CN113398962A - Co @ CuC/Al for preparing isobutyraldehyde with high selectivity2O3Process for preparing catalyst - Google Patents
Co @ CuC/Al for preparing isobutyraldehyde with high selectivity2O3Process for preparing catalyst Download PDFInfo
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- CN113398962A CN113398962A CN202110685070.5A CN202110685070A CN113398962A CN 113398962 A CN113398962 A CN 113398962A CN 202110685070 A CN202110685070 A CN 202110685070A CN 113398962 A CN113398962 A CN 113398962A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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Abstract
The invention belongs to the technical field of catalysis, and particularly relates to Co @ CuC/Al for preparing isobutyraldehyde in a high-selectivity manner2O3A method for preparing the catalyst. Preparing a double-active-center catalyst precursor by using a coprecipitation method, then treating with methane in a plasma reactor to generate stable active metal and carbide, firstly generating stable carbonium ions and hydrogen ions in the metal active center by using propylene in a plasma environment, maintaining the retention time of a secondary carbonium ion intermediate by using copper carbide, adsorbing CO on the active center, activating carbonyl carbon to combine with the secondary carbonium ions, and finally generating isobutyraldehyde with hydrogen dissociated on the copper carbide and cobalt. The selectivity of propylene hydroformylation can be made higher. The catalyst prepared by the method has low costThe catalyst has the advantages of high activity, good catalyst stability, low reaction temperature, low pressure, high selectivity of isobutyraldehyde and good industrial prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to Co @ CuC/Al for preparing isobutyraldehyde in a high-selectivity manner2O3A method for preparing the catalyst.
Background
1938 German scientist Otto Roelen first discovered that the aldehyde group formed by hydroformylation reaction could be further converted into imine, amine, hemiacetal, acetal, aminal, carboxyl, hydroxyl, etc. The existing hydroformylation of propylene aims at preparing n-butyraldehyde. In order to improve the selectivity of the n-butyraldehyde, a rhodium carbonyl-phosphine ligand is used as an active component of a homogeneous catalyst, and the selectivity of the n-butyraldehyde is adjusted through the spatial structure of the phosphine ligand. Although the catalyst has high activity and selectivity, rhodium metal is expensive and the production cost is high. And the phosphine ligand has great toxicity and great harm to the environment. And the catalyst is a homogeneous catalyst, the generated product is difficult to separate from the catalyst, the recovery rate of the noble metal rhodium is not high, and the engineering application is not facilitated.
Isobutyraldehyde is an important chemical raw material, can be used for developing other important organic synthesis intermediates such as spices, medicines, feeds and the like, is a set of device which can produce a series of products according to orders, and has the production characteristics of low yield, multiple varieties and high added value. In the prior art, isobutyraldehyde is an industrial by-product of the oxo synthesis of propylene.
Disclosure of Invention
The invention aims to provide Co @ CuC/Al2O3A method for preparing isobutyraldehyde by catalyzing propylene hydroformylation with high selectivity.
In order to improve the selectivity of isobutyraldehyde when preparing butyraldehyde by propylene hydroformylation, the invention designs Al2O3In the supported bifunctional catalyst, a carrier can improve the generation of secondary carbonium ions by the addition of solid acid and adsorbed propylene, and cobalt carbide has good capability of activating CO and hydrogen.
In order to achieve the purpose, the technical scheme of the invention is as follows:
preparation of Co @ CuC/Al by plasma method2O3A process for the preparation of a catalyst comprising the steps of:
(1) respectively preparing a copper salt solution, a cobalt salt solution, an aluminum nitrate solution and a potassium carbonate solution for later use;
wherein the copper salt is one or more of copper nitrate, copper acetate, copper chloride and copper sulfate, and the mass concentration of the copper salt solution is 1-5 mol/L.
The cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate, and the mass concentration of the cobalt salt solution is 0.1-2 mol/L.
The mass concentration of the aluminum nitrate solution is 1-6 mol/L.
The mass concentration of the potassium carbonate solution is 1-4 mol/L.
Preferably, the mass concentration of the copper salt solution is 1-2mol/L, the mass concentration of the cobalt salt solution is 0.2-0.4mol/L, the mass concentration of the aluminum nitrate solution is 2-4mol/L, and the mass concentration of the potassium carbonate solution is 1.2-2.4 mol/L.
(2) Mixing a copper salt solution, a cobalt salt solution and an aluminum nitrate solution in equal volume to obtain a mixed solution;
(3) injecting the potassium carbonate solution into the mixed solution in the step (2) by using a liquid phase pump under the condition of stirring, and then aging to obtain a precipitate;
the flow rate of the liquid phase pump is 1-5 ml/min. The stirring time is 1-7h, and the aging time is more than 5 h.
