CN111871418B - Coated nano-catalyst for synthesizing isobutyraldehyde by methanol-ethanol one-step method and preparation method - Google Patents
Coated nano-catalyst for synthesizing isobutyraldehyde by methanol-ethanol one-step method and preparation method Download PDFInfo
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Abstract
The invention belongs to the field of catalyst preparation, and in particular relates to a coated nano catalyst for synthesizing isobutyraldehyde by a methanol-ethanol one-step method and a preparation method thereof, wherein Mg (NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O or Zn (NO) 3 ) 2 ·6H 2 O is a coagent precursor, cu (CH) 3 COO) 2 ·H 2 O is a catalytic precursor, ce (CH) 3 COO) 3 As cerium source precursor, adding alkaline matter as precipitant to prepare M x O y @CuO/CeO 2 (m= Mg, al, mn, fe, zn) coated nanocatalyst. The method is simple, the cost of the prepared catalyst is low, the stability and the mechanical strength of the prepared catalyst are high, and the catalyst has excellent catalytic activity and selectivity in the synthesis of isobutyraldehyde from methanol and ethanol.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a coated nano catalyst for synthesizing isobutyraldehyde by a methanol-ethanol one-step method and a preparation method thereof.
Background
Isobutyraldehyde is one of important chemical production raw materials, can be used for manufacturing cellulose ester, essence, spice, rubber vulcanization accelerator and the like, and can be used as a drug intermediate of amino acid, vitamin and the like. In addition, a number of chemical products are derived. Such as: isobutanol, neopentyl glycol and the like. In the industrial production of the prior art, the oxo synthesis method is often adopted for producing the isobutyraldehyde, and the production of the isobutyraldehyde by methanol and ethanol has important significance for the development of coal chemical industry and has attracted the interests of a plurality of researchers.
In the current industrial production of isobutyraldehyde by methanol ethanol, metal oxide catalysts have led to extensive research, but the conversion of isobutyraldehyde in use is low.
Disclosure of Invention
The invention aims to improve the catalytic activity of a copper-based metal oxide catalyst and the selectivity of isobutyraldehyde, and prepares a coated nano catalyst for synthesizing isobutyraldehyde by a methanol-ethanol one-step method, which has high catalytic activity, good stability and long service life, and the preparation method comprises the following steps:
a preparation method of a coated nano catalyst for synthesizing isobutyraldehyde by a methanol-ethanol one-step method comprises the following steps:
(1) Adding a cerium source precursor and a copper source precursor into a proper amount of deionized water at room temperature for dissolution; dropwise adding an alkali solution under the condition of stirring at 40-50 ℃ to regulate the pH value; aging for 1-3 h at 50-60 ℃; filtering, washing to neutrality, drying at 100-120 deg.c, roasting in muffle furnace at 400-500 deg.c for 3-4 hr to obtain catalyst precursor CuO/CeO 2 。
Wherein the cerium source precursor is Ce (CH) 3 COO) 3 The copper source precursor is Cu (CH) 3 COO) 2 ·H 2 O；
The alkali solution is ammonium carbonate solution with the concentration of 3mol/L, and the pH value is regulated to 7.5-8.5;
(2) Isovolumetric dipping the active agent precursor solution into the CuO/CeO prepared in the step (1) 2 Roasting the mixture for 2 to 3 hours at the temperature of between 200 and 350 ℃ to obtain M x O y @CuO/CeO 2 (m= Mg, al, zn, mn) coated nanocatalyst.
Wherein the coagent precursor is Mg (NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O or Zn (NO) 3 ) 2 ·6H 2 One of O.
In the coated nano catalyst prepared by the method, the mass fraction of CuO as the active component of the catalyst is 10-25%, and the mass ratio of Cu, M and Ce is 3-6:1-2:8-11.
The application of the coated nano catalyst is as follows:
adding 0.2-0.5 g of catalyst into a fixed bed tubular reactor, then introducing methanol and ethanol raw materials, reacting at 200-300 ℃ for 3h, and collecting the generated isobutyraldehyde and other byproducts, wherein the catalyst is the coated nano catalyst.
Wherein the ratio of the mass of the methanol to the ethanol is 2.5-3:1.
