CN104907079A - Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction - Google Patents
Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction Download PDFInfo
- Publication number
- CN104907079A CN104907079A CN201510229349.7A CN201510229349A CN104907079A CN 104907079 A CN104907079 A CN 104907079A CN 201510229349 A CN201510229349 A CN 201510229349A CN 104907079 A CN104907079 A CN 104907079A
- Authority
- CN
- China
- Prior art keywords
- thin film
- catalyst
- preparation
- ldhs
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a mixed metal oxide thin film catalyst for a hydrocarbon oxidation reaction, and belongs to the catalyst preparation technical field. The preparation method comprises the steps: firstly, preparing a layered double hydroxides (LDHs) thin film precursor MMnAl-LDHs on an anodic alumina substrate by an in-situ growth technology, carrying out thermal decomposition to obtain a mixed metal oxide (MMO) thin film M<II>MnAl-MMO, taking a reaction of catalyzing aromatic hydrocarbon to be oxidized to synthesize aldehyde or ketone as a probe reaction, and evaluating the catalytic oxidation performance. The ternary LDHs thin film precursor is obtained on the aluminum substrate by the in-situ growth method, and the multi-element MMO thin film is obtained through high temperature calcination. The preparation method has the advantages that the prepared thin film catalyst is applied in catalytic oxidation of ethylbenzene, has the advantages of good stability, high catalytic efficiency, renewable recycling and the like, and has potential application prospects in petroleum industry catalysis.
Description
Technical field
The present invention relates to catalyst preparation technical field, particularly a kind of preparation method for oxidation reactions of hydrocarbons composite metal oxide film catalyst.
Background technology
In organic synthesis, the oxidation of aromatic hydrocarbon is the important reaction that organo-functional group is introduced.Be oxidized the triiron tetroxide formed is important raw material by c h bond in aromatic hydrocarbon in industry manufacture, production of flavor and business application.Comparatively outstanding is, the selective catalytic oxidation of ethylbenzene is very important industrial reaction, because ethylbenzene selectivity oxidation can generate acetophenone, chemical property due to acetophenone excellence makes it industrially have a wide range of applications, such as, acetophenone can as the ultimate constituent of medicine, resin, alcohols, ester class, also can as the solvent etc. of cellulose ethers.More oxidant is used to generally comprise O so far
2, H
2o
2and TBHP, and molecular oxygen and organic matter mix and likely cause burning, and the oxidisability of TBHP is better than O
2.The catalyst that the selective catalytic oxidation being applied to ethylbenzene becomes acetophenone has a lot, uses cobalt acetate as catalyst in current industrial production.But the homogeneous catalyst that ethylbenzene oxidation uses exists catalyst recovery and recycles the problems such as difficult, therefore a kind of more effective in the urgent need to developing, have actual benefit, can reusable catalyst.
Hydrotalcite (LDHs) is otherwise known as di-hydroxyl composite metal oxidate, it is the widely used anionic inorganic stratified material of a class, it is the crystal formed along third dimension ordered arrangement by the laminate of two-dimensional, divalence and the mutual high degree of dispersion of trivalent metal hydroxides are also formed main body laminate with covalent bond, and are rich in positive charge; Interlayer anion is uniformly distributed, and with electrostatic interaction dynamic balance body layer plate electric charge, be crystal is electroneutral.Be composite metal oxide (MMO) by LDHs high-temperature roasting, because it has loose structure, the Modulatory character of laminate metal ion, strong basicity and heat endurance, be widely used in recent years in catalysis and catalyst carrier etc.In document Chinese Chemical Letters 2011,22:401 – 404, the people such as Warangkana Kanjina report the research that O composite metallic oxide catalyst selective catalytic oxidation ethylbenzene obtains acetophenone; At document Journal of Molecular Catalysis A:Chemical 2009, in 30:654 – 61, the people such as K.M.Parida report compound containing manganese to the research of the catalytic oxidation of ethylbenzene, and these catalytic reactions all have good selective and conversion ratio.But MMO powder is easy to run off in catalytic process, and is separated with product difficulty.Therefore, the loss of catalyst activity component in catalytic oxidation process how is avoided to be a problem demanding prompt solution.
