CN106902863A - A kind of meso-porous titanium dioxide manganese and its preparation method and application - Google Patents
A kind of meso-porous titanium dioxide manganese and its preparation method and application Download PDFInfo
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- CN106902863A CN106902863A CN201710182341.9A CN201710182341A CN106902863A CN 106902863 A CN106902863 A CN 106902863A CN 201710182341 A CN201710182341 A CN 201710182341A CN 106902863 A CN106902863 A CN 106902863A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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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
- 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
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Abstract
The invention provides a kind of meso-porous titanium dioxide manganese and its preparation method and application, methods described is included with mesoporous silicon material as template, by the dipping of manganese nitrate solution, dry, roasting obtains presoma after removing maceration extract, then removes template and obtains the meso-porous titanium dioxide manganese；Wherein, mesoporous silicon template can be commercially available acquisition, or be obtained with prior art conventional method.The invention provides ethanol selective oxidation low temperature acetaldehyde catalyst, compared with oxidation of ethanol acetaldehyde is electrolysed Ag and Cu base catalyst with catalyst, meso-porous titanium dioxide Mn catalyst of the present invention can at low temperature produce acetaldehyde, reduce acetaldehyde production energy consumption；Acetaldehyde is not decomposed under making the acetaldehyde higher and low temperature of selectivity, can effectively improve resource utilization.More than 60%, acetaldehyde selectively up to 100% may be up to using meso-porous titanium dioxide manganese catalysis ethanol acetaldehyde of the invention.
Description
Technical field
It is to be related to a kind of meso-porous titanium dioxide manganese and its preparation method and application specifically the present invention relates to chemical field.
Background technology
Acetaldehyde is important organic chemical industry's intermediate, can be used to manufacture multi-chemical or industrial chemicals such as：Acetic acid, acetic acid
Ester, pentaerythrite, Peracetic acid, 1,3 butylene glycol, ketenes, ethyl acetate, crotonaldehyde, crotonaldehyde, trichloroacetaldehyde, acetic acid second
Alkene ester, pyridine etc..Acetaldehyde has industrial application value very high.
The method for synthesizing acetaldehyde mainly has：Ethylene method, oxidation of ethanol method, acetylene hydration process, acetic acid reduction, ethane
Oxidizing process, C3/C4 oxidation of alkanes method, methane and carbon monoxide synthetic method.Wherein, oxidation of ethanol method and ethylene process are to use in the world
In the main method of production acetaldehyde.Due to ethene heavy dependence fossil energy, and ethanol is renewable, so using oxidation of ethanol method
Acetaldehyde processed has certain advantage.In China, it is in the great majority using the enterprise of oxidation of ethanol method production acetaldehyde.
The selection of catalyst is most important to oxidation of ethanol legal system acetaldehyde, directly affects productivity ratio, energy consumption, the money of enterprise
Source utilization rate etc..Physical chemistry teaching and research group of Fudan University (application [J] the stones of Xiang Yifei catalyst for electrolytic silver in acetaldehyde production
Oiling work, 1978,04:323-326.) using electrolysis Ag catalysis ethanol acetaldehyde, catalytic performance is silver-colored better than filigree and float stone,
Reaction temperature has higher conversion and selectivity in the range of 450~640 DEG C, and ethanol unit consumption is 1.188 ton/ton acetaldehyde, by-product
Thing has CO, CO2、CH4Deng.Liu Bingyu and Ye Daen (Liu Bingyu, Ye Daen Oxidative dehydrogenation of ethanol acetaldehyde new technology [J] Jiangsu
Chemical industry, 1982,04:Oxidation of ethanol method 58-59.) is reported using Ag catalyst, reaction temperature at 550~580 DEG C, receive by one way
Rate 70~75%, selectivity 95% or so, ethanol unit consumption is 1.1~1.28 ton/ton acetaldehyde；Also Cu bases catalyst is reported such as
Cu-Cr-Ba catalysis ethanol acetaldehyde performances, under conditions of being 310 DEG C in normal pressure, reaction temperature, ethanol conversion 27~73%,
Acetaldehyde selectivity 65~86%, acetaldehyde 22~57%.The reaction temperature of the catalyst will be less than the reaction temperature of Ag catalyst
Degree, but keeps or close electrolysis Ag catalyst on catalytic performance.(Liu Hongchao, red legend is good, Liu Yong, Liu Zhongmin, Meng for Liu Chaohong etc.
