CN107899575A - Nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester and its preparation method and application - Google Patents

Nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester and its preparation method and application Download PDF

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CN107899575A
CN107899575A CN201711159246.3A CN201711159246A CN107899575A CN 107899575 A CN107899575 A CN 107899575A CN 201711159246 A CN201711159246 A CN 201711159246A CN 107899575 A CN107899575 A CN 107899575A
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aldehyde
solid solution
nano catalyst
oxidative esterification
carrier
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CN107899575B (en
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李玉超
田运
郑艳霞
傅忠君
张苏
黄昊飞
张天
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Shandong University of Technology
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • 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

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Abstract

The present invention relates to chemical industry catalysis technical field, and in particular to a kind of nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester and its preparation method and application.The nano catalyst is using Au as active component, and using cerium base composite solid solution as carrier, the load capacity of Au accounts for Au and 0.1 2wt.% of carrier gross mass；The cerium base composite solid solution is Ce Zr solid solution, Ce Co solid solution, Ce Fe solid solution, Ce Mn solid solution, Ce Ni solid solution or Ce Fe Cu solid solution.The conversion ratio of aldehyde is 98.3 99.8% in the present invention, and the selectivity of ester is 97.6 99.7%, has the characteristics of easy to operate, conversion ratio is higher, and selectivity of product is preferable, and the recycling of catalyst is easy, substantially increases the stability and process economy of reaction.