Have certain orientation with hydrotalcite film prepared by situ synthesis, and film and substrate are combined with covalent bond, adhesion is strong, difficult drop-off.By this there is the hydrotalcite film roasting of orientation after generate composite metal oxide film, still keep original orientation and strong adhesion.Therefore, compared with powder, this composite metal oxide film has following advantage as catalyst: (1) can make catalyst run off in course of reaction to be controlled effectively; (2) the special structural approach feature that this composite metal oxide film has determines the dispersiveness that this film has height, and active component is evenly dispersed in substrate, thus improves activity and the service life of catalyst.Therefore, this film catalyst is expected to carry out catalytic oxidation to ethylbenzene under liquid-phase condition.Up to now, there is no the document applied at Ethylbenzene Catalytic Oxidation about this composite metal oxide film catalyst application and patent report both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of preparation method for oxidation reactions of hydrocarbons composite metal oxide film catalyst.The method employing cost of material is cheap, synthesis technique simple, the ternary anion lamellar compound MMnAl-LDHs of metal ion high degree of dispersion is presoma, prepares the MMnAl-composite oxide film material with higher hydrocarbon catalytic oxidation activity.
First the present invention adopts single droplet method directly to prepare MMnAl-LDHs film on aluminum substrates, then carries out drying to this film, obtains MMnAl composite oxide film finally by high-temperature roasting.
First the present invention adopts in-situ growth technology on anodic oxidation aluminium substrate, to prepare layered double hydroxide (LDHs) film precursor, MMnAl-LDHs, obtains composite metal oxide (MMO) film, M through thermal decomposition
iImnAl-MMO, using the reaction of catalysis aromatic oxidation synthesis aldehydes or ketones as probe reaction, evaluates its catalytic oxidation performance.The step of preparation process of MMnAl composite oxide film is as follows:
A. the aluminium flake adopting purity to be more than or equal to 99.95% is raw material, be cut into rectangular pieces, use absolute ethyl alcohol and deionized water ultrasonic cleaning 5-10min respectively, 1 ~ 3min is soaked again in the sodium hydroxide solution of 0.05 ~ 0.2mol/L, clean by washed with de-ionized water, be kept in drier for subsequent use after drying;
B., in reaction vessel, divalence mixed inorganic MY and MnY is mixed with 0.05 ~ 0.20molL
-1solution, be placed in reaction vessel, then by ammonium nitrate according to [NH
4nO
3]/[M]+[Mn
2+]=1 ~ 10 ratio adds in above-mentioned reaction vessel, and makes it to be dissolved in divalent metal salting liquid;
C. the salting liquid containing ammonium nitrate that step B prepares drips ammoniacal liquor adjust ph to 6.8 ~ 8.8, sealed reaction vessel at 20 ~ 30 DEG C of temperature, and stir dipping 1 ~ 5 hour, area steps A prepared is 200cm
2aluminium flake be placed in solution, at 80 ~ 160 DEG C of temperature react 12 ~ 24 hours; After solution cooling, take out aluminium flake, with deionized water rinsing, dry, thus obtain MMnAl-LDHs film on aluminium surface;
D. the MMnAl-LDHs film catalyst prepared by step C is placed in Muffle furnace, at 400-550 DEG C, with the sintering that heats up under the heating rate of 2 ~ 10 DEG C/min, constant temperature 2 ~ 4 hours, slowly be down to room temperature with stove cooling afterwards, obtain thickness at micron order, uniform MMnAl composite oxide film.
The composite oxide film prepared is as structural catalyst catalysis oxidation reaction of ethylbenzene, and reaction condition is as follows: the ethylbenzene of 10mL acetonitrile and 1.2mL (10mol) adds in the single port flask of 50mL, is 200cm by two-sided area
2film catalyst is cut into small pieces and puts into flask, and backflow adds the oxidant TBHP (TBHP) of 2.7mL (20mol) after being warming up to 120 DEG C.Constant temperature oxidation took out fluid sample after 12 hours, utilized gas-chromatography and GC-MS to detect the ingredients of a mixture and content, the transformation efficiency comparatively powder catalyst raising 1.5 ~ 2.5 times of ethylbenzene.