White crane, Li Lina, Liu Shiping, a kind of all intelligent ethanol direct dehydrogenations of prepare preparation and its application [P] Liaoning of acetaldehyde catalyst:
CN103127945A, 2013-06-05.) sol-gal process is used, with Cu as active component, P is auxiliary agent, SiO2、Al2O3、ZrO2
One of them is carrier, is prepared for Cu loaded catalysts, the mol ratio of the 0.1wt%~30wt%, P and Cu of Cu load total amounts
It is 0.001~3.The catalyst reacts for ethanol acetaldehyde, and at 200~350 DEG C, ethanol conversion is more than reaction temperature
55%, acetaldehyde is selectively more than 93% in product.At present, oxidation of ethanol acetaldehyde technology is ripe, is above-mentioned with catalyst
Ag or Cu base catalyst.
Although Ag and Cu base catalyst has good oxidation of ethanol acetaldehyde performance, its optimal reaction temperature is higher than
300 DEG C, energy consumption is higher, and by-product species are more.Especially Ag catalyst reaction temperatures are up to 600 DEG C or so, observable index Cu bases
Catalyst is higher and acetaldehyde is readily decomposed to CH4And CO.
Therefore, in order to further reduce energy consumption, improve resource utilization, oxidation of ethanol acetaldehyde clean manufacturing is promoted
The development of technology, finds a kind of efficient, ethanol Selective Oxidation acetaldehyde catalyst under cryogenic, is that this area still needs to
One of problem to be solved.
The content of the invention
It is an object of the present invention to provide a kind of meso-porous titanium dioxide manganese；
Preparation method another object of the present invention is to provide the meso-porous titanium dioxide manganese；
A further object of the present invention is to provide the application of the meso-porous titanium dioxide manganese；The present invention uses the meso-porous titanium dioxide
Manganese is used for ethanol acetaldehyde, and ethanol selective oxidation low temperature acetaldehyde being capable of reducing energy consumption, reduction accessory substance yield, raising acetaldehyde
Yield and acetaldehyde selectivity.
It is up to above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of meso-porous titanium dioxide manganese, wherein, it is described
Method is included with mesoporous silicon material as template, by the dipping of manganese nitrate solution, before dry after removing maceration extract, roasting is obtained
Body is driven, template is then removed and is obtained the meso-porous titanium dioxide manganese；Wherein, after presoma is obtained, the presoma that will be obtained is again
With manganese nitrate solution impregnate, remove maceration extract after dry, roasting, dipping, dry, roasting the step of repeat 0-5 times.
Wherein it is understood that 0 time repeated in 0-5 times of the present invention refers to that the step is not repeated,
That is after presoma is obtained, " presoma that will be obtained is impregnated with manganese nitrate solution again, removes dry, roasting after maceration extract
Burn " in process in quotation marks and do not exist, i.e. after methods described obtains presoma, presoma is directly removed template and is done again
It is dry to obtain the meso-porous titanium dioxide manganese；
And according to some specific embodiments of the invention, wherein after presoma is obtained, the presoma that will be obtained uses nitre again
Sour manganese solution is impregnated, and is dried after evaporation removing maceration extract, is calcined, and the step (the step of impregnating, dry, being calcined) is repeated 1-3 times.
Wherein it is understood that repetition of the present invention, is that after presoma is obtained, " presoma will again be used into nitre
The step of sour manganese solution dipping, dry after removing maceration extract, roasting ", is repeatedly；For example when being repeated 3 times, it is：Before obtaining
After driving body, presoma is impregnated with manganese nitrate solution again, dried after removing maceration extract, roasting, then by the presoma after roasting
Impregnated with manganese nitrate solution again, dried after removing maceration extract, then roasting is impregnated with manganese nitrate solution again, after removing maceration extract
Dry, then roasting removes template and obtain the meso-porous titanium dioxide manganese.
Manganese nitrate of the invention includes non-hydrate and its various hydrate forms, for example four water manganese nitrates, six water nitric acid
Manganese etc..
