 11 h. Under otherwise identical reaction conditions, the conversion of styrene was 99.9% and the selectivity to styrene oxide was 66.3%.
Example 17
Example 1 was repeated, except that the catalytic reaction time was 12 h. Under otherwise identical reaction conditions, the conversion of styrene was 99.9% and the selectivity to styrene oxide was 61.5%.
Example 18
Example 1 was repeated, except that 0.4g of urea was added to the catalytic reaction system. Under the same other reaction conditions, the conversion rate of the styrene at the 8 th hour is 90.6 percent, and the selectivity of the styrene oxide is 80.9 percent; the conversion of styrene in the 9 th hour was 96.0%, and the selectivity to styrene oxide was 81.3%; the conversion of styrene in 10h was 98.1% and the selectivity to styrene oxide was 83.8%; the conversion of styrene in 11h was 99.0% and the selectivity to styrene oxide was 84.9%; the conversion of styrene at 12h was 99.1% with a selectivity to styrene oxide of 82.1%.
It will be readily appreciated by those skilled in the art that the above-described embodiments are merely illustrative of the present invention and are not intended to limit the present invention, and any extension, modification, replacement, improvement, etc. made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (6)
1. The application of the cobalt-doped modified tin dioxide catalyst in the preparation of styrene oxide by selective oxidation of styrene is characterized in that the specific application method comprises the following steps: uniformly mixing styrene, acetonitrile and tert-butyl hydroperoxide, adding a cobalt-doped modified tin dioxide catalyst, and reacting at 70-90 ℃ for 6-12 h to obtain a product styrene oxide, wherein the dosage of the cobalt-doped modified tin dioxide catalyst is 3.2-9.6 wt.% of styrene, and the cobalt-doped modified tin dioxide catalyst is prepared by the following steps:
(1) cobalt nitrate hexahydrate and polyvinylpyrrolidone PVPK30 dissolving in a mixed solution of water and ethanol;
(2) SnO 2 Dispersing the powder in the solution obtained in the step (1), and continuously stirring under a heating condition until the solution is completely evaporated to dryness;
(3) and (3) calcining the sample obtained in the step (2) in a crucible at 400-600 ℃ for 2h to obtain the cobalt-doped modified tin dioxide catalyst, wherein the mass fraction of Co is 1.0-5.0 wt.%.
2. The use according to claim 1, wherein in step (1), the volume ratio of water to ethanol is 1: 1.
3. The use according to claim 1, wherein in step (2), SnO 2 The mass ratio of the polyvinyl pyrrolidone to the polyvinyl pyrrolidone is 1:1, and the heating temperature is 60-80 ℃.
4. Use according to claim 1, wherein in step (3) the calcination temperature is 500 ℃.
5. The use according to claim 1, wherein in step (3), the mass fraction of Co is 2.0-3.0 wt.%.
6. The use of claim 1, wherein urea is added to the catalytic system, and the mass ratio of urea to cobalt-doped modified tin dioxide catalyst is 4: 1.
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| CN109939693B (en) * | 2019-03-29 | 2021-09-28 | 扬州大学 | CoMn2O4Bimetallic oxide catalyst, preparation method and application |
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