The molar concentration rate { [M of bivalent metal ion molar concentration sum and trivalent metal ion in composite oxide film of the present invention
2+]+[Mn
2+]/[Al
3+] be 2 ~ 4, [Mn
2+]/{ [M
2+]+[Mn
2+] mol ratio be 0-1, M is Co
2+, Ni
2+and Zn
2+in any one.
Film catalyst of the present invention has carried out the analysis of structure and composition, confirm the successful synthesis of MMnAl composite metal oxide, and the catalyst oxidation ethylbenzene performance made is evaluated, result shows that this catalyst has showed higher catalytic activity and longer catalytic life.
The invention has the advantages that: directly utilize aluminium flake as aluminium source using single droplet method, prepare MMnAl-LDHs film as presoma, the adjustable control being realized serial MMnAl composite metal oxide film material by the relative amount of metal ion in selective regulation presoma is standby, and then realize the regulation and control of its catalytic oxidation performance, filter out efficient to Ethylbenzene Catalytic Oxidation, stable catalyst.
Accompanying drawing explanation
Fig. 1 is Co in the embodiment of the present invention 1
1.0mn
1.0the XRD spectra of Al-MMO film catalyst;
Fig. 2 is Co in the embodiment of the present invention 1
1.0mn
1.0the SEM photo of Al-MMO film catalyst;
Fig. 3 is that the conversion ratio of film catalyst Oxidation Ethylbenzene reaction in the embodiment of the present invention 1 is with the curve in reaction time and the selective of the acetophenone curve with the reaction time;
Fig. 4 is the conversion ratio figure of film catalyst and the reaction of powder catalyst oxidation ethylbenzene in the embodiment of the present invention.
Detailed description of the invention
Embodiment 1
The 7.0275g CoSO taken
47H
2o, 4.2255g MnSO
4h
2o and 24.012g NH
4nO
3be mixed with solution, be configured to solution by 500mL deionized water, this mixed solution is poured in homemade glass container, in stirred at ambient temperature, drip ammoniacal liquor adjust ph to 8.5, by 200cm
2aluminium flake vertically puts into solution, floods 4 hours, reacts 24 hours at 140 DEG C of temperature; After solution cooling, take out aluminium flake, with deionized water rinsing, dry, thus obtain LDHs film on aluminium surface.Then with the heating rate of 2 DEG C/min, LDHs film is slowly heated up, at 500 DEG C, be incubated 4h, slowly get back to room temperature with stove cooling afterwards, obtain Co through 500 DEG C of roastings
1.0mn
1.0al-MMO film catalyst.The conversion ratio of the catalytic oxidation of its ethylbenzene after 12 hours is up to 79.3%, is 2.25 times of corresponding powder catalyst.
Embodiment 2
Take 14.055g CoSO
47H
2o and 24.012g NH
4nO
3be mixed with solution, prepare LDHs film with embodiment 1 the same terms, obtain Co through 500 DEG C of roastings
1.75mn
0.25al-MMO film catalyst.The conversion ratio of the catalytic oxidation of its ethylbenzene after 12 hours reaches 62.5%, is 1.49 times of corresponding powder catalyst.
Embodiment 3:
The 10.5412g CoSO taken
47H
2o, 2.1127g MnSO
4h
2o and 24.012g NH
4nO
3, be configured to solution by 500mL deionized water, prepare CoMnAl-LDHs film with embodiment 1 the same terms, obtain Co through 500 DEG C of roastings
1.5mn
0.5al-MMO film catalyst.The conversion ratio of the catalytic oxidation of its ethylbenzene after 12 hours reaches 55.7%, is 1.96 times of corresponding powder catalyst.
Embodiment 4:
The 3.5137g CoSO taken
47H
2o, 6.3382g MnSO
4h
2o and 24.012g NH
4nO
3be mixed with solution, prepare Co with embodiment 1 the same terms
0.5mn
1.5al-LDHs film, obtains Co through 500 DEG C of roastings
0.5mn
1.5al-MMO film catalyst.The conversion ratio of the catalytic oxidation of its ethylbenzene after 12 hours reaches 20.2%, is 2.16 times of corresponding powder catalyst.