According to some specific embodiments of the invention, wherein, methods described is included with mesoporous silicon material as template, passes through
Then the dipping of manganese nitrate solution, dry roasting removes template, by filtering and is dried to obtain the meso-porous titanium dioxide
Manganese, pore volume is 0.1~0.3cm3/ g, specific surface area is 40~100m2/ g, pore-size distribution is in 1.9~12nm.
According to some specific embodiments of the invention, wherein, wash filter cake with water after filtration, then it is dried to obtain described
Meso-porous titanium dioxide manganese.
According to some specific embodiments of the invention, wherein, wash with water after filtration filter cake to pH be 7-9.
According to some specific embodiments of the invention, wherein, the mesoporous silicon material is selected from KIT-6, SBA-15, SBA-
16th, the mixing of one or more in MCM-41 and MCM-48.
According to some specific embodiments of the invention, wherein, manganese nitrate solution concentration is 0.25~1.0mol/L, and quality is used
Measure is 0.45~1.8 times of template quality.
According to some specific embodiments of the invention, wherein, the dipping is impregnated under ultrasound condition.
According to some specific embodiments of the invention, wherein, it is the aqueous solution soaking presoma with inorganic base to remove mould
Plate agent.
According to some specific embodiments of the invention, wherein, it is to stir 30- after presoma to be placed in the aqueous solution of inorganic base
120min is removing template.
According to some specific embodiments of the invention, wherein, the inorganic base is selected from NaOH or potassium hydroxide.
According to some specific embodiments of the invention, wherein, after obtaining presoma, with the aqueous solution soaking forerunner of inorganic base
Body, filters after stirring, by filter cake again with the aqueous solution soaking of inorganic base, is filtered after stirring 30-120min, and by filter cake with inorganic
The step of being filtered after the aqueous solution soaking stirring of alkali repeats 0-5 times.
Wherein it is understood that 0 time repeated in 0-5 times of the present invention refers to the step and do not exist, also
It is to say the process of " by being filtered after the aqueous solution soaking stirring of filter cake inorganic base " and do not exist, i.e. methods described obtains forerunner
After body, with the aqueous solution soaking presoma of inorganic base, filtered after stirring, by filter cake again with the aqueous solution soaking of inorganic base, stirring
Convection drying is filtered after 30-120min and obtains the meso-porous titanium dioxide manganese.
But according to some specific embodiments of the invention, wherein, after the aqueous solution soaking stirring of filter cake inorganic base
The step of filtering, repeats 1-3 times.
According to some specific embodiments of the invention, wherein, the roasting is to be calcined 4-8h at 200-400 DEG C；It is preferred that
It is roasting 6h.
According to some specific embodiments of the invention, wherein, methods described is included with mesoporous silicon material as template, passes through
The dipping of manganese nitrate solution, dries at 60-100 DEG C, is then calcined, then remove template, by filtering and is dried to obtain institute
Give an account of hole manganese dioxide.
Removing maceration extract of the present invention can use conventional method, for example filter, and some are specific according to the present invention
Embodiment, wherein, the present invention is the solvent during evaporation removes maceration extract.
Described manganese nitrate solution can be any solution of manganese nitrate, for example the aqueous solution or other solvents.
Described mesoporous silicon can be commercially available acquisition, or be obtained with prior art conventional method.
And according to some specific embodiments of the invention, when the mesoporous silicon material is KIT-6, its preparation includes：
With tetraethoxysilane (TEOS) as silicon source, with triblock copolymer EO20PO70EO20Be (P123) soft template,
With n-butanol as structure directing agent, with salt acid for adjusting pH value, synthesized using hydro-thermal method and obtained.Step is as follows：
(1) triblock copolymer P123 is dissolved in hydrochloric acid solution as soft template, stirring makes triblock copolymer
Thing P123 is completely dissolved, and forms homogeneous phase solution A；
(2) in 30~40 DEG C of water bath with thermostatic control, to adding n-butanol as structure directing agent in homogeneous phase solution A, continue to stir
Mix to solution after being well mixed, then TEOS is instilled with dropping funel, continuously stir 1 day；
(3) mixing liquid is poured into crystallizing kettle carries out hydro-thermal reaction, after cooling, suction filtration, washing, drying, calcination process
Obtain pure mesoporous silicon material KIT-6.