The preparation method of the coated catalyst has the beneficial effects that:
the invention prepares CuO/CeO firstly 2 Coating catalyst MgO@CuO/CeO obtained by impregnating catalyst precursor and auxiliary agent 2 、Al 2 O 3 @CuO/CeO 2 、MnO@CuO/CeO 2 、Fe 2 O 3 @CuO/CeO 2 、ZnO@CuO/CeO 2 Has better catalytic activity and stability. In the prepared coated catalyst, cuO is coated with a metal oxide as a first active component, avoiding rapid deactivation of the catalyst, greatly enhancing its stability and service life, as demonstrated in fig. 1.
The metal oxide coated on the surface of the CuO is used as a second active component, and the coated nano catalyst prepared by the method has the advantages of a bifunctional catalyst, so that the catalytic activity of the catalyst is greatly improved, and the conversion rate of ethanol and the selectivity of isobutyraldehyde are greatly improved. Meanwhile, the nano cerium oxide introduced by the invention has more excellent performance, larger specific surface area, good dispersity of surface active components and higher oxygen-philic capability, so that the cerium oxide shows excellent performance in experiments as a catalyst carrier. And the mechanical property of the catalyst is greatly enhanced by introducing the cerium oxide, so that the catalyst has extremely small loss in the use process and is easy to recycle and reuse.
In addition, copper oxide, surface metal oxide and cerium oxide showed good synergy in the process of preparing isobutyraldehyde from methanol and ethanol, and are obviously shown in experiments of examples 1 to 5 and comparative example 6 and comparative example 7.
Drawings
FIG. 1 shows the ethanol conversion over time over two different catalysts.
Detailed Description
The invention is further described below in connection with examples, but is not limited thereto.
Example 1
The preparation method of the coated nano catalyst comprises the following steps:
1) 2.54g Ce (CH) were added at room temperature 3 COO) 3 And 0.92g Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding 3mol/L ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering to neutrality with absolute ethyl alcohol, drying at 110 deg.c, roasting in a muffle furnace at 450 deg.c for 3 hr to obtain catalyst precursor CuO/CeO 2 ；
5) 0.51g of Mg (NO 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 2 hours at the temperature of 300 ℃ to obtain coated MgO@CuO/CeO 2 The mass fraction of CuO of the nano catalyst is 20 percent, and the same is true.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g MgO@CuO/CeO was added 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 95.5%, and the selectivity of isobutyraldehyde is 71.7%. The reaction time was 200 hours, and the ethanol conversion was 89.8%.
Example 2
Steps 1) -4) are the same as in example 1.
Step 5) adding 0.20g Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 2 hours at 300 ℃ to obtain coated Fe 2 O 3 @CuO/CeO 2 A nano catalyst.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g of Fe was added 2 O 3 @CuO/CeO 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 94.5%, and the selectivity of isobutyraldehyde is 70.8%.
Example 3
Steps 1) -4) are the same as in example 1.
Step 5) 0.27g of Al (NO) 3 ) 3 ·9H 2 O is dissolved in 2g deionized water to obtain active agent precursor solution, and the active agent precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting at 300 ℃ for 2 hours to obtain coated Al 2 O 3 @CuO/CeO 2 A nano catalyst.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g of Al was added 2 O 3 @CuO/CeO 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 96.7%, and the selectivity of isobutyraldehyde is 73.5%.
Example 4
Steps 1) -4) are the same as in example 1.
Step 5) 0.26g Mn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 2 hours at the temperature of 300 ℃ to obtain coated MnO@CuO/CeO 2 A nano catalyst.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g MnO@CuO/CeO was added 2 Catalyst, reaction temperature is 260 ℃, reaction pressure is 2MPa, reaction time is 3h, and methanol and ethanol are mixedThe mass ratio of the substances is 2.7:1, the produced mixed products such as isobutyraldehyde and the like are collected, condensed and separated, the conversion rate of the ethanol is 97.8%, and the selectivity of the isobutyraldehyde is 74.3%.
Example 5
Steps 1) -4) are the same as in example 1.
Step 5) 0.30g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 2 hours at the temperature of 300 ℃ to obtain coated ZnO@CuO/CeO 2 A nano catalyst.
The application of the coated nano catalyst of the experimental example is as follows:
in a fixed bed tubular reactor, 0.4g ZnO@CuO/CeO was added 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 98.6%, and the selectivity of isobutyraldehyde is 76.0%.
Example 6
1) 3.49g of Ce (CH) 3 COO) 3 And 0.6g Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding an ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering to neutrality with absolute ethyl alcohol, drying at 100 ℃, placing in a muffle furnace, roasting at 400 ℃ for 4 hours, and preparing the catalyst precursor CuO/CeO 2 。
5) 0.40g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 3 hours at the temperature of 200 ℃ to obtain coated ZnO@CuO/CeO 2 Nano catalyst, cuO mass fraction 10%.