Claims (3)
1. for a preparation method for oxidation reactions of hydrocarbons composite metal oxide film catalyst, it is characterized in that, processing step is as follows:
A. the aluminium flake adopting purity to be more than or equal to 99.95% is raw material, be cut into rectangular pieces, use absolute ethyl alcohol and deionized water ultrasonic cleaning 5-10min respectively, 1 ~ 3min is soaked again in the sodium hydroxide solution of 0.05 ~ 0.2mol/L, clean by washed with de-ionized water, be kept in drier for subsequent use after drying;
B., in reaction vessel, divalence mixed inorganic MY and MnY is mixed with 0.05 ~ 0.20molL
-1solution, be placed in reaction vessel, then by ammonium nitrate according to [NH
4nO
3]/[M]+[Mn
2+]=1 ~ 10 ratio adds in above-mentioned reaction vessel, and makes it to be dissolved in divalent metal salting liquid;
C. the salting liquid containing ammonium nitrate that step B prepares drips ammoniacal liquor adjust ph to 6.8 ~ 8.8, sealed reaction vessel at 20 ~ 30 DEG C of temperature, and stir dipping 1 ~ 5 hour, area steps A prepared is 200cm
2aluminium flake be placed in solution, at 80 ~ 160 DEG C of temperature react 12 ~ 24 hours; After solution cooling, take out aluminium flake, with deionized water rinsing, dry, thus obtain MMnAl-LDHs film on aluminium surface;
D. the MMnAl-LDHs film catalyst prepared by step C is placed in Muffle furnace, at 400-550 DEG C, with the sintering that heats up under the heating rate of 2 ~ 10 DEG C/min, constant temperature 2 ~ 4 hours, slowly be down to room temperature with stove cooling afterwards, obtain thickness at micron order, uniform MMnAl composite oxide film.
2. method according to claim 1, is characterized in that, in bivalent inorganic salt MY, M is Co
2+, Ni
2+, Zn
2+in any one; Y is Cl
-, NO
3 -, SO
4 2-in any one.
3. method according to claim 1, is characterized in that, the molar concentration rate { [M of bivalent metal ion molar concentration sum and trivalent metal ion in composite oxide film
2+]+[Mn
2+]/[Al
3+] be 2 ~ 4, [Mn
2+]/{ [M
2+]+[Mn
2+] mol ratio be 0-1, M is Co
2+, Ni
2+and Zn
2+in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510229349.7A CN104907079A (en) | 2015-05-07 | 2015-05-07 | Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510229349.7A CN104907079A (en) | 2015-05-07 | 2015-05-07 | Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104907079A true CN104907079A (en) | 2015-09-16 |
Family
ID=54076763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510229349.7A Pending CN104907079A (en) | 2015-05-07 | 2015-05-07 | Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104907079A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560065A (en) * | 2019-08-23 | 2019-12-13 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
| CN113502469A (en) * | 2021-07-21 | 2021-10-15 | 中国石油大学(华东) | Preparation method of self-repairable super-hydrophobic/super-oleophylic aluminum alloy net for oil-water separation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792449A (en) * | 2005-12-06 | 2006-06-28 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
| CN1923363A (en) * | 2006-09-27 | 2007-03-07 | 北京化工大学 | Preparation of catalyst for synthesizing hydrotalcite thin film by alcohol oxidation reaction |
| CN101016629A (en) * | 2007-01-12 | 2007-08-15 | 北京化工大学 | Ultra-hydrophobic high sticking composite metal oxide thin film and preparing method thereof |
| WO2008129034A1 (en) * | 2007-04-20 | 2008-10-30 | Euro Support Catalyst Group Bv | Hydrotalcite-like layered double hydroxide (ldh) composition and process of making same |
| CN102343283A (en) * | 2011-07-21 | 2012-02-08 | 北京化工大学 | Vertically aligned layered double hydroxides (LDHs) film and application thereof in structured catalysis |
-
2015
- 2015-05-07 CN CN201510229349.7A patent/CN104907079A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792449A (en) * | 2005-12-06 | 2006-06-28 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
| CN1923363A (en) * | 2006-09-27 | 2007-03-07 | 北京化工大学 | Preparation of catalyst for synthesizing hydrotalcite thin film by alcohol oxidation reaction |