The invention provides the preparation method of the pure mesoporous silicon materials of KIT-6, hydrothermal temperature is controlled at 40~140 DEG C
(preferably 40 DEG C), reaction time control is at 24~72h (preferably 48h), and the pH value control of hydro-thermal reaction mixed liquor is (excellent 1~5
Elect as 3).After hydro-thermal reaction, crystallizing kettle natural cooling, vavuum pump suction filtration is simultaneously washed with deionized 4 times, 90~110 DEG C of drying
(preferably 100 DEG C), 530~580 DEG C of roastings (preferably 550 DEG C).The time of roasting be 4~6h, heating rate be 2 DEG C/
min。
The method of the present invention can be specifically included：
(1) the pure mesoporous silicon material such as KIT-6 is added and is dissolved in the manganese nitrate solution of water or other solvents (preferred alcohol),
By after excessive dipping, ultrasonic vibration, superfluous water or other solvents are evaporated, then dried at 60~100 DEG C, 200~400 DEG C
Lower roasting (preferably 200 DEG C), obtains mesoporous Mn oxide presoma；
(2) in manganese nitrate being dissolved in into water or other solvents (preferred alcohol), mesoporous Mn oxide presoma is added, was passed through
Amount dipping, after ultrasonic vibration, superfluous water or other solvents are evaporated, then dried at 60~100 DEG C, be calcined at 200~400 DEG C
(preferably 380 DEG C), obtain the mesoporous Mn oxide presoma with compactedness high.Above step is repeated 0~3 time.
(3) mesoporous Mn oxide presoma is soaked with sodium hydroxide solution, 30~120min of magnetic agitation is (preferably
60min), filter, obtain filter cake.Filter cake is soaked once with same sodium hydroxide solution again, and 30~120min of magnetic agitation is (excellent
Select 60min), refilter, the filter cake is washed with deionized more than 4 times, is dried at 50~90 DEG C, obtains final product mesoporous MnO2Powder
End.
On the other hand, present invention also offers the meso-porous titanium dioxide manganese that the preparation method is prepared.
Another aspect, present invention also offers described meso-porous titanium dioxide manganese answering in the reaction of catalysis ethanol acetaldehyde
With.
According to some specific embodiments of the invention, wherein, the reaction is carried out at 50-150 DEG C.
According to some specific embodiments of the invention, wherein, reaction pressure is 1 atmospheric pressure.
Be passed through for ethanol and air and be loaded with the mesoporous MnO by the present invention2The reactor of catalyst, directly can temperature production second
Aldehyde.Ethanol Selective Oxidation acetaldehyde target product acetaldehyde may be up to more than 60%, acetaldehyde selectively up to 100%.
In sum, the invention provides a kind of meso-porous titanium dioxide manganese and its preparation method and application.It is of the invention mesoporous
Manganese dioxide has the following advantages that：
The invention provides ethanol selective oxidation low temperature acetaldehyde catalyst, with oxidation of ethanol acetaldehyde catalyst electricity
Solution Ag with Cu base catalyst is compared, and can at low temperature produce acetaldehyde, reduces acetaldehyde production energy consumption；Make acetaldehyde selectivity it is higher and
Acetaldehyde is not decomposed under low temperature, can effectively improve resource utilization.Using meso-porous titanium dioxide manganese catalysis ethanol system of the invention
Acetaldehyde may be up to more than 60%, acetaldehyde selectively up to 100%.
Brief description of the drawings
Fig. 1 is the mesoporous MnO that the pure mesoporous silicon material KIT-6 that embodiment 1 is synthesized with 40 DEG C of crystallization temperatures is prepared as template2
XRD spectra and SEM figure；
Fig. 2 be the pure mesoporous silicon material KIT-6 that is synthesized with 100 DEG C of crystallization temperatures of embodiment 2 as template prepare it is mesoporous
MnO2XRD spectra and SEM figure；
Fig. 3 be the pure mesoporous silicon material KIT-6 that is synthesized with 140 DEG C of crystallization temperatures of embodiment 3 as template prepare it is mesoporous
MnO2XRD spectra and SEM figure；
Fig. 4 is the mesoporous MnO that embodiment 4 is prepared with commercial pure mesoporous silicon material SBA-15 as template2SEM figure.
Specific embodiment
Implementation process of the invention and the beneficial effect for producing are described in detail below by way of specific embodiment, it is intended to which help is read
Reader more fully understands essence of the invention and feature, not as to this case can practical range restriction.