Description

Nano catalyst and its preparation side for one step oxidative esterification of aldehyde and alcohol generation ester Method and application
Technical field
The present invention relates to chemical industry catalysis technical field, and in particular to a kind of to generate ester for one step oxidative esterification of aldehyde and alcohol Nano catalyst and its preparation method and application.
Background technology
Ester type compound is a kind of important chemical industry and organic synthesis intermediate, traditional synthetic method be first by aldehyde or Alcohol oxidation prepares the derivative of acid or acid, is then esterified the derivative of acid or acid, but the preparation process is complicated, and mistake Many harmful by-products are produced in journey.
There is the catalyst that multinomial patent is related to aldehyde oxidation and esterification generation ester since 1970, such as Golden series catalysts involved in JP20000154164, JP2003192632, JP2003361086；JP-B-4-72578, JP-A- Palladium series catalyst involved in 61-243044, US4638085.Mentioned in Japan Patent JP2005008557 using Au catalyst The reaction of metering system aldehyde oxidation and esterification synthetic ester is catalyzed, the conversion ratio of reaction is only 32.8%, its conversion ratio is relatively low, nothing Method realizes industrialized production.
Catalyst in above-mentioned patent produces a large amount of accessory substances during the reaction, has and easily inactivates, and reclaimer operation is multiple Miscellaneous, reaction speed is slow, the shortcomings such as conversion ratio is low.
Chinese patent CN101618328A discloses a kind of load type nano gold catalyst and preparation method thereof.The support type is received Rice Au catalyst is by active component nanogold, auxiliary agent and γ-Al2O3Carrier forms.Its preparation method includes γ-Al2O3Carrier changes Property, nanogold activity component impregnation, reduction, washing, drying.The patent is with γ-Al2O3Carrier, for turning for micro CO Change, although containing Fe2O3、MnO2、CuO、Co2O3、CeO2Or the auxiliary agent such as NiO, but the component of its carrier and Fe2O3、MnO2、 CuO、Co2O3、CeO2, NiO effect and content with the present invention have essence difference.
Chinese patent CN103801326A discloses a kind of load type nano gold catalyst and preparation method thereof.The support type is received The preparation method of rice Au catalyst is included under conditions of deposition sedimentation, by carrier and tetra chlorauric acid aqueous solution in Rotary Evaporators Middle contact, obtains the mixed liquor containing solid sediment, and then evaporation removes water, and the solid that dry, calcining obtains successively.Should The carrier of load type nano gold catalysis is FeOOH, di-iron trioxide, cerium oxide and sodium niobate.With hydroxyl oxygen in the patent Change iron, di-iron trioxide, cerium oxide as carrier, the alkalescence of its carrier is weaker, and the negligible amounts of the active oxygen provided, unfavorable Carried out in reaction.
The content of the invention
The object of the present invention is to provide a kind of nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester, have The characteristics of reaction speed is fast, high conversion rate, and selectivity is good, and service life is long, present invention simultaneously provides its preparation method and application.
Nano catalyst of the present invention for one step oxidative esterification of aldehyde and alcohol generation ester, using Au as activearm Point, using cerium base composite solid solution as carrier, the load capacity of Au accounts for Au and the 0.1-2wt.% of carrier gross mass；The cerium base is answered Conjunction solid solution is Ce-Zr solid solution, Ce-Co solid solution, Ce-Fe solid solution, Ce-Mn solid solution, Ce-Ni solid solution or Ce-Fe- Cu solid solution.
The preparation method of nano catalyst of the present invention for one step oxidative esterification of aldehyde and alcohol generation ester includes Following steps：
(1) preparation of carrier
The soluble-salt of metal is dissolved in ionic liquid solution, adds sodium hydroxide solution, hydro-thermal reaction, centrifugation obtains Solid, dry, calcining, obtains carrier；
(2) preparation of nano catalyst
In HAuCl4Protective agent, reducing agent are sequentially added in aqueous solution, adds the carrier that step (1) obtains, then through HCl Solution adjusts pH value, is stirred at room temperature, filtration washing, dry, and roasting, obtains nano catalyst.
Wherein：
