Process for preparing a catalyst from metal-organic framework material for use in a catalytic synthesis of cyclic carbonates

Abstract

A process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to the present invention provides the catalyst which comprises a metal-organic framework material and an amino group-containing ionic liquid as components, whereby the metal-organic framework material can be prepared from a sulfonic acid, a metal compound, and an inorganic acid, and the amino group-containing ionic liquid, which can be prepared from a heterocyclic compound and a halogen group-containing amine compound. The amino group-containing ionic liquid is then structurally linked to the metal-organic framework material. The catalyst according to the present invention is applied to catalyse the synthesis of cyclic carbonates from carbon dioxide. It can also help reduce the global warming problem by converting greenhouse gas like carbon dioxide into commercially high-value products.

Description

[0001] PROCESS FOR PREPARING A CATALYST FROM METAL-ORGANIC FRAMEWORK MATERIAL FOR USE IN A CATALYTIC SYNTHESIS OF CYCLIC CARBONATES

[0002] TECHNICAL FIELD

[0003] Chemistry related to a process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates.

[0004] BACKGROUND OF THE INVENTION

[0005] At present, global warming is a critical problem that affects the living of humans across the world, which is caused by the emission of greenhouse gas arising from human activities e.g., transportation, industrial factories, solid waste, or deforestation. Greenhouse gas, that is a critical problem, is carbon dioxide. Thus, to reduce the amount of such carbon dioxide from human activities, a variety of methods have been invented to help reduce carbon dioxide gas emission into the atmosphere e.g., using renewal energy, travelling with low-carbon vehicles, converting carbon dioxide to other commercially valuable products, e g., methanol, carbon nanotubes, etc. Moreover, there are inventions that mention the synthesis of cyclic carbonate compound using carbon dioxide gas as a precursor to reduce the amount of carbon dioxide emission into the atmosphere, and to add commercial value to carbon dioxide as cyclic carbonate which is a chemical that can be utilized in various industries.

[0006] Cyclic carbonate is an important precursor that can be utilized in various industries, e.g., using as a precursor in the production of polycarbonate plastic which is a strong, robust and translucent material used for making CDs, eyeglasses, or safety glasses, used as electrolyte in a lithium battery which is a high efficiency, long-lasting and light weight battery, and used in electronic devices, e.g., mobile phones, laptops, or electric vehicles; or using as a precursor in the production of dimethyl carbonate which is an additive in the production process of fuel oil to improve the quality of fuel for a better combustion efficacy, a reduction of corrosion in an engine, and a reduction of pollution from combustion, etc.

[0007] It is well-known that the synthesis of cyclic carbonates generally can be prepared from a reaction between an epoxide and carbon dioxide using a catalyst via a cycloaddition reaction. The examples of epoxide used in the synthesis of cyclic carbonates are ethylene oxide, propylene oxide, and styrene oxide, which the synthesized cyclic carbonates will be consistent with epoxides, e.g., ethylene carbonate, propylene carbonate or styrene carbonate, etc. The catalyst commonly used in the synthesis of cyclic carbonates usually are nanoparticles on an acidic or basic support which will help increase the synthesis efficacy Moreover, the used catalyst can also be isolated from the obtained product and reused. Example of catalyst used in the synthesis of cyclic carbonates are copper nanoparticles on titanosilicate support or magnesium nanoparticles on alkaline support.

[0008] From the study of prior arts, it was found that there are patent inventions that disclose the process of synthesizing catalysts from metal-organic framework materials for use in the catalytic synthesis of cyclic carbonates as in examples according to the following inventions.

[0009] CN 111514939 A discloses a catalyst synthesis method that mixes an ionic liquid which contains diamino function with a metal-organic framework material, MIL-101 (Cr), and takes such catalyst to synthesize cyclic carbonates using carbon dioxide and epichlorohydrin compound as precursors.

[0010] CN 116586113 A discloses a preparation of bifunctional heterogenous catalyst by linking an ionic liquid to a metal-organic framework material using ZIF-8 through a solid-phase synthesis process for preparing an IL-MOF composite material to catalyze the cycloaddition reaction of carbon dioxide gas and epoxide for synthesizing cyclic carbonates.

[0011] Moreover, there are inventions that disclose the process of synthesizing cyclic carbonates with the catalyst from the metal-organic framework materials as in examples according to the following inventions.

[0012] CN 105481821 B discloses the method of synthesizing the cyclic carbonate compound through metal-organic framework material using carbon dioxide gas and epoxide compound as precursors in which the metal-organic framework material used is metal-organic framework material, MIL-101 where the ionic liquid containing amine as a functional group was attached into the material structure.