Embodiment 1
Present embodiments provide with the pure mesoporous silicon material KIT-6 of 40 DEG C of crystallization temperatures synthesis as template prepare it is mesoporous
MnO2, it is prepared according to following steps：
It is dissolved in 7.2g P123 as soft template in 270ml, 1.9wt% hydrochloric acid solution, stirring makes P123 completely molten
Solution, forms homogeneous phase solution A；In 38 DEG C of water bath with thermostatic control, to addition 7.0g n-butanols in homogeneous phase solution A as structure directing
Agent, continuation is stirred to solution after being well mixed, then instills 7.0g TEOS with dropping funel, is continuously stirred 1 day；By mixing liquid
Crystallizing kettle is poured into, 40 DEG C carry out hydro-thermal reaction, then natural cooling；With vavuum pump, deionized water suction filtration, wash 4 times, at 90 DEG C
12h, 550 DEG C of roastings are dried, pure mesoporous silicon material KIT-6 is obtained final product.
8.0g KIT-6 mesoporous silicons are added to the Mn (NO of 80ml, 0.91mol/L3)2·4H2In O ethanol solutions, pass through
After excessive dipping, ultrasonic vibration, 50 DEG C of evaporation excess ethyl alcohols, in 100 DEG C of dryings, 200 DEG C of roastings, before obtaining mesoporous Mn oxide
Drive body；The mesoporous Mn oxide presoma of gained is added to the Mn (NO of 80ml, 0.91mol/L3)2·4H2In O ethanol solutions, warp
After excessive dipping, ultrasonic vibration, then 50 DEG C of evaporation unnecessary alcohols are calcined at 100 DEG C of dryings, 380 DEG C, and obtaining has height
The mesoporous Mn oxide presoma of compactedness.Mesoporous Mn oxide presoma is soaked with the NaOH solution of 2.0mol/L, magnetic force
Stirring 60min, filtering obtains filter cake.Filter cake is soaked once with same NaOH solution again, and magnetic agitation 60min is refiltered,
The filter cake is washed with deionized more than 4 times, is dried at 90 DEG C, obtains final product mesoporous MnO2Powder.
Using X-ray powder diffraction (XRD) to above-mentioned mesoporous MnO2Powder detected, characterizes crystalline phase.According to difference
The diffraction maximum of position and the intensity of diffraction maximum may determine that mesoporous material formation whether with the degree of order.Beneficial to scanning electron microscopy
Mirror (SEM) can observe the shape characteristic of mesoporous material.
Fig. 1 is that the pure mesoporous silicon material KIT-6 synthesized with 40 DEG C of crystallization temperatures prepares mesoporous MnO2XRD spectra and SEM
Figure.XRD spectra shows that the catalyst 2 θ has two small-angle diffraction peaks at 0.6 °, 1 ° or so place respectively, and this is attributed to 40 DEG C of crystalline substances
There is time network structure and this structural instability in the pure mesoporous silicon material KIT-6 for changing temperature synthesis.With this KIT-6 as template
The mesoporous MnO for preparing2Because the unstability of template has resulted in two diffraction maximums of angle.Two diffraction maximums have certain peak
Value, illustrates that material pore passage structure is still present certain regularity.The presence of this unstable pore passage structure has urges beneficial to raising
The low-temperature reduction of agent simultaneously can strengthen the conversion ratio and acetaldehyde of ethanol low-temperature oxidation acetaldehyde.SEM captions should
Catalyst is mesoporous material.
Embodiment 2
Present embodiments provide with the pure mesoporous silicon material KIT-6 of 100 DEG C of crystallization temperatures synthesis as template prepare it is mesoporous
MnO2, hydrothermal crystallizing temperature in its template KIT-6 building-up processes is 100 DEG C, other preparation processes and technological parameter with implement
Example 1 is identical.
Fig. 2 is that the pure mesoporous silicon material KIT-6 synthesized with 100 DEG C of crystallization temperatures prepares mesoporous MnO2XRD spectra and SEM
Figure.XRD spectra shows that the θ of catalyst 2 stronger diffraction maximum occurs in 1 °, 1.85 °, and it is 211 Hes of template KIT-6 that its is corresponding
332 characteristic diffraction peaks, this illustrates that the catalyst replicates the mesopore orbit structure of KIT-6 templates completely.SEM captions should
Catalyst is mesoporous material.
