CN109569585A - Preparation method of micro-nano monodisperse manganese-based catalyst and products thereof and application - Google Patents
Preparation method of micro-nano monodisperse manganese-based catalyst and products thereof and application Download PDFInfo
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- CN109569585A CN109569585A CN201811576721.1A CN201811576721A CN109569585A CN 109569585 A CN109569585 A CN 109569585A CN 201811576721 A CN201811576721 A CN 201811576721A CN 109569585 A CN109569585 A CN 109569585A
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
Abstract
The invention discloses preparation methods of a kind of micro-nano monodisperse manganese-based catalyst and products thereof and application, introduce the manganese nitrate that redox reaction can occur with azomethine base in situ during aldimine condensation prepares schiff bases silica, regulate and control coverage, the ratio of azomethine base and manganese nitrate of azomethine base on the surface of the material, it is ensured that manganese can be carried on silica supports in the form of monodispersed.Gained micro-nano monodisperse manganese-based catalyst of the invention has the characteristics that load capacity is high, is uniformly dispersed, active component is single.This method preparation method is simple, is easy to large-scale production, has a good application prospect.
Description
Technical field
The present invention relates to a kind of micro-nano preparation methods of monodisperse catalyst, and in particular to a kind of micro-nano monodisperse manganese
Preparation method of base catalyst and products thereof and application.
Background technique
Nanocatalyst refers to that at least one dimension is in nanoscale range (1nm ~ 100nm) or by it in three dimensions
As basic unit constitute catalyst.Nanocatalyst has the height of the low coordination of more high-specific surface area and more surfaces living
Property site, shows the excellent catalytic performance different from conventional material.With the reduction of catalyst size, surface is free
It can dramatically increase, be also easy to produce agglomeration.Loaded catalyst, can because there is strong interaction between its active component and carrier
To effectively prevent assembling, the dispersibility, high activity and stability of active component are maintained, is widely used in the industry.
However, actual negative supported catalyst is generally difficult to obtain evenly dispersed active component, partial size is usually by more than ten
A nanometer is mixed to several nanometers or even sub-nanometer cluster etc..The Modulatory character that this will lead to catalyst is poor, goal response
The unfavorable results such as more than selectively low, side reaction once.And active component homogeneity is precisely one of notable feature of homogeneous catalysis, but
It is that homogeneous catalysis has the shortcomings that dimerization inactivation, reaction efficiency are low, catalyst recycling separation is difficult.
Dispersed nano catalyst, i.e. active component loaded in the form of monodispersed with carrier on, be active component high score
The scattered limit is heterogeneous catalysis and the common objective that homogeneous catalysis is pursued.The isolated effect of the existing nanocatalyst of monodisperse catalyst
Answer, synergistic effect, surface and interface effect and easily recycling separation the features such as, while have both homogeneous catalyst activated centre it is uniform and
The features such as target product selectivity is high is the important directions of catalytic field development.
Since 2011 Nian Zhangtao seminars are put forward for the first time " monatomic catalyst " concept [Nat. Chem., 3
(2011) 634-641], monatomic/monodisperse catalysis is being developed rapidly, and becomes the research hotspot of heterogeneous catalysis field.
But monatomic at present/monodisperse catalyst exists or loading is relatively low or preparation process is more complicated or reaction process
The disadvantages of structure is not sufficiently stable.
Summary of the invention
For disadvantages mentioned above existing for current monodisperse catalyst, it is an object of that present invention to provide a kind of micro-nano monodisperses
The preparation method of manganese-based catalyst.
Another object of the present invention is: the micro-nano monodisperse manganese-based catalyst for providing a kind of above method preparation produces
Product.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of preparation method of micro-nano monodisperse manganese-based catalyst, in aldehyde
Original position introduces the manganese nitrate that redox reaction can occur with azomethine base during amine condensation prepares schiff bases silica,
Regulate and control coverage, the ratio of azomethine base and manganese nitrate of azomethine base on the surface of the material, it is ensured that manganese can be with monodispersed shape
Formula is carried on silica supports, comprising the following steps:
The first step weighs in a certain amount of 3- aminopropyl triethoxysilane (APTES) Yu Shiliang deionized water, under stirring condition
Sufficiently dissolution, is made into the APTES solution of 0.3mol/L；
Second step weighs a certain amount of formaldehyde (HCHO) solution in appropriate deionized water, stirs evenly, be made into 0.3mol/L's
Formalin；
Above two solution is sufficiently mixed by third step, is stirred 1-2 hours at room temperature；
Suitable 50% manganese nitrate (Mn (NO is added in 4th step3)2) solution, 50-80 DEG C reaction 1-2 hours, be transferred to water heating kettle
In, the reaction was continued under 80-110 DEG C of hydrothermal condition 12-16 hours, obtains micro-nano monodisperse manganese-based catalyst.
