CN112642481A - Catalyst for preparing dialkyl carbonate from dialkyl oxalate, preparation method thereof and method for preparing dialkyl carbonate - Google Patents
Catalyst for preparing dialkyl carbonate from dialkyl oxalate, preparation method thereof and method for preparing dialkyl carbonate Download PDFInfo
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- CN112642481A CN112642481A CN201910957152.3A CN201910957152A CN112642481A CN 112642481 A CN112642481 A CN 112642481A CN 201910957152 A CN201910957152 A CN 201910957152A CN 112642481 A CN112642481 A CN 112642481A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
Abstract
The invention relates to the field of preparation of dialkyl carbonate, in particular to a catalyst for preparing dialkyl carbonate from dialkyl oxalate, a preparation method thereof and a method for preparing dialkyl carbonate. The catalyst comprises a carrier and an alkali metal compound loaded on the carrier, wherein the carrier is a multi-walled carbon nanotube. When the catalyst is used in the reaction of preparing dialkyl carbonate from dialkyl oxalate, higher raw material conversion rate and product selectivity can be obtained, and the yield of dialkyl carbonate is obviously improved.
Description
Technical Field
The invention relates to the field of preparation of dialkyl carbonate, in particular to a catalyst for preparing dialkyl carbonate from dialkyl oxalate, a preparation method thereof and a method for preparing dialkyl carbonate.
Background
Dimethyl carbonate is an important organic starting material. The processes for industrially producing dimethyl carbonate at present mainly include phosgene method, ester exchange method, methanol oxidative carbonylation method and the like. Among them, the phosgene method is an early production method, not only has a complicated process, but also has a high toxicity of raw materials, and is not favorable for safe production, so that it belongs to a process which is eliminated. The preparation cost and the operation cost of the catalyst used in the methanol oxidation carbonylation method are high, and certain limitation is caused to the application of the catalyst. And the transesterification method with the maximum total energy is easily influenced by the price of ethylene carbonate serving as a raw material, and the yield is low.
CN102212009A provides a process for co-producing dimethyl carbonate and dimethyl ether by a urea alcoholysis method, which comprises adding methanol and urea into a reaction apparatus, reacting methanol and urea to generate methyl carbamate and by-product ammonia, and further reacting the generated methyl carbamate with methanol to generate dimethyl carbonate and by-product ammonia. CN106946706A discloses a method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol, which comprises the steps of placing methanol, N-dialkyl imidazole bicarbonate ionic liquid and carbon dioxide in a high-pressure kettle, wherein the pressure of the carbon dioxide is 0.1-5 MPa, and the dimethyl carbonate is prepared by direct reaction at the temperature of room temperature to 100 ℃ by taking the N, N-dialkyl imidazole bicarbonate ionic liquid as a catalyst and a dehydrating agent through continuous stirring. However, the two methods have the problems of harsh conditions, low yield and the like, and the realization of industrialization is still difficult.
There are also some prior art disclosures of dimethyl carbonate from dimethyl oxalate by decarbonylation, the equation being:
the reaction process is simple, convenient to operate and has a good application prospect. However, in the existing literature, activated carbon is mostly used as a catalyst carrier, and the catalyst of the type has the problems of poor selectivity, low stability and the like, so that the industrial application of the catalyst is limited, and the research on the reaction is in a laboratory stage at present.
Therefore, a catalyst for preparing dimethyl carbonate from dimethyl oxalate through decarbonylation reaction with high catalytic activity and high product selectivity is needed.
Disclosure of Invention
The invention aims to overcome the problems of complex process, low product yield and the like in the process for preparing dialkyl carbonate, particularly dimethyl carbonate in the prior art, and provides a catalyst for preparing dialkyl carbonate, a preparation method thereof and a method for preparing dialkyl carbonate.
In order to achieve the above object, a first aspect of the present invention provides a catalyst comprising a support and an alkali metal compound supported on the support, the support being a multiwalled carbon nanotube.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the invention, the process comprising: the alkali metal compound is supported on the multi-walled carbon nanotubes using an impregnation method.
A third aspect of the present invention provides a method for preparing dialkyl carbonate, the method comprising: under the decarbonylation reaction condition, contacting gas-phase dialkyl oxalate raw material with a catalyst, wherein the catalyst is the catalyst of the first aspect of the invention and/or the catalyst prepared by the method of the second aspect of the invention.