In step (1), the sum of metal molar number, ionic liquid, the ratio between the molal quantity of sodium hydroxide are 1:1-3:5-10.
In step (1), soluble-salt is nitrate, hydrochloride or sulfate.
In step (1), for ionic liquid by anion and cation composition, the anion is Cl-、Br-、BF4 -、PF6 -、 TfO-(CF3SO3 -)、NfO-(C4F9SO3 -)、SbF6 -、AsF6 -、CH3COO-、NO3 -Or SO4 -, the cation is [NR4]+、 [bmim]+、[emim]+、[Rpy]+、[C8mim]+、[C10mim]+、[C12mim]+Or [C14mim]+。
In step (1), hydrothermal temperature is 100-200 DEG C, the hydro-thermal reaction time 20-28h；Drying temperature is 40- 100 DEG C, drying time 10-14h；Calcining heat is 350-450 DEG C, calcination time 2-6h.
In step (2), protective agent PVA, reducing agent NaBH4；The mass ratio of PVA and Au is 1:2, NaBH4With rubbing for Au You are than being 5:1.
In step (2), HCl solution is used to adjust pH value as 4-6.
In step (2), it is 0.5-4h that the time, which is stirred at room temperature, and drying temperature is 40-100 DEG C, drying time 10-14h；Roasting It is 250-300 DEG C to burn temperature, roasting time 2-6h.
The application of nano catalyst of the present invention for one step oxidative esterification of aldehyde and alcohol generation ester：In 0.1- In the presence of 0.5MPa oxygen, nano catalyst is added in aldehydes, alcohol solution, is heated to reflux.
The aldehydes, alcohols can be the aldehyde and alcohols of any one saturation.
Beneficial effects of the present invention are as follows：
(1) present invention when preparing carrier using ionic liquid as template and ion hardening agent there is structure directing to make With.The soluble-salt of metal is dissolved in the ionic liquid solution, reduces the dosage of alkali, obtained carrier has micro hole knot Structure, increases the specific surface area of carrier, enhances the load capacity of carrier；And nano Au particle is supported on the micro hole knot of carrier In structure, the increase of nano Au particle is effectively prevented.In addition, ionic liquid can strengthen the phase interaction of carrier and nano Au particle More stablized with so that nano Au particle, the service life of catalyst is longer, catalytic activity is more preferable.
The present invention is that the soluble-salt of metal is dissolved in the overall situation of ionic liquid, is not to add ionic liquid solution Enter into the soluble salt solutions of metal, not only reduce the dosage of alkali, and cause the soluble-salt of metal forming carrier During acted on completely by ionic liquid solution.
(2) present invention is by adjusting hydrothermal temperature, ionic liquid species and its dosage come the big of control vector aperture It is small, increase the specific surface area of carrier；
(3) present invention selects the metal-doped cerium base composite solid solutions such as Zr, Co, Fe as metals such as carrier, Zr, Co, Fe After atom enters cerium oxide lattice so that carrier surface oxygen vacancies is more, adds the quantity of active oxygen, enhances catalyst load The load capacity of body, improves the reactivity worth of catalyst, improves the catalytic activity of catalyst, and improves catalyst Way of recycling.
(4) conversion ratio of aldehyde is 98.3-99.8% in the present invention, and the selectivity of ester is 97.6-99.7%, has operation letter The characteristics of list, conversion ratio is higher, and selectivity of product is preferable, substantially increase the stability and process economy of reaction.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the magnetic Nano Au catalyst in embodiment 1.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation method of the nano catalyst for being used for one step oxidative esterification of aldehyde and alcohol generation ester includes following step Suddenly：
(1) preparation of carrier
By 1.8g [C10Mim] Cl ionic liquids are dissolved in 10ml deionized waters, then by 0.87g cerous nitrates, 0.46g Nitric Acid Oxidations Zirconium is dissolved in above-mentioned ionic liquid, adds 0.6g sodium hydroxides and the sodium hydroxide solution of 70g water configuration, mixed solution is put into In the water heating kettle of the polytetrafluoro liner of 100ml, hydro-thermal reaction 24h at 100 DEG C, then by centrifugation, washing, the solid that will be obtained Dry 12h, calcines 4h at 400 DEG C, obtains the bar-shaped cerium zirconium sosoloid carrier with pore structure at 80 DEG C.
(2) preparation of nano catalyst