On the basis of above scheme, APTES, formaldehyde, the proportionate relationship of manganese nitrate are as follows: (nHCHO+ n Mn (NO3)2):
NAPTES=1:1, nMn (NO3)2:nAPTES=1:36-1:14。
The present invention provides a kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is characterised in that including following step
It is rapid: to weigh 3.51g APTES in 52.8mL deionized water, sufficiently dissolved under stirring condition, the APTES for being made into 0.3mol/L is molten
Liquid；The formalin of 1.25g 37% is weighed in 49.7mL deionized water, stirs evenly, is made into the formalin of 0.3mol/L；
Above two solution is sufficiently mixed, is stirred 1 hour at room temperature；50% manganese nitrate solution of 0.33g is added, 50 DEG C of reactions 1 are small
When, it is transferred in water heating kettle, the reaction was continued under 80 DEG C of hydrothermal conditions 12 hours, obtains micro-nano monodisperse manganese-based catalyst.
The present invention provides a kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is characterised in that including following step
It is rapid: to weigh 3.47g APTES in 52.2mL deionized water, sufficiently dissolved under stirring condition, the APTES for being made into 0.3mol/L is molten
Liquid；The formalin of 1.23g 37% is weighed in 48.9mL deionized water, stirs evenly, is made into the formalin of 0.3mol/L；
Above two solution is sufficiently mixed, is stirred 1 hour at room temperature；50% manganese nitrate solution of 0.39g is added, 50 DEG C of reactions 1 are small
When, it is transferred in water heating kettle, the reaction was continued under 100 DEG C of hydrothermal conditions 12 hours, obtains micro-nano monodisperse manganese-based catalyst.
The present invention provides a kind of micro-nano monodisperse manganese-based catalyst, is prepared according to any of the above-described the method.
The present invention provides a kind of application of micro-nano monodisperse manganese-based catalyst in formaldehyde improvement as catalyst, condition
As follows: total gas flow rate is 500 mL/min, and reaction pressure is normal pressure -1atm, and the initial concentration of formaldehyde is 5 mg/m3, sample
Dosage: 0.1 g.
Micro-nano monodisperse manganese-based catalyst obtained by this patent has load capacity is high, be uniformly dispersed, active component is single etc.
Feature.Rationally coverage, the ratio and reaction condition of azomethine base and manganese nitrate of control azomethine base on the surface of the material,
It is carried on manganese on silica supports in the form of monodispersed, gained micro-nano monodisperse manganese-based catalyst has both nano-catalytic
With the advantage of homogeneous catalysis.With azomethine base oxygen can occur in situ introduce during aldimine condensation prepares schiff bases silica
Change the manganese nitrate of reduction reaction, gained micro-nano monodisperse manganese-based catalyst active component manganese has stronger phase interaction with carrier
With catalyst stability is good.This method active component manganese load capacity is high, preparation method is simple, is easy to large-scale production, has very
Good application prospect.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1:
A kind of preparation method of micro-nano monodisperse manganese-based catalyst is prepared former in schiff bases silica process in aldimine condensation
Position introduces the manganese nitrate that redox reaction can occur with azomethine base, regulation azomethine base coverage on the surface of the material,
The ratio of azomethine base and manganese nitrate, it is ensured that manganese can be carried on silica supports in the form of monodispersed, by following step
It is rapid:
3.51g APTES is weighed in 52.8mL deionized water, is sufficiently dissolved under stirring condition, the APTES of 0.3mol/L is made into
Solution；
The formalin of 1.25g 37% is weighed in 49.7mL deionized water, is stirred evenly, the formaldehyde for being made into 0.3mol/L is molten
Liquid；
Above two solution is sufficiently mixed, is stirred 1 hour at room temperature；
50% manganese nitrate solution of 0.33g is added, 50 DEG C are reacted 1 hour, are transferred in water heating kettle, are continued under 80 DEG C of hydrothermal conditions
Reaction 12 hours.Obtain micro-nano monodisperse manganese-based catalyst Mn1/SiO2-1。
Embodiment 2:
A kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is approximate with embodiment 1, according to the following steps:
3.60g APTES is weighed in 54.2mL deionized water, is sufficiently dissolved under stirring condition, the APTES of 0.3mol/L is made into
Solution；
The formalin of 1.30g 37% is weighed in 51.8mL deionized water, is stirred evenly, the formaldehyde for being made into 0.3mol/L is molten
Liquid；
Above two solution is sufficiently mixed, is stirred 2 hours at room temperature；
50% manganese nitrate solution of 0.16g is added, 80 DEG C are reacted 2 hours, are transferred in water heating kettle, are continued under 110 DEG C of hydrothermal conditions
Reaction 16 hours.Obtain micro-nano monodisperse manganese-based catalyst Mn1/SiO2-2。
Embodiment 3:
A kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is approximate with embodiment 1, according to the following steps:
3.54g APTES is weighed in 53.3mL deionized water, is sufficiently dissolved under stirring condition, the APTES of 0.3mol/L is made into
Solution；
