CN111974409B - Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof - Google Patents

Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof Download PDF

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CN111974409B
CN111974409B CN202010815314.2A CN202010815314A CN111974409B CN 111974409 B CN111974409 B CN 111974409B CN 202010815314 A CN202010815314 A CN 202010815314A CN 111974409 B CN111974409 B CN 111974409B
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manganese
nickel oxide
styrene
catalyst
doped nickel
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CN111974409A (en
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刘江永
王海洋
王理霞
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Yangzhou University
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Yangzhou University
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    • 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof. The catalyst is in a sheet porous structure, wherein the atomic ratio of Mn to Ni is 0.019 to 1 to 0.086, and the catalyst comprises the following steps: and (3) taking the flaky NiO as a precursor, carrying out manganese doping by soaking manganese nitrate tetrahydrate, and roasting at a certain temperature to obtain the flaky porous manganese-doped nickel oxide catalyst. The catalyst shows excellent reaction effect in the selective oxidation reaction of styrene, and comprises higher reaction activity, higher product selectivity, good recycling performance and the like.

Description

Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof
Technical Field
The invention relates to a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof, and belongs to the technical field of preparation of organic reaction catalysts.
Background
The epoxy phenylethane is used as an important intermediate of medicines and spices, can be used as an epoxy resin diluent, a flavoring agent and a stabilizing agent, and is widely applied to the preparation of phenethyl alcohol, levamisole hydrochloride and the like.
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, equipment corrosion, environmental pollution and the like exist. In order to solve the problems of the conventional methods, in recent years, extensive attention has been paid to a method for producing styrene oxide by performing styrene epoxidation reaction by using an environmentally-friendly, economical and reasonable catalytic system. For example, chinese patent CN101181687A discloses Ag-Fe 3 O 4 Magnetic nano-catalyst and application in styrene epoxidation. The catalyst comprises Ag and Fe, wherein Ag is a specific active component, and is prepared by a solvothermal method. Although the catalyst has better catalytic activity in the styrene epoxidation reaction, the Ag as a noble metal element has limited reserves and higher price, and further application of the Ag is limited.In various catalysts studied at present, metalloporphyrin complexes have complex structures and more factors influencing the activity of the metalloporphyrin complexes, heteropoly acid catalysts and noble metal catalysts have high cost, and metal oxide catalysts have relatively simple preparation conditions and relatively low economic cost, so that great attention is paid to the metalloporphyrin complexes. However, the reaction performance of a simple metal oxide catalyst in the selective oxidation of styrene is still far from the same as that of other catalyst systems. For example, the document cat. Commun. 10 (2008) 205-207 uses NiO nanoparticles for styrene selective oxidation with an epoxystyrene yield of only 44.6%; document mater. Lett. 80 (2012) 23-25 use NiO hollow nanodiscs for the selective oxidation of styrene with an epoxystyrene yield of 53.8%; the document Micropor, mesopor, mater, 238 (2017) 69-77 adopts a complex preparation method to embed NiO nano-particles in mesoporous SiO 2 When the catalyst is used for the selective oxidation of styrene, the yield of epoxy styrene is 63.0 percent. Therefore, how to upgrade and modify the metal oxide catalyst by a simple and effective method to improve the reaction performance has very important significance.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a flaky porous manganese-doped nickel oxide catalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a manganese-doped nickel oxide catalyst is in a sheet-shaped porous structure, wherein the atomic ratio of Mn to Ni is (0.019) - (1) - (0.086).
The preparation method of the flaky porous manganese-doped nickel oxide catalyst comprises the following steps:
(1) The flake NiO was dispersed in a mixed solution of deionized water and ethanol, and then a certain amount of polyvinylpyrrolidone (PVP,K30 ) and stirring uniformly;
(2) Adding manganese nitrate tetrahydrate into the solution, and continuously stirring at 60 ℃ until the solution is completely evaporated to dryness;
(3) The obtained powder is dried at 100 ℃ for 12 h, and then is roasted in the air at 500 to 700 ℃ for 2 to 4 hours to obtain the flaky porous manganese-doped nickel oxide catalyst.
Preferably, in step (1), the volume ratio of water to ethanol is 1:1.
Preferably, in the step (1), the mass ratio of NiO to polyvinylpyrrolidone is 1:1.
Preferably, in the step (2), the mass ratio of the manganese nitrate tetrahydrate to the NiO is 0.12.
Preferably, in the step (3), the calcination temperature of the catalyst is 600 ℃, and the calcination time is 3 h.
The invention also provides application of the flaky porous manganese-doped nickel oxide catalyst in preparation of styrene oxide through selective oxidation of styrene.
The reaction process comprises the following steps: uniformly mixing styrene, acetonitrile and tert-butyl hydroperoxide, then adding the prepared catalyst, and reacting for a period of time at a certain temperature to obtain the target product styrene oxide.
Preferably, the amount of the catalyst is 3.2 to 12.8 wt.% of styrene.
Preferably, the reaction temperature is 60 to 90 ℃.
Preferably, the reaction time is 6 to 10 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the flaky porous manganese-doped nickel oxide catalyst is simple and has low preparation cost.
(2) The catalytic system of the invention has simple reaction conditions, does not add any solvent or additive, takes tert-butyl hydroperoxide as an oxidant and is environment-friendly.