| CN101016629A (en) * | 2007-01-12 | 2007-08-15 | 北京化工大学 | Ultra-hydrophobic high sticking composite metal oxide thin film and preparing method thereof |
| WO2008129034A1 (en) * | 2007-04-20 | 2008-10-30 | Euro Support Catalyst Group Bv | Hydrotalcite-like layered double hydroxide (ldh) composition and process of making same |
| CN102343283A (en) * | 2011-07-21 | 2012-02-08 | 北京化工大学 | Vertically aligned layered double hydroxides (LDHs) film and application thereof in structured catalysis |
Non-Patent Citations (2)
| Title |
|---|
| WARANGKANA KANJINA ET AL.: "Mixed metal oxide catalysts for the selective oxidation of ethylbenzene to acetophenone", 《CHINESE CHEMICAL LETTERS》 * |
| 马建军等: "乙苯催化氧化合成苯乙酮中绿色氧化体系研究进展", 《甘肃科技》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560065A (en) * | 2019-08-23 | 2019-12-13 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
| CN110560065B (en) * | 2019-08-23 | 2022-08-05 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
| CN113502469A (en) * | 2021-07-21 | 2021-10-15 | 中国石油大学(华东) | Preparation method of self-repairable super-hydrophobic/super-oleophylic aluminum alloy net for oil-water separation |
| CN113502469B (en) * | 2021-07-21 | 2022-12-02 | 中国石油大学(华东) | Preparation method of self-repairable super-hydrophobic/super-oleophylic aluminum alloy net for oil-water separation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104148060B (en) | A kind of platinum catalyst that is carried on double oxide complex carrier and its preparation method and application | |
| CN102921408B (en) | Preparation method and application of layered manganese oxide porous material catalyst | |
| CN100382890C (en) | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method | |
| CN102247858B (en) | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof | |
| CN104971727B (en) | A kind of preparation method of Ni-based catalyst for hydrogen production from methane vapor reforming | |
| CN103007921B (en) | Method for synthesizing carbon-doped BiVO4 photocatalyst by using microwave hydrothermal method | |
| CN103203232B (en) | High dispersion supported nano noble metal catalyst and preparation method and application thereof | |
| CN104162444A (en) | Layered catalyst for selectively oxidizing 4-methylguaiacol-to-vanillin, and preparation method thereof | |
| CN107983387B (en) | Preparation method and application of carbon nitride/bismuth selenate composite material | |
| CN103663560A (en) | Molybdate and preparation method thereof | |
| CN105013509A (en) | Catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and preparation method and application method thereof | |
| CN103447026B (en) | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof | |
| CN101966460B (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| CN103055847A (en) | Manganese-based oxide catalyst used for catalytic oxidation of ethanol, and preparation method and application thereof | |
| CN107497439A (en) | A kind of copper-based catalysts for reverse water-gas-shift reaction and preparation method thereof | |
| CN104795575A (en) | Preparation method of high-activity composite electrode material of Co3S4 and graphene | |
| CN106563455B (en) | Slurry bed system Cu base CO adds hydrogen CH4Catalyst and preparation method and application | |
| CN113385185A (en) | High-activity and selective perovskite type photo-thermal catalyst and preparation method and application thereof | |
| CN105921155A (en) | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof | |
| CN104646046A (en) | Novel method for selective oxidation of cyclohexene | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN107497468A (en) | A kind of preparation method and applications of the graphite phase carbon nitride composite photo-catalyst of nickel hydroxide modification | |
| CN103143381B (en) | Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method | |
| CN104907079A (en) | Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction | |
| Ko et al. | Synthesis of metal–organic frameworks (MOFs) and their application in the selective catalytic reduction of NO x with NH 3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150916 |
|
| WD01 | Invention patent application deemed withdrawn after publication |