The application of the coated nano catalyst is as follows:
at the fixing positionAdding 0.4g ZnO@CuO/CeO into a fixed bed tubular reactor 2 The catalyst has the reaction temperature of 200 ℃, the reaction pressure of 2MPa, the reaction time of 5h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products such as isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 94.6%, and the selectivity of isobutyraldehyde is 71.8%.
Example 7
1) 2.86g Ce (CH) 3 COO) 3 And 0.86g Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding an ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering to neutrality with absolute ethyl alcohol, drying at 120 deg.C, roasting in a muffle furnace at 500 deg.C for 3 hr to obtain catalyst precursor CuO/CeO 2 。
5) 0.37g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 2 hours at the temperature of 350 ℃ to obtain coated ZnO@CuO/CeO 2 The mass fraction of CuO of the nano catalyst is 17.5%.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g ZnO@CuO/CeO was added 2 The catalyst has the reaction temperature of 200 ℃, the reaction pressure of 2MPa, the reaction time of 5h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 96.1%, and the selectivity of isobutyraldehyde is 73.3%.
Example 8
1) 2.54g Ce (CH) were added at room temperature 3 COO) 3 And 1.2g Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding an ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering to neutrality with absolute ethyl alcohol, drying at 100 ℃, placing in a muffle furnace, roasting at 400 ℃ for 4 hours, and preparing the catalyst precursor CuO/CeO 2 。
5) 0.34g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active auxiliary agent, and the precursor solution is immersed in the prepared CuO/CeO in an equal volume 2 Roasting the mixture for 3 hours at the temperature of 200 ℃ to obtain coated ZnO@CuO/CeO 2 The mass fraction of CuO of the nano catalyst is 25%.
The application of the coated nano catalyst is as follows:
in a fixed bed tubular reactor, 0.4g ZnO@CuO/CeO was added 2 The catalyst has the reaction temperature of 200 ℃, the reaction pressure of 2MPa, the reaction time of 5h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products such as isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 96.8%, and the selectivity of isobutyraldehyde is 74.2%.
Comparative example 1
1) 0.30g Zn (NO) 3 ) 2 ·6H 2 O、0.92g Cu(CH 3 COO) 2 ·H 2 Mixing O and 2.54g of cerium acetate, adding 50mL of deionized water and stirring;
2) Preparing ammonia water and ammonium carbonate (n) with mass fraction of 10% Ammonia water :n Ammonium carbonate =4:1) mixed solution;
3) Simultaneously dripping the solution obtained in the step 1) and the solution obtained in the step 2) into a three-neck flask for precipitation at 50 ℃ under strong stirring, and controlling the pH value to be 8-9 to enable the solution to completely generate precipitation;
4) Transferring the mixed solution to a stainless steel reaction kettle at 60 ℃ for crystallization for 8-10 h;
5) Washing with deionized water and ethanol, suction filtering to neutrality, and standing overnight at 100deg.C;
6) Roasting in a muffle furnace at 300 ℃ for 2 hours to obtain ZnO-CuO-CeO 2 A type catalyst.
0.4g ZnO-CuO-CeO prepared by a coprecipitation method is added into a fixed bed tubular reactor 2 Catalyst, reaction temperature is 260 ℃, reaction pressure is 2MPa, and reaction is carried out3h between, collecting and condensing mixed products such as isobutyraldehyde and the like generated by the condensation separation of the mixed products, wherein the mass ratio of methanol to ethanol is 2.7:1, and the conversion rate of ethanol is 96.3 percent and the selectivity of isobutyraldehyde is 71.5 percent. The reaction time was 22 hours, and the conversion of ethanol was 76.1%.
Comparative example 2
Catalyst MgO@CuO/CeO used in experimental example 1 2 Replaced by MgO-CuO-CeO 2 The method is characterized by comprising the following steps:
adding 0.4g of MgO-CuO-CeO2 catalyst prepared by a coprecipitation method into a fixed bed tubular reactor, then introducing methanol and ethanol raw materials, wherein the reaction temperature is 260 ℃, the reaction pressure is 2MPa, the reaction time is 3h, the mass ratio of methanol to ethanol substances is 2.7:1, collecting and condensing and separating the produced mixed products such as isobutyraldehyde, the conversion rate of ethanol is 91.7%, and the selectivity of isobutyraldehyde is 67.9%.