(3) The reaction effect of the sheet-shaped porous manganese-doped nickel oxide catalyst synthesized by the method is obviously superior to that of an undoped nickel oxide catalyst, the catalytic effect is not obviously reduced after the catalyst is repeatedly used for many times, and the stability is good; under the same reaction condition, the comprehensive catalytic performance of the catalyst is obviously superior to that of the related catalytic system reported at present, and the catalyst has good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of the flaky porous manganese-doped nickel oxide (Mn-NiO) catalysts prepared in examples 1 to 4 of the present invention.
FIG. 2 is an SEM image of an Mn-NiO-2 catalyst prepared in example 1 of the present invention.
FIG. 3 is a HRTEM image of the Mn-NiO-2 catalyst prepared in example 1 of the present invention.
FIG. 4 is an SEM image of an Mn-NiO-1 catalyst prepared in example 2 of the invention.
FIG. 5 is an SEM image of an Mn-NiO-3 catalyst prepared in example 3 of the present invention.
FIG. 6 is an SEM image of an Mn-NiO-4 catalyst prepared in example 4 of the present invention.
Detailed Description
The technical solution of the present invention is explained in detail below with reference to the accompanying drawings and examples.
Example 1
The flake NiO powder 0.5 g was weighed out and dispersed in a mixed solvent (20 mL deionized water and 20 mL ethanol), followed by the addition of 0.5 g polyvinylpyrrolidone (PVP,K30 And stirred until uniform. Then 0.117 g Mn (NO) was added 3 ) 2 ·4H 2 O, stirring at the constant temperature of 60 ℃ until the solution is evaporated to dryness, then drying at 100 ℃ for 12 h, and then roasting at 600 ℃ for 3 h under the air condition to obtain the flaky porous manganese-doped nickel oxide catalyst, wherein the mark is Mn-NiO-2. Through inductively coupled plasma-atomic emission spectroscopy testing, the atomic ratio of Mn to Ni is 0.030.
The prepared catalyst is used for the selective oxidation reaction of styrene. Firstly, 1.56 g styrene, 6.24 g tert-butyl hydroperoxide and 16 mL acetonitrile are mixed, then 0.1 g of Mn-NiO-2 catalyst is added, 8 h is reacted under the condition of 80 ℃ constant temperature water bath, and the product is analyzed by gas chromatography, and as a result, the conversion rate of the styrene reaches 96.4%, and the selectivity of the ethylene oxide reaches 77.8%. In addition, in order to test the catalyst recycling performance, the reacted catalyst was filtered off, and washed thoroughly with hot water and acetone, and then dried at 100 ℃ for 24 h for the next test. As a result, the Mn-NiO-2 catalyst is not obviously reduced in catalytic activity and selectivity to the styrene oxide after being recycled for five times.
The XRD pattern of the Mn-NiO-2 catalyst prepared in example 1 is contained in FIG. 1.
FIG. 2 is an SEM image of the Mn-NiO-2 catalyst prepared in example 1.
FIG. 3 is a HRTEM image of the Mn-NiO-2 catalyst prepared in example 1.
Comparative example 1
In example 1, a blank experiment was performed, i.e. without the addition of catalyst, showing that: the styrene conversion was 17.9% and the ethylene oxide selectivity was 72.2%.
Comparative example 2
The flake NiO was used directly as a catalyst for performance testing under the same reaction conditions as in example 1, and the results show that: the styrene conversion was 31.5% and the styrene oxide selectivity was 76.2%.
Example 2
Example 1 was repeated, except that 0.058 g of Mn (NO) was added 3 ) 2 ·4H 2 And O is added into the preparation system to obtain the Mn-NiO-1 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 89.2 percent, and the selectivity of the epoxyphenylethane reaches 74.4 percent.
The XRD pattern of the Mn-NiO-1 catalyst prepared in example 2 is contained in FIG. 1.
FIG. 4 is an SEM image of the Mn-NiO-1 catalyst prepared in example 2.
Example 3
Example 1 was repeated, except that 0.175 g of Mn (NO) was added 3 ) 2 ·4H 2 And O is added into the preparation system to obtain the Mn-NiO-3 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 91.2, and the selectivity of the epoxyphenylethane reaches 66.7 percent.
The XRD pattern of the Mn-NiO-3 catalyst prepared in example 3 is contained in FIG. 1.
FIG. 5 is an SEM image of the Mn-NiO-3 catalyst prepared in example 3.
Example 4
Example 1 was repeated, except that 0.233 g of Mn (NO) was added 3 ) 2 ·4H 2 And O is added into the preparation system to obtain the Mn-NiO-4 catalyst. Under the same reaction conditions, the conversion rate of the styrene reaches 67 percent5%, the selectivity of the epoxy styrene reaches 78.0%.
The XRD pattern of the Mn-NiO-4 catalyst prepared in example 4 is contained in FIG. 1.
FIG. 6 is an SEM image of the Mn-NiO-4 catalyst prepared in example 4.
Example 5
Example 1 was repeated except that the temperature of the styrene epoxidation reaction was set to 60 c, at which time the styrene conversion reached 42.5% and the styrene oxide selectivity reached 54.4%.
Example 6
Example 1 was repeated except that the temperature of the styrene epoxidation reaction was set to 90 c, at which the styrene conversion reached 99.1% and the styrene oxide selectivity reached 72.3%.
Example 7
Example 1 was repeated except that the reaction time was 6 h at which time the styrene conversion reached 82.9% and the styrene oxide selectivity reached 80.4%.
Example 8
Example 1 was repeated except that the reaction time was 10 h at which time the styrene conversion reached 99.4% and the styrene oxide selectivity reached 70.7%.
Example 9
Example 1 was repeated except that t-butyl hydroperoxide was added at 2.08 g where styrene conversion reached 49.6% and styrene oxide selectivity reached 76.0%.
Example 10
Example 1 was repeated except that t-butyl hydroperoxide was added at 8.32 g where styrene conversion was 94.7% and styrene oxide selectivity was 74.1%.
Example 11
Example 1 was repeated except that 0.05 g of NiO/NMO-2 catalyst was added, at which point the styrene conversion reached 70.8% and the ethylene oxide selectivity reached 77.6%.
Example 12
Example 1 was repeated, except that 0.20 g of NiO/NMO-2 catalyst was added, at which point the styrene conversion reached 99.9% and the ethylene oxide selectivity reached 59.1%.
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 (10)