Prepared using the method for sol precipitation, using PVA as protective agent, with NaBH4For reducing agent.Under stirring, to 1 × 10- 4mol/LHAuCl41wt.%PVA aqueous solutions are added in aqueous solution so that PVA/Au (wt/wt)=0.5:1, stir after five minutes, Add 0.1mol/L NaBH4Aqueous solution, becomes claret liquid, wherein, NaBH4/ Au (mol/mol)=5:1.Stir half small Shi Hou, adds the cerium zirconium sosoloid carrier that step (1) obtains.Solution ph is adjusted to 5 with 0.1mol/L HCl, is stirred at room temperature 1h is mixed, filtering is then washed with deionized, until not having remaining Cl in solution-, solid will be obtained in 80 DEG C of drying boxes Dry 12h, finally roasts 4h at 300 DEG C, obtains nano catalyst, wherein Au load capacity is 1wt.%.Obtained nanometer The transmission electron microscope picture of Au catalyst is as shown in Figure 1.
The application of the nano catalyst for being used for one step oxidative esterification of aldehyde and alcohol generation ester：
Carried out in the stainless steel clamp set tripping batch reactors of 50ml according to common process.Add above-mentioned catalyst, different Butyraldehyde and MeOH.The stable oxygen gas flow rate 10mol/min of mass flowmenter control, and keep preferable gas point using distributor Cloth state.Magnetic stirring apparatus heating stirring keeps the good contact of gas-liquid-solid three-phase, and reaction outlet tail gas is cooled back with condenser pipe Stream, prevents the volatilization of raw material and reaction product, and condenser pipe is followed by a pressure maintaining valve, controls the pressure in reactor.Reaction is filled Put it is closed after, pass first into oxygen to 0.3MPa, then start the cycle over heating water bath, open stirring, reaction starts.React 2h Afterwards, stop air inlet and stirring, close heating, be passed through circulating water, cool down, vent gas, takes out sample and carry out gas phase color Spectrum analysis.Detection data are shown in Table 1.
Embodiment 2
Make the zirconyl nitrate in embodiment 1 into ferric nitrate, prepare ferrocerium solid solution carrier, remaining step is the same as embodiment 1.
Embodiment 3
Make the zirconyl nitrate in embodiment 1 into ferric nitrate, [C10Mim] dosage of Cl is changed to 3.6g, prepare ferrocerium solid solution Body carrier, remaining step is the same as embodiment 1.
Embodiment 4
Make the zirconyl nitrate in embodiment 1 into ferric nitrate, ionic liquid is changed to [C14Mim] Cl, dosage is changed to 2.2g, makes Standby ferrocerium solid solution carrier, remaining step is the same as embodiment 1.
Embodiment 5
Make the zirconyl nitrate in embodiment 1 into cobalt nitrate, ionic liquid is changed to [C10mim]BF4, dosage is changed to 2.2g, Cerium cobalt solid solution carrier is prepared, remaining step is the same as embodiment 1.
Embodiment 6
Make the zirconyl nitrate in embodiment 1 into cobalt nitrate, ionic liquid is changed to [C10mim]BF4, dosage is changed to 4.4g, Cerium cobalt solid solution carrier is prepared, remaining step is the same as embodiment 1.
Embodiment 7
Make the zirconyl nitrate in embodiment 1 into cobalt nitrate, ionic liquid is changed to [emim] SbF6, dosage is changed to 2.6g, Cerium cobalt solid solution carrier is prepared, remaining step is the same as embodiment 1.
Embodiment 8
Make the zirconyl nitrate in embodiment 1 into manganese nitrate, ionic liquid is changed to [C8mim]PF6, dosage is changed to 2.4g, makes Standby cerium manganese solid solution carrier, remaining step is the same as embodiment 1.
Embodiment 9
Make the zirconyl nitrate in embodiment 1 into manganese nitrate, ionic liquid is changed to [C8mim]SbF6, dosage is changed to 3.0g, Cerium manganese solid solution carrier is prepared, remaining step is the same as embodiment 1.
Embodiment 10
Make the zirconyl nitrate in embodiment 1 into nickel nitrate, ionic liquid is changed to [C14mim]SbF6, dosage is changed to 3.6g, Cerium ni solid solution carrier is prepared, remaining step is the same as embodiment 1.
Embodiment 11
Make the zirconyl nitrate in embodiment 1 into nickel nitrate, ionic liquid is changed to [Rpy] NO3, dosage is changed to 1.6g, makes Standby cerium ni solid solution carrier, remaining step is the same as embodiment 1.
Embodiment 12
By the ionic liquid in embodiment 1 by 1.8g [C10Mim] Cl makes 3.6g [C into12Mim] Cl, by 0.87g cerous nitrates, 0.46g zirconyl nitrates make 1.32g cerous nitrates, 0.606g ferric nitrates and 0.935g copper nitrates into, and hydro-thermal reaction at 140 DEG C, prepares Ce-Fe-Cu solid solution carriers, remaining step is the same as embodiment 1.
Data such as table 1 is detected in embodiment 1-12.
Table 1 detects tables of data
Embodiment The conversion ratio (%) of aldehyde The selectivity (%) of ester
1 98.6 98.2
2 98.7 98.1
3 99.1 98.6
4 99.5 99.3
5 99.4 99.1
6 99.5 99.2
7 98.9 98.4
8 99.3 98.9
9 99.4 99.1
10 99.8 99.7
11 98.3 97.6
12 99.4 99.0
Wherein：