Preferably, the flow rate of the liquid phase pump is 2-4ml/min, the stirring time is 2-3h, and the aging time is 5-12 h.
(4) Filtering and washing the precipitate prepared in the step (3) to a pH value of 4-8, and drying to obtain a catalyst precursor;
the drying temperature is 80-200 ℃.
Preferably, the pH of the washing is 5-7 and the temperature of the drying is 100-150 ℃.
(5) Putting the catalyst precursor prepared in the step (4) into plasma, introducing mixed gas of methane and hydrogen for carbonization and reduction to obtain Co @ CuC/Al2O3A catalyst.
Setting the temperature of the plasma device at 20-100 ℃, and setting the voltage of the plasma at 10-40 KV; in a mixed gas of methane and hydrogen, CH4And H2The volume ratio of (A) to (B) is 1: 20-100; the flow rate of the introduced mixed gas is 20-200mL/min, and the concentration of the mixed gas is 60-150 mL/min.
Preferably, the temperature of the plasma device is 40-70 ℃, and the voltage is 20-30 KV; in a mixed gas of methane and hydrogen, CH4And H2The volume ratio of (A) to (B) is 1: 40-80.
Methane can carbonize copper and can insert more nano carbon particles between the layered structures under the action of a cobalt catalyst in plasma, and the nano carbon particles can enable the copper carbide to be more stable.
The catalyst prepared by the method is used for preparing isobutyraldehyde with high selectivity by a plasma method. The specific application method comprises the following steps: loading the catalyst into a plasma device, and introducing propylene, CO and H2The mixed gas is reacted to obtain the product isobutyraldehyde, wherein the reaction temperature is 20-100 ℃, and the pressure is normal pressure. Propylene, CO, H2The molar ratio of (1-3: 1-3): 1-3. The feeding speed of propylene is 20-200mL/min, the feeding speed of synthesis gas is 20-200mL/min, and the plasma discharge voltage is 2-60 KV.
The invention has the advantages that:
the method for preparing isobutyraldehyde by using the plasma method has high selectivity, and the product is a liquid phase, so that the tail gas from gas-liquid separation can be recycled as the raw material.
The catalyst is prepared by a plasma method, wherein alumina is used as a carrier, active centers of the catalyst are cobalt and copper carbide, the copper carbide can generate a stable secondary carbonium ion intermediate, the alumina promotes the generation of the secondary carbonium ion, CO is adsorbed on the active centers, carbonyl carbon is activated to be combined with the secondary carbonium ion, and finally isobutyraldehyde is generated with hydrogen dissociated from the cobalt on the copper carbide. The catalyst has greater economic value due to the reaction carried out under normal pressure and low temperature. The active centers of the catalyst are cobalt and copper carbide, so that the catalyst not only can provide activated hydrogen ions, but also can increase the retention time of a secondary carbonium ion intermediate, thereby improving the selectivity of isobutyraldehyde products.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst prepared in example 1 of the present invention.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
Respectively preparing a copper nitrate solution with the concentration of 2mol/L, a cobalt nitrate solution with the concentration of 0.2mol/L and an aluminum nitrate solution with the concentration of 4mol/L, mixing the solutions in an equal body manner, slowly dripping an excessive potassium carbonate solution with the concentration of 2mol/L into the mixed solution at the flow rate of 2mL/min by using a liquid phase pump, stirring the mixed solution for 5 hours, aging the mixed solution for 8 hours, drying the mixed solution in a 120 ℃ oven, putting the prepared precursor into a plasma device, and performing plasma treatment at the temperature of 30 ℃ and the voltage of 25KV and CH4：H2The ratio of the carbon to the carbon is 1:100, and the flow rate is 60mL/min for 2 h.
The prepared catalyst is reacted in plasma, and propylene, CO and H are introduced2The mixed gas is 1:1.2:1.2, the flow rate is 50mL/min, wherein the reaction temperature is 70 ℃, the voltage is 25KV, the liquid phase is the product after the reaction through a gas-liquid separator, the gas phase is the reaction raw material, and the reaction is continued.
Example 2
The procedure of example 1 was repeated except that 2mol/L of copper nitrate was replaced with 2mol/L of copper chloride.
Example 3
The procedure of example 1 was repeated except that 2mol/L copper sulfate was used instead of 2mol/L copper nitrate in example 1.
Example 4
The procedure of example 1 was repeated except that 0.2mol/L cobalt acetate was used instead of 0.2mol/L cobalt nitrate in example 1.