1. The manganese-doped nickel oxide catalyst is characterized by having a sheet-shaped porous structure, wherein the atomic ratio of Mn to Ni is (1) - (0.019);
the manganese-doped nickel oxide catalyst is prepared by the following steps:
(1) Dispersing the flaky NiO in a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone, and uniformly stirring;
(2) Adding manganese nitrate tetrahydrate into the solution, and continuously stirring at 60 ℃ until the solution is completely evaporated to dryness;
(3) Drying the obtained powder at 100 ℃ for 12 h, and then roasting in the air at 500-700 ℃ for 2-4 h to obtain the manganese-doped nickel oxide catalyst.
2. A method of preparing the manganese-doped nickel oxide catalyst of claim 1, comprising the steps of:
(1) Dispersing the flaky NiO in a mixed solution of deionized water and ethanol, adding polyvinylpyrrolidone, and uniformly stirring;
(2) Adding manganese nitrate tetrahydrate into the solution, and continuously stirring at 60 ℃ until the solution is completely evaporated to dryness;
(3) Drying the obtained powder at 100 ℃ for 12 h, and then roasting in the air at 500-700 ℃ for 2-4 h to obtain the manganese-doped nickel oxide catalyst.
3. The method of claim 2, wherein in step (1), the volume ratio of deionized water to ethanol is 1:1.
4. The method of claim 2, wherein in step (1), the mass ratio of NiO to polyvinylpyrrolidone is 1:1.
5. The method of claim 2, wherein in the step (2), the mass ratio of the manganese nitrate tetrahydrate to the NiO is (0.12) - (1-0.47).
6. Use of the manganese-doped nickel oxide catalyst of claim 1 in the selective oxidation of styrene to styrene oxide.
7. The use according to claim 6, wherein the reaction is carried out by: uniformly mixing styrene, acetonitrile and tert-butyl hydroperoxide, adding a manganese-doped nickel oxide catalyst, and reacting at a certain temperature for a period of time to obtain a target product, namely styrene oxide.
8. The use according to claim 7, wherein the manganese-doped nickel oxide catalyst is used in an amount of 3.2 to 12.8 wt.% based on styrene.
9. The use as claimed in claim 7, wherein the reaction temperature is from 60 to 90 ℃.
10. The use according to claim 7, wherein the reaction time is from 6 to 10 hours.
CN202010815314.2A 2020-08-13 2020-08-13 Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof Active CN111974409B (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
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CN107252690A (en) * 2017-05-09 2017-10-17 北京化工大学 A kind of base catalyst of supported copper oxide containing auxiliary agent and preparation method thereof
CN107381662A (en) * 2016-07-01 2017-11-24 淮阴师范学院 The preparation method and applications of the magnetic oxygenated nickel of additive Mn
CN111007122A (en) * 2019-12-04 2020-04-14 山西大学 Three-dimensional flower-like nano composite material and preparation method and application thereof

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101463020A (en) * 2007-12-18 2009-06-24 中国科学院兰州化学物理研究所 Method for synthesizing epoxy styrene by direct oxidation of phenylethylene
CN107381662A (en) * 2016-07-01 2017-11-24 淮阴师范学院 The preparation method and applications of the magnetic oxygenated nickel of additive Mn
CN107252690A (en) * 2017-05-09 2017-10-17 北京化工大学 A kind of base catalyst of supported copper oxide containing auxiliary agent and preparation method thereof
CN111007122A (en) * 2019-12-04 2020-04-14 山西大学 Three-dimensional flower-like nano composite material and preparation method and application thereof

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