Embodiment 3
Present embodiments provide with the pure mesoporous silicon material KIT-6 of 140 DEG C of crystallization temperatures synthesis as template prepare it is mesoporous
MnO2, hydrothermal crystallizing temperature in its template KIT-6 building-up processes is 140 DEG C, other preparation processes and technological parameter with implement
Example 1 is identical.
Fig. 3 is that the pure mesoporous silicon material KIT-6 synthesized with 140 DEG C of crystallization temperatures prepares mesoporous MnO2XRD spectra and SEM
Figure.XRD spectra shows that the catalyst diffraction maximum is weaker, illustrates that the mesoporous regularity of the catalyst is poor.SEM captions
The catalyst is mesoporous material, but its mesoporous regularity is poor.
Embodiment 4
Present embodiments provide the mesoporous MnO prepared as template with commercial pure mesoporous silicon material SBA-152, its be according to
What lower step was prepared：
The commercial pure mesoporous silicon SBA-15 of 8.0g are added to the Mn (NO of 80ml, 0.91mol/L3)2·4H2O ethanol solutions
In, by after excessive dipping, ultrasonic vibration, 50 DEG C of evaporation excess ethyl alcohols, in 100 DEG C of dryings, 200 DEG C of roastings, obtain mesoporous manganese
Oxide precursor；The mesoporous Mn oxide presoma of gained is added to the Mn (NO of 80ml, 0.91mol/L3)2·4H2O ethanol
In solution, by after excessive dipping, ultrasonic vibration, then 50 DEG C of evaporation unnecessary alcohols are calcined at 100 DEG C of dryings, 380 DEG C,
Obtain the mesoporous Mn oxide presoma with compactedness high.By the mesoporous Mn oxide presoma NaOH solution of 2.0mol/L
Immersion, magnetic agitation 60min, filtering obtains filter cake.Filter cake is soaked once with same NaOH solution again, magnetic agitation
60min, refilters, and the filter cake is washed with deionized more than 4 times, is dried at 90 DEG C, obtains final product mesoporous MnO2Powder.
Fig. 4 is the mesoporous MnO prepared as template with commercial pure mesoporous silicon material SBA-152SEM figure.As seen from the figure, should
Catalyst is ordered mesoporous material.
Embodiment 5
Ethanol Selective Oxidation acetaldehyde reaction evaluating experiment on various catalyst
The mesoporous MnO prepared to above-described embodiment 1~42The ethanol Selective Oxidation acetaldehyde reactivity of catalyst is carried out
Test.Reaction condition：It is filling 0.5g catalyst in the quartz ampoule fixed bed reactors of 8mm in internal diameter, under normal pressure, reaction temperature
It is 130 DEG C, concentration of alcohol 600ppm, air speed 50000h-1.After stable reaction, reaction raw materials and product utilization on-line chromatograph are analyzed,
Reaction result is shown in Table 1.
The ethanol selective oxidation low temperature acetaldehyde performance of the catalyst of the present invention of table 1
| Catalyst is numbered | Ethanol conversion/% | Acetaldehyde selectivity/% | Acetaldehyde/% |
| Embodiment 1 | 82 | 77 | 63 |
| Embodiment 2 | 71 | 80 | 57 |
| Embodiment 3 | 53 | 87 | 46 |
| Embodiment 4 | 64 | 95 | 61 |
Embodiment 6
The ethanol Selective Oxidation acetaldehyde reaction evaluating experiment of catalyst under different temperatures
The mesoporous MnO for being prepared to above-described embodiment 1 at different temperatures2The ethanol Selective Oxidation acetaldehyde reaction of catalyst
Activity is tested.Reaction condition：In internal diameter to load 0.5g catalyst in the quartz ampoule fixed bed reactors of 8mm, under normal pressure,
Reaction temperature is 80 DEG C~150 DEG C, concentration of alcohol 600ppm, air speed 50000h-1.After stable reaction, reaction raw materials and product are sharp
Online chromatography is used, reaction result is shown in Table 2.As shown in Table 2, as the rising of temperature, ethanol conversion gradually increase, arrive
150 DEG C reach 100%；80 DEG C of acetaldehyde selectivity is 100%, is reduced with the rising of temperature, and 38% is down to 150 DEG C；
Between 80 DEG C~150 DEG C, acetaldehyde is higher at 120 DEG C~140 DEG C, and up to more than 60%.