The catalyst can be simply and conveniently obtained under mild conditions, and in the reaction for preparing dialkyl carbonate from dialkyl oxalate, higher raw material conversion rate and product selectivity can be obtained, and the yield of dialkyl carbonate is obviously improved. In a preferred embodiment, the conversion of dimethyl oxalate in the reaction for the preparation of dimethyl carbonate from dimethyl oxalate reaches 99.9% and the selectivity of dimethyl carbonate reaches 96.3%.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst, which comprises a carrier and an alkali metal compound loaded on the carrier, wherein the carrier is a multi-wall carbon nano tube.
Herein, the "multi-walled carbon nanotube" may be understood as a carbon nanotube formed by rolling two or more layers of graphene sheets. "single-walled carbon nanotubes" are understood to be carbon nanotubes formed by the rolling of a single graphene sheet.
According to the invention, the specific surface area of the multi-walled carbon nanotube is preferably 200-1000m2G, preferably 200-700m2(ii)/g; more preferably 300-600m2/g。
In the present invention, the specific surface area is measured by the BET method.
According to the present invention, in order to further improve the activity and stability of the catalyst, it is preferred that the outer diameter of the multi-walled carbon nanotubes is 4 to 30nm, preferably 4 to 15 nm. In this context, "outer diameter" may be understood as the diameter of the outermost tube.
In order to further improve the activity and stability of the catalyst according to the present invention, it is preferable that the content of the support is 70 to 90 wt%, preferably 80 to 90 wt%, based on the total weight of the catalyst; the alkali metal compound is present in an amount of 10 to 30 wt%, and may be, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, or any one of the ranges consisting of any two of the foregoing values; preferably, the alkali metal compound is present in an amount of 10 to 20 wt%, more preferably 10 to 15 wt%.
According to the present invention, preferably, the alkali metal element in the alkali metal compound is selected from at least one of potassium, rubidium and cesium. The alkali metal compound is preferably an alkali metal salt such as at least one of a sulfate, a nitrate and a chloride.
Preferably, the alkali metal compound is at least one selected from the group consisting of potassium carbonate, potassium nitrate, potassium sulfate, potassium chloride, potassium hydroxide, potassium acetate, rubidium carbonate, rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium hydroxide, rubidium acetate, cesium carbonate, cesium nitrate, cesium sulfate, cesium chloride, cesium hydroxide, and cesium acetate; more preferably, the alkali metal compound is selected from potassium carbonate, potassium acetate, rubidium carbonate, rubidium acetate, cesium carbonate and cesium acetate.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the invention, the process comprising: the alkali metal compound is supported on the multi-walled carbon nanotubes using an impregnation method.
According to the invention, the specific surface area of the multi-walled carbon nanotube is preferably 200-1000m2G, preferably 200-700m2(ii)/g; more preferably 300-600m2/g。
According to the invention, the impregnation method may be an isovolumetric impregnation method or an excess impregnation method, preferably an isovolumetric impregnation method.
According to the method for preparing the catalyst, the alkali metal compound is preferably loaded on the multi-wall carbon nanotube by using an impregnation method and is dried; preferably, the drying conditions include: the temperature is 70-200 ℃, and the time is 6-48 h; more preferably at a temperature of 80-150 ℃ for 12-24 h.
In a preferred embodiment, an alkali metal compound is prepared into an impregnation solution, the carrier is placed in the impregnation solution to be mixed, and then the obtained mixture is dried at 70-200 ℃ to obtain the catalyst.
The solvent used for preparing the impregnation solution is not particularly limited in the present invention as long as it can achieve dispersion of the alkali metal compound and good loading at the same time, and may be, for example, water, methanol, ethanol, or a mixture thereof. In one embodiment, the solvent used to prepare the impregnation solution is water, and the multi-walled carbon nanotubes need to be activated with an acid, for example nitric acid.
The concentration of the alkali metal compound in the impregnation liquid is not particularly limited as long as a preferable loading can be achieved.
The catalyst of the invention does not need a roasting step, but can be obtained by directly drying after loading an alkali metal compound on a carrier.
A third aspect of the present invention provides a method for preparing dialkyl carbonate, the method comprising: under the decarbonylation reaction condition, contacting gas-phase dialkyl oxalate raw material with a catalyst, wherein the catalyst is the catalyst of the first aspect of the invention and/or the catalyst prepared by the method of the second aspect of the invention.