Example 5
The procedure of example 1 was repeated except that 0.2mol/L cobalt nitrate was replaced with 0.2mol/L cobalt chloride.
Example 6
The procedure of example 1 was repeated except that the flow rate of the liquid phase pump used in example 1 was changed to 4mL/min, and the flow rate of the liquid phase pump used in example 1 was changed to 2 mL/min.
Example 7
The drying in an oven at 80 ℃ is used for replacing the drying in an oven at 120 ℃ in the example 1, and the other steps are the same as the example 1.
Example 8
The drying in the oven at 160 ℃ is used for replacing the drying in the oven at 120 ℃ in the example 1, and the other steps are the same as the example 1.
Example 9
The same procedure as in example 1 was repeated except that the temperature was 70 ℃ and the voltage was 20KV, instead of 70 ℃ and 25KV in example 1.
Example 10
The same procedure as in example 1 was repeated except that the temperature was 70 ℃ and the voltage was 35KV, instead of 70 ℃ and 25KV in example 1.
Example 11
By introducing propylene, CO, H2The mixed gas is 1:1:1 instead of the propylene, CO and H introduced in the example 12The mixture ratio was 1:1.2:2, and the other steps were the same as in example 1.
Example 12
By introducing propylene, CO, H2The mixed gas is 1:1:3 instead of the propylene, CO and H introduced in the example 12The mixture ratio was 1:1.2:2, and the other steps were the same as in example 1.
Comparative example 1
The procedure of example 1 was repeated except that a copper nitrate solution having a concentration of 2mol/L, a cobalt nitrate solution having a concentration of 0.2mol/L and an aluminum nitrate solution having a concentration of 4mol/L were prepared in each of example 1, and the mixture was isovolumetric mixed with a copper nitrate solution having a concentration of 2mol/L and an aluminum nitrate solution having a concentration of 4mol/L, respectively.
Comparative example 2
The same procedure as in example 1 was repeated except that a cobalt nitrate solution having a concentration of 0.2mol/L and an aluminum nitrate solution having a concentration of 4mol/L were prepared and mixed in an isocratic manner in place of the copper nitrate solution having a concentration of 2mol/L, the cobalt nitrate solution having a concentration of 0.2mol/L and the aluminum nitrate solution having a concentration of 4mol/L prepared in example 1.
Comparative example 3
The procedure of example 1 was repeated except that the flow rate of the liquid phase pump used in example 1 was changed to 8mL/min, and the flow rate of the liquid phase pump used in example 1 was changed to 2 mL/min.
Comparative example 4
The reaction temperature in example 1 was replaced by 150 ℃ and the other steps were the same as in example 1.
Comparative example 5
The procedure of example 1 was repeated except that a nickel nitrate solution having a concentration of 2mol/L, a cobalt nitrate solution having a concentration of 0.2mol/L and an aluminum nitrate solution having a concentration of 4mol/L were prepared and mixed in an isocratic manner, instead of preparing a copper nitrate solution having a concentration of 2mol/L, a cobalt nitrate solution having a concentration of 0.2mol/L and an aluminum nitrate solution having a concentration of 4mol/L in example 1 and mixing in an isocratic manner.
Comparative example 6
Respectively preparing a copper nitrate solution with the concentration of 2mol/L, a cobalt nitrate solution with the concentration of 0.2mol/L and an aluminum nitrate solution with the concentration of 4mol/L, mixing the solutions in an equal body manner, slowly dripping an excessive potassium carbonate solution with the concentration of 2mol/L into the mixed solution at the flow rate of 2mL/min by using a liquid phase pump, stirring the mixed solution for 5 hours, aging the mixed solution for 8 hours, drying the mixed solution in a 120 ℃ oven, putting the prepared precursor into a plasma device, and adding CH without voltage at the temperature of 30 ℃ in a plasma device4：H2The ratio of the carbon to the carbon is 1:100, and the flow rate is 60mL/min for 2 h.
The prepared catalyst is reacted in plasma, and propylene, CO and H are introduced2The mixed gas is 1:1.2:1.2, the flow rate is 50mL/min, the reaction temperature is 70 ℃, the voltage is 25KV, the mixed gas passes through a gas-liquid separator after reaction, the liquid phase is the product, the gas phase is the reaction raw material, and the mixed gas continuously participates in the reaction.