The formalin of 1.27g 37% is weighed in 50.6mL deionized water, is stirred evenly, the formaldehyde for being made into 0.3mol/L is molten
Liquid；
Above two solution is sufficiently mixed, is stirred 1.5 hours at room temperature；
Be added 0.26g 50% manganese nitrate solution, 65 DEG C react 1.5 hours, be transferred in water heating kettle, under 90 DEG C of hydrothermal conditions after
Continuous reaction 14 hours.Obtain micro-nano monodisperse manganese-based catalyst Mn1/SiO2-3。
Embodiment 4:
A kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is approximate with embodiment 1, according to the following steps:
3.47g APTES is weighed in 52.2mL deionized water, is sufficiently dissolved under stirring condition, the APTES of 0.3mol/L is made into
Solution；
The formalin of 1.23g 37% is weighed in 48.9mL deionized water, is stirred evenly, the formaldehyde for being made into 0.3mol/L is molten
Liquid；
Above two solution is sufficiently mixed, is stirred 1 hour at room temperature；
50% manganese nitrate solution of 0.39g is added, 50 DEG C are reacted 1 hour, are transferred in water heating kettle, are continued under 100 DEG C of hydrothermal conditions
Reaction 12 hours.Obtain micro-nano monodisperse manganese-based catalyst Mn1/SiO2-4。
Application examples
It is prepared for the micro-nano monodisperse manganese base formula catalyst of embodiment 1-4 using the above method, is filled in continuous flow fixed bed
It is tested in setting in room temperature low concentration formaldehyde purifying property.Test condition is as follows: total gas flow rate is 500 mL/min, reaction
Pressure is normal pressure ~ 1atm, and the initial concentration of formaldehyde is 5 mg/m3, amount of samples: 0.1 g.Test result is as follows shown in table:
。
Claims (6)
1. a kind of preparation method of micro-nano monodisperse manganese-based catalyst, it is characterised in that prepare schiff bases dioxy in aldimine condensation
It is in situ during SiClx to introduce the manganese nitrate that redox reaction occur with azomethine base, regulate and control azomethine base in material table
Coverage, the ratio of azomethine base and manganese nitrate in face, it is ensured that manganese can be carried on silica supports in the form of monodispersed
On, comprising the following steps:
The first step weighs in a certain amount of 3- aminopropyl triethoxysilane (APTES) Yu Shiliang deionized water, under stirring condition
Sufficiently dissolution, is made into the APTES solution of 0.3mol/L；
Second step weighs a certain amount of formaldehyde (HCHO) solution in appropriate deionized water, stirs evenly, be made into 0.3mol/L's
Formalin；
Above two solution is sufficiently mixed by third step, is stirred 1-2 hours at room temperature；
Suitable 50% manganese nitrate (Mn (NO is added in 4th step3)2) solution, 50-80 DEG C reaction 1-2 hours, be transferred to water heating kettle
In, the reaction was continued under 80-110 DEG C of hydrothermal condition 12-16 hours, obtains micro-nano monodisperse manganese-based catalyst.
2. preparation method according to claim 1, it is characterised in that the ratio of APTES, formaldehyde, manganese nitrate are as follows: (nHCHO+
½ n Mn(NO3)2): nAPTES=1:1, nMn (NO3)2:nAPTES=1:36-1:14。
3. preparation method according to claim 1 or 2, it is characterised in that the following steps are included: weigh 3.51g APTES in
It in 52.8mL deionized water, is sufficiently dissolved under stirring condition, is made into the APTES solution of 0.3mol/L；Weigh the first of 1.25g 37%
Aldehyde solution stirs evenly in 49.7mL deionized water, is made into the formalin of 0.3mol/L；Above two solution is sufficiently mixed
It closes, stirs 1 hour at room temperature；50% manganese nitrate solution of 0.33g is added, 50 DEG C are reacted 1 hour, are transferred in water heating kettle, 80 DEG C
The reaction was continued under hydrothermal condition 12 hours, obtains micro-nano monodisperse manganese-based catalyst.
4. preparation method according to claim 1 or 2, it is characterised in that the following steps are included: weigh 3.47g APTES in
It in 52.2mL deionized water, is sufficiently dissolved under stirring condition, is made into the APTES solution of 0.3mol/L；Weigh the first of 1.23g 37%
Aldehyde solution stirs evenly in 48.9mL deionized water, is made into the formalin of 0.3mol/L；Above two solution is sufficiently mixed
It closes, stirs 1 hour at room temperature；50% manganese nitrate solution of 0.39g is added, 50 DEG C are reacted 1 hour, are transferred in water heating kettle, 100
The reaction was continued 12 hours under DEG C hydrothermal condition, obtains micro-nano monodisperse manganese-based catalyst.
5. a kind of micro-nano monodisperse manganese-based catalyst, it is characterised in that -4 any the methods are prepared into according to claim 1
It arrives.
6. a kind of micro-nano monodisperse manganese-based catalyst according to claim 5 answering as catalyst in formaldehyde improvement
With condition is as follows: total gas flow rate is 500 mL/min, and reaction pressure is normal pressure -1atm, and the initial concentration of formaldehyde is 5 mg/
m3, amount of samples: 0.1 g.
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| CN110833841A (en) * | 2019-11-12 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Micro-nano monodisperse ruthenium phosphide catalyst and preparation method and application thereof |
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