In theory, the catalyst of the present invention can be used to prepare any dialkyl carbonate. Preferably, the alkyl group in the dialkyl carbonate is an alkyl group having 1 to 6 carbon atoms, and more preferably, the dialkyl carbonate is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and dipentyl carbonate. In particular, when the catalyst is used for preparing dimethyl carbonate by decarbonylation of dimethyl oxalate, the catalyst of the invention can obtain obviously better catalytic effect, for example, the conversion rate of the dimethyl oxalate reaches 99.9 percent, and the selectivity of the dimethyl carbonate reaches 97.5 percent.
According to the method for preparing dialkyl carbonate of the present invention, preferably, the dialkyl oxalate raw material is dialkyl oxalate and/or a dialkyl oxalate solution.
Preferably, the solvent in the dialkyl oxalate solution is selected from at least one of methanol, ethanol, and dialkyl carbonate. Preferably, the dialkyl carbonate as solvent is the same species as the target product dialkyl carbonate.
In order to prevent a large amount of side reactions such as hydrolysis of the dialkyl oxalate from occurring while maintaining the stability of the catalyst, it is preferable that the content of water in the dialkyl oxalate raw material is not more than 1 wt%, more preferably not more than 0.3 wt%.
In a preferred embodiment, the dialkyl carbonate is dimethyl carbonate, and the dialkyl oxalate starting material is a methanol solution of dialkyl oxalate.
In a preferred embodiment, the dialkyl carbonate is dimethyl carbonate and the decarbonylation conditions comprise: the reaction temperature is 160-210 ℃, the pressure is 0-0.5MPa, and the space velocity is 0.05-2h-1(ii) a Preferably, the decarbonylation reaction conditions include: the reaction temperature is 160-190 ℃, the pressure is 0-0.2MPa, and the mass space velocity is 0.05-2h-1。
In this context, unless otherwise specified, the pressures are both gauge pressures.
To keep the production continuous and stable, the process for preparing dialkyl carbonate is preferably carried out in a fixed bed reactor.
For ease of transport and storage, the reaction product is preferably converted to a liquid state by condensation.
When the catalyst is used in the reaction for preparing dimethyl carbonate by decarbonylation of gaseous dimethyl oxalate, the reaction conditions required by the catalyst are mild, for example, the temperature is 160-; in addition, the catalyst of the invention has obviously improved conversion rate of dimethyl oxalate and obviously higher selectivity of dimethyl carbonate.
The present invention will be described in detail below by way of examples. The raw materials are all commercial products.
Example 1
Preparing catalyst by isovolumetric impregnation method, dissolving 1.5g potassium acetate in appropriate amount of ethanol to obtain impregnation solution, and adding 8.5g potassium acetate with specific surface area of 200m2Soaking the multi-wall carbon nano-tube (the outer diameter is 10-30 nm)/g in the soaking solution, and drying at 120 ℃ to obtain the catalyst A1.
Example 2
The process described with reference to example 1, except that a specific surface area of 1000m was used2Catalyst A2 was obtained as a multi-walled carbon nanotube (outer diameter 4-6 nm)/g.
Example 3
The process described with reference to example 1, except that a specific surface area of 300m was used2/gThe multi-walled carbon nanotube (outer diameter 8 to 15nm) of (2) was used to obtain catalyst A3.
Examples 4 to 12
Referring to the process described in example 1, the different set conditions are shown in Table 1, and the conditions not given in Table 1 are the same as in example 1 (the amounts of the raw materials are adjusted to match the contents of the metal components in the finally formed catalyst in examples 8 to 10), to finally obtain catalysts A4 to A12, respectively.
Comparative example 1
The process described in example 4 is referred to, except that single-walled carbon nanotubes (400 m specific surface area) are used2In terms of/g). Catalyst D1 was obtained as a result.
TABLE 1
Performance of the catalyst
Examples 13 to 31, comparative example 2
The catalysts A1-A12 and D1 prepared as described above were tested for their catalytic performance in accordance with the following methods.
The catalyst was placed in the middle of the tubular reactor, and the reaction temperature and reaction pressure shown in Table 2 were set, and nitrogen gas was introduced into the reactor at a rate of 100mL/min in order to promote the flow of the materials and prevent the influence of air. Introducing the dehydrated methanol solution with the dimethyl oxalate content of 20 wt% into a reactor at a certain mass airspeed, and gasifying the methanol solution to reach a catalyst bed layer. The product after the reaction was cooled and separated from the gas and liquid, and the analysis results are shown in table 2.
