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 PDFInfo
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- 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
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- 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
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- 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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- 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
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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
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)
- 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.
- 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 carrierThe 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 catalystIn 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. 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. 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. 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. 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. 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. 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. 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. 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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