[0013] US 8697884 B2 discloses the process in synthesizing the cyclic carbonate compound using carbon dioxide gas together with epoxide compound, as precursors under the ionic liquid polymer catalyst containing amine as a functional group, in catalyzing the synthesis of cyclic carbonate.

[0014] From the above-disclosed patent documents related to the synthesis of catalyst from the metal-organic framework materials for use in a catalytic synthesis of cyclic carbonates, it can be clearly seen that there is no invention or prior art that mentions the use of catalyst that uses the sulfonic acid-containing metal-organic framework materials to synthesize cyclic carbonates. Such use of sulfonic acid is deemed as the important element to increase the efficacy of cyclic carbonate synthesis. Thus, the process for preparing a catalyst from the metal-organic framework materials for use in a catalytic synthesis of cyclic carbonates has been developed using the metal-organic framework material and the amino group-containing ionic liquid, whereby the metal-organic framework material can be prepared from a sulfonic acid, a metal compound, and an inorganic acid, and the amino group-containing ionic liquid can be prepared from the heterocyclic compound and the halogen group-containing amine compound.

[0015] SUMMARY OF THE INVENTION

[0016] The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to the present invention, provides the catalyst which comprises the metal-organic framework material and the amino group-containing ionic liquid. The metal-organic framework material can be prepared from a sulfonic acid, a metal compound, and an inorganic acid. The amino group-containing ionic liquid can be prepared from a heterocyclic compound and a halogen group-containing amine compound. The amino group- containing ionic liquid is then structurally linked to the metal-organic framework material.

[0017] An objective of the present invention is to synthesize the catalyst from the metal-organic framework material, wherein this catalyst can be recycled without losing the initial efficacy while maintaining the high efficacy of cyclic carbonate synthesis. The catalyst according to the present invention is used to catalyze the synthesis of cyclic carbonate from carbon dioxide gas which helps reduce the global warming problem by converting greenhouse gas like carbon dioxide into a commercially high-value agent e.g., cyclic carbonate which is useful in various industries

[0018] DETAILED DESCRIPTION

[0019] The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates is described according to the aspects of the invention as follows.

[0020] Any aspect shown herein shall encompass the application to other aspects of the present invention as well, unless otherwise specified.

[0021] The technical terms or scientific terms used herein have the same definition as understood by a person of ordinary skill in the art, unless otherwise specified. Any tools, devices, methods, or chemicals mentioned herein shall mean tools, devices, methods, or chemicals that are commonly practiced or used by a person of ordinary skill in the art, unless it is expressly specified that the tools, devices, methods, or chemicals are special or specific to the present invention.

[0022] The following shows a detailed description without aiming to limit the scope of the invention in any way.

[0023] The present invention relates to the process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates, the process comprising the following steps: a) preparing the catalyst from the metal-organic framework material by adding a sulfonic acid, a metal compound, and an inorganic acid at a temperature of 100-220°C under a pressure of 1-50 bars for 0.5-24 hours, then heating at a temperature of 150-220°C for 4-9 days, harvesting a product by centrifugation; b) preparing the catalyst from the metal-organic framework material by dissolving the product from step a) in an inorganic acid and drying it overnight at a temperature of 100-150°C in a vacuum condition; c) preparing the amino group-containing ionic liquid by adding a heterocyclic compound, a halogen group-containing amine compound, and an alcohol solution, causing a reaction by heating at a temperature of 50-100°C for 8-15 hours, and adjusting a pH to be in the range of 6.0-8.0; d) preparing the amino group-containing ionic liquid by centrifuging the prepared agent from step c), evaporating a resulting product, and washing with an ether compound; and e) linking an ionic liquid structure to a catalyst structure by adding the catalyst from step b) and adding the ionic liquid from step d), mixing at a temperature of 20-60°C for 1-10 hours, centrifuging and washing with an alcohol solution, drying at a temperature of 50-100°C for 8-24 hours.

[0024] According to another exemplary aspect, the sulfonic acid is selected from benzenesulfonic acid, methanesulfonic acid, toluenesulfonic acid, aminomethanesulfonic acid, laurylbenzenesulfonic acid, dioctylsulfonic acid, monosodium 2-sulfoterephthalic acid, or a mixture thereof. In another exemplary aspect of the invention, the sulfonic acid is preferably monosodium 2-sulfoterephthalic acid

[0025] According to an example in another aspect, the metal compound is selected from chromium metal compound, aluminium metal compound, or a mixture thereof.