Claims (10)

  1. A kind of 1. nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester, it is characterised in that：Using Au as activearm Point, using cerium base composite solid solution as carrier, the load capacity of Au accounts for Au and the 0.1-2wt.% of carrier gross mass；The cerium base is answered Conjunction solid solution is Ce-Zr solid solution, Ce-Co solid solution, Ce-Fe solid solution, Ce-Mn solid solution, Ce-Ni solid solution or Ce-Fe- Cu solid solution.
  2. A kind of 2. preparation side of the nano catalyst for being used for one step oxidative esterification of aldehyde and alcohol generation ester described in claim 1 Method, it is characterised in that comprise the following steps：
    (1) preparation of carrier
    The soluble-salt of metal is dissolved in ionic liquid solution, adds sodium hydroxide solution, hydro-thermal reaction, centrifugation is consolidated Body, dry, calcining, obtains carrier；
    (2) preparation of nano catalyst
    In HAuCl4Protective agent, reducing agent are sequentially added in aqueous solution, adds the carrier that step (1) obtains, then adjusts pH value, It is stirred at room temperature, filters, wash, dry, roasting, obtains nano catalyst.
  3. 3. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (1), metal, ionic liquid, the ratio between the molal quantity of sodium hydroxide are 1:1-3:5-10.
  4. 4. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (1), soluble-salt is nitrate, hydrochloride or sulfate.
  5. 5. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (1), for ionic liquid by anion and cation composition, the anion is Cl-、Br-、 BF4 -、PF6 -、TfO-(CF3SO3 -)、NfO-(C4F9SO3 -)、SbF6 -、AsF6 -、CH3COO-、NO3 -Or SO4 -, the cation is [NR4]+、[bmim]+、[emim]+、[Rpy]+、[C8mim]+、[C10mim]+、[C12mim]+Or [C14mim]+。
  6. 6. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (1), hydrothermal temperature is 100-200 DEG C, the hydro-thermal reaction time 20-28h；Drying temperature For 40-100 DEG C, drying time 10-14h；Calcining heat is 350-450 DEG C, calcination time 2-6h.
  7. 7. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (2), protective agent PVA, reducing agent NaBH4；The mass ratio of PVA and Au is 1:2, NaBH4With The molar ratio of Au is 5:1.
  8. 8. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (2), HCl solution is used to adjust pH value as 4-6.
  9. 9. the preparation side of the nano catalyst according to claim 2 for one step oxidative esterification of aldehyde and alcohol generation ester Method, it is characterised in that：In step (2), it is 0.5-4h that the time, which is stirred at room temperature, and drying temperature is 40-100 DEG C, drying time 10- 14h；Calcination temperature is 250-300 DEG C, roasting time 2-6h.
  10. 10. a kind of application of the nano catalyst for being used for one step oxidative esterification of aldehyde and alcohol generation ester described in claim 1, its It is characterized in that：In the presence of 0.1-0.5MPa oxygen, nano catalyst is added in aldehydes, alcohol solution, is heated to reflux.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109772345A (en) * 2019-01-05 2019-05-21 山东理工大学 The preparation of the Raney nickel of oxidation of aldehydes lactate synthesis ester and its application that catalyst system is total to ionic liquid
CN110105207A (en) * 2019-04-22 2019-08-09 山东理工大学 A kind of technique and application of one step oxidative esterification of parahydroxyben-zaldehyde
CN111330574A (en) * 2020-04-07 2020-06-26 山东理工大学 Method for preparing core-shell cerium-gold catalyst by reverse microemulsion method and application of catalyst
CN111495390A (en) * 2020-04-21 2020-08-07 浙江师范大学 Supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compound and preparation and application thereof
CN111514930A (en) * 2020-04-30 2020-08-11 山东理工大学 Ionic liquid stable single-atom catalyst and preparation method and application thereof
CN111774069A (en) * 2020-07-08 2020-10-16 上海纳米技术及应用国家工程研究中心有限公司 Manganese-cerium solid solution loaded cobalt catalyst for catalyzing and oxidizing volatile organic compounds by ozone and preparation method and application thereof
CN112871167A (en) * 2021-01-14 2021-06-01 浙江理工大学 MOFs (metal-organic frameworks) -packaged ultrafine alloy nanoparticles as well as preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1868588A (en) * 2006-07-03 2006-11-29 浙江工业大学 Method for preparing nickel catalyst carried in ion liquid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1868588A (en) * 2006-07-03 2006-11-29 浙江工业大学 Method for preparing nickel catalyst carried in ion liquid