The data after the reaction in the examples and comparative examples were analyzed, and the results are shown in table 1:
TABLE 1 comparison of propylene conversion and isobutyraldehyde Selectivity in examples and comparative examples
| Propylene conversion rate,% | Isobutyraldehyde selectively,% | |
| Example 1 | 28 | 92 |
| Example 2 | 22 | 87 |
| Example 3 | 25 | 81 |
| Example 4 | 17 | 83 |
| Example 5 | 13 | 71 |
| Example 6 | 21 | 79 |
| Example 7 | 25 | 80 |
| Example 8 | 26 | 72 |
| Example 9 | 11 | 75 |
| Example 10 | 14 | 79 |
| Example 11 | 21 | 60 |
| Example 12 | 15 | 80 |
| Comparative example 1 | 20 | 41 |
| Comparative example 2 | 19 | 59 |
| Comparative example 3 | 26 | 74 |
| Comparative example 4 | 14 | 66 |
| Comparative example 5 | 16 | 47 |
| Comparative example6 | 7 | 36 |
As can be seen from table 1, the catalyst not only provides a stable secondary carbonium ion intermediate, but also allows CO to be adsorbed on the catalyst more easily, activating carbonyl carbon to bind to the secondary carbonium ion, and finally generating isobutyraldehyde with the hydrogen dissociated from cobalt on copper carbide. The active center of the catalyst is the generated cobalt and copper carbide, the bimetallic catalyst can provide activated hydrogen ions and can increase the retention time of a secondary carbonium ion intermediate, and meanwhile, the adsorption characteristic of the metal carbide on CO improves the selectivity of isobutyraldehyde products. The catalyst is simple to prepare, low in cost, mild in reaction condition and high in industrial value.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. Co @ CuC/Al2O3The preparation method of the catalyst is characterized by comprising the following steps:
(1) respectively preparing a copper salt solution, a cobalt salt solution, an aluminum nitrate solution and a potassium carbonate solution for later use;
(2) mixing a copper salt solution, a cobalt salt solution and an aluminum nitrate solution in equal volume to obtain a mixed solution;
(3) injecting the potassium carbonate solution into the mixed solution in the step (2) by using a liquid phase pump under the condition of stirring, stirring and aging to obtain a precipitate;
(4) filtering, washing and drying the precipitate prepared in the step (3) to obtain a catalyst precursor;
(5) putting the catalyst precursor prepared in the step (4) into plasma, and introducing methane and hydrogen to mixThe resultant gas is carbonized and reduced to obtain Co @ CuC/Al2O3A catalyst.
2. Co @ CuC/Al as in claim 12O3The preparation method of the catalyst is characterized in that the copper salt in the step (1) is one or more of copper nitrate, copper acetate, copper chloride and copper sulfate; the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate.
3. Co @ CuC/Al as in claim 12O3The preparation method of the catalyst is characterized in that the mass concentration of the copper salt solution in the step (1) is 1-5mol/L, the mass concentration of the cobalt salt solution is 0.1-2mol/L, the mass concentration of the aluminum nitrate solution is 1-6mol/L, and the mass concentration of the potassium carbonate solution is 1-4 mol/L.
4. Co @ CuC/Al as in claim 12O3The preparation method of the catalyst is characterized in that the flow rate of the liquid phase pump in the step (3) is 1-5ml/min, the stirring time is 1-7h, and the aging time is 5-12 h.
5. Co @ CuC/Al as in claim 12O3The preparation method of the catalyst is characterized in that the drying temperature in the step (4) is 80-200 ℃.
6. Co @ CuC/Al as in claim 12O3The preparation method of the catalyst is characterized in that CH in the mixed gas of methane and hydrogen in the step (5)4And H2The volume ratio is 1:20-100, and the flow of the introduced mixed gas is 20-200 mL/min; the carbonization temperature is 20-100 ℃, the carbonization treatment time is 1-8h, and the voltage of plasma is 10-40 KV.
7. Co @ CuC/Al prepared according to the method of claim 12O3The application of the catalyst is characterized in that the catalyst is used for catalyzing propylene hydroformylation to prepare isobutyraldehyde in a high-selectivity mode.
8. Co @ CuC/Al as in claim 72O3The application of the catalyst is characterized in that the method for preparing isobutyraldehyde comprises the following steps: mixing Co @ CuC/Al2O3The catalyst is loaded into a plasma device, and propylene, CO and H are introduced2The mixed gas reacts to prepare isobutyraldehyde.
9. Co @ CuC/Al as in claim 82O3The application of the catalyst is characterized in that the reaction temperature is 20-100 ℃, the pressure is normal pressure, and the reaction is carried out by propylene, CO and H2The molar ratio of (1-3: 1-3): 1-3, the flow rate of propylene is 20-200mL/min, the flow rate of the mixture of carbon monoxide and hydrogen is 20-200mL/min, and the plasma discharge voltage is 2-60 KV.
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