The ethanol selective oxidation low temperature acetaldehyde performance of the catalyst of 2 embodiment of the present invention of table 1
| Temperature/DEG C | Ethanol conversion/% | Acetaldehyde selectivity/% | Acetaldehyde/% |
| 80 | 35 | 100 | 35 |
| 100 | 48 | 90 | 43 |
| 120 | 63 | 95 | 60 |
| 140 | 91 | 69 | 63 |
| 150 | 100 | 38 | 38 |
The method of the present invention is the best result of the current ethanol Selective Oxidation acetaldehyde reported, reaction temperature is than existing skill
Much lower, the acetaldehyde selectively up to 100% of art report, target product acetaldehyde can be with traditional electrolysis Ag or Cu base
Catalyst matches in excellence or beauty, even more high.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright, should be understood that and the foregoing is only specific embodiment of the invention, the guarantor being not intended to limit the present invention
Shield scope, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc., should be included in this
Within the protection domain of invention.
Claims (10)
1. a kind of meso-porous titanium dioxide manganese preparation method, wherein, methods described is included with mesoporous silicon material as template, through pernitric acid
The dipping of manganese solution, dry, roasting obtains presoma after removing maceration extract, then removes template and obtains the meso-porous titanium dioxide
Manganese；Wherein, after presoma is obtained, the presoma that will be obtained is impregnated with manganese nitrate solution again, removes dry, roasting after maceration extract
Burn, dipping, dry, roasting the step of repeat 0-5 times, preferably repeatedly 1-3；It is preferred that methods described is included with mesoporous silicon material as mould
Plate agent, by the dipping of manganese nitrate solution, then dry roasting removes template, is given an account of by filtering and being dried to obtain
Hole manganese dioxide；It is preferred that washing filter cake with water after filtration, the meso-porous titanium dioxide manganese is then dried to obtain；Further preferably in filtering
After wash with water filter cake to pH be 7-9.
2. preparation method according to claim 1, wherein, the mesoporous silicon material be selected from KIT-6, SBA-15, SBA-16,
One or more in MCM-41 and MCM-48 of mixing.
3. preparation method according to claim 1, wherein, manganese nitrate solution concentration is 0.25~1.0mol/L, and quality is used
Measure is 0.45~1.8 times of template quality.
4. preparation method according to claim 1, wherein, the dipping is impregnated under ultrasound condition.
5. preparation method according to claim 1, wherein, it is the aqueous solution soaking presoma with inorganic base to remove template
Agent；30-120min is stirred to remove template after presoma to be preferably placed in the aqueous solution of inorganic base；It is preferred that the inorganic base
Selected from NaOH or potassium hydroxide；It is also preferred that the molar concentration of inorganic base is 1~3mol/L.
6. preparation method according to claim 5, wherein, after obtaining presoma, with the aqueous solution soaking forerunner of inorganic base
Body, filters after stirring, by filter cake again with the aqueous solution soaking of inorganic base, is filtered after stirring 30-120min, and by filter cake with inorganic
The step of being filtered after the aqueous solution soaking stirring of alkali repeats 0-5 times；It is preferred that repeating 1-3 times.
7. preparation method according to claim 1, wherein, the roasting is calcined at 200-400 DEG C；It is preferred that when being calcined
Between be 4-8h.
8. preparation method according to claim 1, wherein, methods described is included with mesoporous silicon material as template, passes through
The dipping of manganese nitrate solution, dries at 60-100 DEG C, is then calcined, then remove template, by filtering and is dried to obtain institute
Give an account of hole manganese dioxide.
9. the meso-porous titanium dioxide manganese that preparation method described in claim 1~8 any one is prepared；It is preferred that the mesoporous dioxy
The pore volume for changing manganese is 0.1~0.3cm3/ g, specific surface area is 40~100m2/ g, pore-size distribution is in 1.9~12nm.
10. application of the meso-porous titanium dioxide manganese described in claim 9 in the reaction of catalysis ethanol acetaldehyde；It is preferred that the reaction is
Carried out at 50-150 DEG C；More preferably reaction pressure is 1 atmospheric pressure.
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