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PERALA VENKATASWAMY ET AL.: "Nanostructured Ce0.7Mn0.3O2−δ and Ce0.7Fe0.3O2−δ solid solutions fordiesel soot oxidation", 《APPLIED CATALYSIS A: GENERAL》 *
QIAO DONGSHENG等: "Effect of water vapor on the CO and CH4 catalytic oxidation over CeO2-MOx(M=Cu, Mn, Fe, Co, and Ni) mixed oxide", 《JOURNAL OF RARE EARTHS》 *
SITTHIPHONG PENGPANICH ET AL.: "Catalytic oxidation of methane over CeO2-ZrO2 mixed oxide solid solution catalysts prepared via urea hydrolysis", 《APPLIED CATALYSIS A: GENERAL》 *
YUCHAO LI ET AL.: "Oxidative esterification of methacrolein to methyl methacrylate over supported gold catalysts prepared by colloid deposition", 《CHEMCATCHEM》 *

Cited By (13)

* Cited by examiner, † Cited by third party
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CN109772345B (en) * 2019-01-05 2022-03-04 山东理工大学 Preparation of nickel catalyst for synthesizing ester by aldehyde oxidation esterification and application of nickel catalyst and ionic liquid co-catalysis system
CN109772345A (en) * 2019-01-05 2019-05-21 山东理工大学 The preparation of the Raney nickel of oxidation of aldehydes lactate synthesis ester and its application that catalyst system is total to ionic liquid
CN110105207A (en) * 2019-04-22 2019-08-09 山东理工大学 A kind of technique and application of one step oxidative esterification of parahydroxyben-zaldehyde
CN110105207B (en) * 2019-04-22 2022-03-04 山东理工大学 One-step oxidation esterification process and application of p-hydroxybenzaldehyde
CN111330574B (en) * 2020-04-07 2023-05-05 山东理工大学 Method for preparing core-shell cerium-gold catalyst by reverse microemulsion method and application of catalyst
CN111330574A (en) * 2020-04-07 2020-06-26 山东理工大学 Method for preparing core-shell cerium-gold catalyst by reverse microemulsion method and application of catalyst
CN111495390A (en) * 2020-04-21 2020-08-07 浙江师范大学 Supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compound and preparation and application thereof
CN111495390B (en) * 2020-04-21 2023-08-25 浙江师范大学 Supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compound and preparation and application thereof
CN111514930A (en) * 2020-04-30 2020-08-11 山东理工大学 Ionic liquid stable single-atom catalyst and preparation method and application thereof
CN111514930B (en) * 2020-04-30 2023-07-25 山东理工大学 Ionic liquid stable monoatomic catalyst and preparation method and application thereof
CN111774069B (en) * 2020-07-08 2023-02-14 上海纳米技术及应用国家工程研究中心有限公司 Manganese-cerium solid solution loaded cobalt catalyst for catalyzing and oxidizing volatile organic compounds by ozone and preparation method and application thereof
CN111774069A (en) * 2020-07-08 2020-10-16 上海纳米技术及应用国家工程研究中心有限公司 Manganese-cerium solid solution loaded cobalt catalyst for catalyzing and oxidizing volatile organic compounds by ozone and preparation method and application thereof
CN112871167A (en) * 2021-01-14 2021-06-01 浙江理工大学 MOFs (metal-organic frameworks) -packaged ultrafine alloy nanoparticles as well as preparation method and application thereof

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