Comparative example 3
Experimental example 2 catalyst Fe 2 O 3 @CuO/CeO 2 Replaced by Fe 2 O 3 -CuO-CeO 2 The method is characterized by comprising the following steps:
0.4g ZnO-CuO-CeO prepared by a coprecipitation method is added into a fixed bed tubular reactor 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 90.5%, and the selectivity of isobutyraldehyde is 66.3%.
Comparative example 4
Experimental example 3 catalyst Al 2 O 3 @CuO/CeO 2 Replaced by Al 2 O 3 -CuO-CeO 2 The method is characterized by comprising the following steps:
in a fixed bed tubular reactor, 0.4g of Al prepared by coprecipitation was added 2 O 3 -CuO-CeO 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 93.0%, and the selectivity of isobutyraldehyde is 69.4%.
Comparative example 5
Experimental example 4 catalyst MnO@CuO/CeO 2 Replaced by MnO-CuO-CeO 2 The method is characterized by comprising the following steps:
in a fixed bed tubular reactor, 0.4g MnO-CuO-CeO prepared by a coprecipitation method is added 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 94.7%, and the selectivity of isobutyraldehyde is 70.2%.
Comparative example 6
1) 2.54g Ce (CH) were added at room temperature 3 COO) 3 And 0.92g Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding an ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering with absolute ethyl alcohol to neutrality, drying at 110 ℃, placing in a muffle furnace, roasting at 300 ℃ for 2h, and preparing the catalyst CuO/CeO 2 。
In a fixed bed tubular reactor, 0.4g of CuO/CeO was added 2 The catalyst has the reaction temperature of 260 ℃, the reaction pressure of 2MPa, the reaction time of 3h, the mass ratio of methanol to ethanol of 2.7:1, and the mixed products of isobutyraldehyde and the like which are generated by collecting, condensing and separating, wherein the conversion rate of ethanol is 93.2%, and the selectivity of isobutyraldehyde is 67.5%. The reaction time was 200 hours, and the ethanol conversion was 70.5%.
Comparative example 7
1) 0.92g of Cu (CH) 3 COO) 2 ·H 2 O is added into 50mL of deionized water for dissolution;
2) Dropwise adding an ammonium carbonate aqueous solution under the condition of stirring at 45 ℃ to adjust the pH to 8;
3) Aging the mixed solution obtained in the step 2) for 3 hours at 60 ℃;
4) Filtering with absolute ethyl alcohol to be neutral, drying at 110 ℃, and placing in a muffle furnace to be roasted at 400 ℃ for 4 hours to prepare the catalyst CuO.
5) 0.30g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 2mL of deionized water to obtain a precursor solution of the active agent, the precursor solution is immersed in the prepared CuO in an equal volume, and the CuO is roasted for 2 hours at 300 ℃ to obtain the ZnO@CuO catalyst.
In a fixed bed tubular reactor, 0.4g of ZnO@CuO catalyst is added, the reaction temperature is 260 ℃, the reaction pressure is 2MPa, the reaction time is 3h, the mass ratio of methanol to ethanol is 2.7:1, the obtained mixed products such as isobutyraldehyde and the like are collected, condensed and separated, the conversion rate of ethanol is 89.3%, the selectivity of isobutyraldehyde is 64.5%, and the conversion rate of ethanol is 66.7% after 200 hours of reaction.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (5)
1. The application of the coated nano catalyst in synthesizing isobutyraldehyde by a methanol-ethanol one-step method is characterized in that: the application method comprises the following steps: adding a catalyst into a fixed bed tubular reactor, then introducing methanol and ethanol for reaction, and collecting the generated isobutyraldehyde;
the dosage of the catalyst is 0.2-0.5 g, and the ratio of the mass of methanol to the mass of ethanol is 2.5-3:1; the reaction temperature is 200-300 ℃ and the reaction time is 3h;
the preparation method of the coated nano catalyst comprises the following steps:
(1) Adding a cerium source precursor and a copper source precursor into a solvent, uniformly stirring, adding an alkaline substance to adjust the pH, aging for 1-3 hours at 50-60 ℃, filtering, washing, drying at 100-120 ℃, and placing in a muffle furnace to bake for 3-4 hours at 400-500 ℃ to obtain CuO/CeO 2 A catalyst precursor;
(2) Dipping a precursor of a reactive auxiliary agent to prepare CuO/CeO 2 Then roasting it to obtain M x O y @CuO/CeO 2 A coated nanocatalyst, wherein m= Mg, al, mn, fe, zn.