TABLE 2
TABLE 2
| Example 25 | A4 | 180 | 0.2 | 0.05％ | 0.5 | 97.8 | 95.8 |
| Example 26 | A4 | 180 | 0.5 | 0.05％ | 0.5 | 96.1 | 96.7 |
| Example 27 | A4 | 160 | 0 | 0.05％ | 0.5 | 86.3 | 97.1 |
| Example 28 | A4 | 200 | 0 | 0.05％ | 0.5 | 99.9 | 83.2 |
| Example 29 | A4 | 120(liquid) | 0 | 0.05％ | 0.5 | 0 | - |
| Example 30 | A4 | 180 | 0 | 1.2％ | 0.5 | 99.1 | 73.6 |
| Example 31 | A4 | 180 | 0 | 0.05％ | 2 | 79.2 | 97.3 |
| Comparative example 2 | D1 | 180 | 0 | 0.05％ | 0.5 | 68.5 | 70 |
As can be seen from the results in Table 2, the catalyst of the present invention can catalyze the gaseous dimethyl oxalate to react under mild conditions (e.g., temperature of 160-.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A catalyst comprises a carrier and an alkali metal compound loaded on the carrier, wherein the carrier is a multi-wall carbon nanotube.
2. The catalyst as claimed in claim 1, wherein the multi-walled carbon nanotube has a specific surface area of 200-1000m2G, preferably 300-600m2/g；
Preferably, the multi-walled carbon nanotubes have an outer diameter of 4 to 30 nm.
3. The catalyst according to claim 1 or 2, wherein the alkali metal compound is present in an amount of 10-30 wt.%, preferably 10-20 wt.%, and the support is present in an amount of 70-90 wt.%, preferably 80-90 wt.%, based on the total weight of the catalyst.
4. The catalyst according to claim 1 or 2, wherein the alkali metal element in the alkali metal compound is at least one selected from potassium, rubidium and cesium;
preferably, the alkali metal compound is at least one selected from the group consisting of potassium carbonate, potassium nitrate, potassium sulfate, potassium chloride, potassium hydroxide, potassium acetate, rubidium carbonate, rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium hydroxide, rubidium acetate, cesium carbonate, cesium nitrate, cesium sulfate, cesium chloride, cesium hydroxide, and cesium acetate;
more preferably, the alkali metal compound is selected from potassium carbonate, potassium acetate, rubidium carbonate, rubidium acetate, cesium carbonate and cesium acetate.
5. A method of preparing the catalyst of any one of claims 1-4, the method comprising: loading the alkali metal compound on the multi-walled carbon nanotubes using an impregnation method;
preferably, the specific surface area of the multi-walled carbon nanotube is 200-1000m2G, preferably 300-600m2/g。
6. A method of making a dialkyl carbonate, the method comprising: contacting a dialkyl oxalate feedstock in vapor phase with a catalyst under decarbonylation reaction conditions, wherein the catalyst is the catalyst of any one of claims 1 to 4 and/or the catalyst prepared by the method of claim 5.
7. The method of claim 6, wherein the dialkyl carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and dipentyl carbonate.
8. The method according to claim 6 or 7, wherein the dialkyl oxalate starting material is a dialkyl oxalate and/or a dialkyl oxalate solution;
preferably, the solvent in the dialkyl oxalate solution is selected from at least one of methanol, ethanol and dialkyl carbonate;
preferably, the water content of the dialkyl oxalate feed does not exceed 1 wt%.
9. The process according to any one of claims 6 to 8, wherein the dialkyl carbonate is dimethyl carbonate and the decarbonylation reaction conditions comprise: the reaction temperature is 160-210 ℃, the pressure is 0-0.5MPa, and the mass space velocity is 0.05-2h-1。
10. The process of claim 9, wherein the decarbonylation reaction is carried out in a fixed bed reactor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113956161A (en) * | 2021-11-22 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Method and system for continuously producing dimethyl carbonate |
| CN115779883A (en) * | 2022-12-13 | 2023-03-14 | 新疆至臻化工工程研究中心有限公司 | Catalyst for directionally synthesizing alkyl carbonate from alkyl oxalate |
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