2. The use of the coated nanocatalyst of claim 1 in a one-step methanol-ethanol synthesis of isobutyraldehyde, wherein the cerium source precursor of step (1) is Ce (CH) 3 COO) 3 The copper source precursor is Cu (CH) 3 COO) 2 ·H 2 O。
3. The application of the coated nano catalyst in the one-step synthesis of isobutyraldehyde by methanol and ethanol according to claim 1, wherein the alkaline substance in the step (1) is ammonium carbonate, and the pH is adjusted to 7.5-8.5.
4. The use of the coated nano-catalyst according to claim 1 in the one-step synthesis of isobutyraldehyde from methanol and ethanol, wherein the catalyst in step (2) is baked for 2-3 hours at 200-300 ℃.
5. The use of the coated nanocatalyst of claim 1 in a one-step methanol-ethanol process for the synthesis of isobutyraldehyde, wherein the coagent precursor of step (2) is Mg (NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O or Zn (NO) 3 ) 2 ·6H 2 One of O.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200425951A (en) * | 2003-02-20 | 2004-12-01 | Nippon Kayaku Kk | Catalyst for producing methacrylic acid and preparation method thereof |
| CN109675579A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | It is a kind of to prepare isobutylaldehyde catalyst method |
| CN113289631A (en) * | 2021-06-16 | 2021-08-24 | 润泰新材料股份有限公司 | Supported metal oxide catalyst for synthesizing isobutyraldehyde by methanol and ethanol one-step method and preparation method and application thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK112519B (en) * | 1957-07-10 | 1968-12-23 | Hoechst Ag | Process for the production of aldehydes and ketones by oxidation of olefins. |
| US5559275A (en) * | 1995-02-21 | 1996-09-24 | Uop | Process for the conversion of lower alcohols to higher branched oxygenates |
| CN1101262C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
| CN100584456C (en) * | 2006-11-17 | 2010-01-27 | 南化集团研究院 | Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof |
| CN101385976A (en) * | 2008-10-30 | 2009-03-18 | 上海应用技术学院 | Preparation method of cuprum cerium composite oxides catalyst |
| CN102258998B (en) * | 2011-05-09 | 2012-12-19 | 福州大学 | Ammonia synthesis catalyst and preparation method thereof |
| PL2782670T3 (en) * | 2011-11-21 | 2024-01-29 | Basf Corporation | Coper-zicornia catalyst and method of use and manufacture |
| CN102716749B (en) * | 2011-11-24 | 2014-08-06 | 昆明理工大学 | Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol |
| JP6017777B2 (en) * | 2011-11-30 | 2016-11-02 | 住友化学株式会社 | Method for producing catalyst composition for ammonia production and method for producing ammonia |
| CN102614888A (en) * | 2012-03-12 | 2012-08-01 | 上海应用技术学院 | Method for preparing loaded CuO/CeO2 catalyst |
| CN104096566A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing copper series methanol synthesis catalyst through precipitation-impregnation process |
| CN103623831A (en) * | 2013-11-26 | 2014-03-12 | 中国科学院福建物质结构研究所 | Copper oxide-cerium oxide compound and preparation method thereof as well as application of compound in catalytic field |
| CN105126897B (en) * | 2015-07-29 | 2017-08-25 | 中国科学院山西煤炭化学研究所 | A kind of molecular sieve carried copper-based catalysts of SBA 15 and preparation method and application |
| CN107899583A (en) * | 2017-11-22 | 2018-04-13 | 山东玉皇化工有限公司 | It is a kind of to prepare catalyst of ethanol and preparation method thereof for methyl methanol syngas |
| CN110743557A (en) * | 2019-10-24 | 2020-02-04 | 浙江工业大学 | Catalyst for synthesizing isobutanol by continuous catalytic dehydrogenation and condensation of methanol and ethanol fixed bed and preparation method and application thereof |
-
2020
- 2020-06-29 CN CN202010602188.2A patent/CN111871418B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200425951A (en) * | 2003-02-20 | 2004-12-01 | Nippon Kayaku Kk | Catalyst for producing methacrylic acid and preparation method thereof |
| CN109675579A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | It is a kind of to prepare isobutylaldehyde catalyst method |
| CN113289631A (en) * | 2021-06-16 | 2021-08-24 | 润泰新材料股份有限公司 | Supported metal oxide catalyst for synthesizing isobutyraldehyde by methanol and ethanol one-step method and preparation method and application thereof |
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