[0026] In another exemplary aspect, the metal compound is preferably the chromium compound.

[0027] An example in another aspect, the chromium compound can be selected from chromiumtrichloride or chromiumtrioxide.

[0028] In another aspect, the chromium compound is preferably chromiumtrioxide.

[0029] For another exemplary aspect of the invention, the inorganic acid is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, chloric acid, or a mixture thereof.

[0030] An example in another aspect of the invention, the inorganic acid is preferably hydrochloric acid.

[0031] In another aspect, step c) provides the pH adjustment of solution to the pH value in the range of 6.0-8.0 with a basic solution that can be selected from metal hydroxide compound, preferably potassium hydroxide.

[0032] An example in another aspect of the invention, the heterocyclic compound is selected from pyrimidine compound, imidazole compound, pyrazole compound, or a mixture thereof, wherein the heterocyclic compound is preferably imidazole compound.

[0033] According to another exemplary aspect of the invention, the imidazole compound is selected from methylimidazole, phenylimidazole, bisimidazole, bis(triphenylphosphine) imidazole, or a mixture thereof.

[0034] An example in another aspect of the invention, wherein imidazole compound is preferably methylimidazole

[0035] In another aspect of the invention, the halogen group-containing amine compound is selected from fluoroamine, chloramine, bromoamine, iodoamine, or a mixture thereof.

[0036] Another example, the halogen group-containing amine compound is preferably bromoamine compound.

[0037] In another examples, the bromoamine compound may be selected from monobromoamine, dibromoamine, bromochloroamine, bromoethylamine, or

[0038] 2 -bromoethylamine hydrobromide. An example in another aspect of the invention, the bromoamine compound is preferably 2 -bromoethylamine hydrobromide.

[0039] An example in another aspect of the invention, the alcohol solution is selected from alcohols having 1 to 4 carbon atoms, or a mixture thereof.

[0040] In another aspect, the alcohol solution is preferably ethanol solution.

[0041] An example in another aspect of the invention, the ether compound is diethyl ether.

[0042] The following will describe the invention in more details by referring to the experimental example. However, these examples are not intended to limit the scope of the present invention in any way.

[0043] Example 1 - Preparation of the catalyst from the recyclable metal-organic framework material for the synthesis of cyclic carbonates

[0044] The preparation of the catalyst from the recyclable metal-organic framework material comprises the preparation of monosodium 2-sulfoterephthalic acid, chromium compound, and inorganic acid, with the following steps: a. preparing 10.00-25.00% w / v monosodium 2-sulfoterephthalic acid, 2.50-5.00% w / v chromiumtrioxide, and 0.50-2.00% w / v hydrochloric acid, and mixing them in an autoclave; b. adding distilled water into the ingredient and heating for 4-9 days at a temperature of 150-220°C in an oven; c. harvesting the product by centrifugation at 5,000-8,000 rpm for 5-15 mins and washing with dimethylformamide and methanol three times, then drying at a room temperature; d. reacting the resulting product in 0.01-0.20 M hydrochloric acid solution dissolved in methanol; and e. drying the resulting product from step d. overnight at a temperature of 100-150°C under a vacuum condition.

[0045] Example 2 - Preparation of the amino group-containing ionic liquid for the synthesis of cyclic carbonates

[0046] The preparation of the amino group-containing ionic liquid comprises the preparation of the halogen group-containing amine compound with the following steps: a. preparing 5.00-20.00% w / v 1 -methylimidazole and 2.50-30.00% w / v 2-bromoethylamine hydrobromide and mixing them in ethanol solution; b. heating the mixed solution at a temperature of 50-120°C for 8-20 hours; c. adding 0.05-0.25 mol of potassium hydroxide to obtain a neutral suspension; d. centrifuging the resulting mixture at 5,000-8,000 rpm for 5-15 mins, then evaporating it to isolate imidazolium bromide from potassium bromide; and e. washing the resulting product from step d. with diethyl ether.

[0047] Example 3 - Linkage of the ionic liquid structure to the catalyst structure from the recyclable metal-organic framework material

[0048] This step comprises the preparation of the metal-organic framework material and ionic liquid with the following steps: a. preparing 2.00-8.00% w / v metal-organic framework material and preparing 1.00-3.00% w / v ionic liquid, and mixing them in distilled water; b. stirring the mixed solution for 1-10 hours at a temperature of 20-60 °C; c. harvesting the product by centrifuging at 5,000-8,000 rpm for 5-15 mins, then washing with ethanol solution 3 times; and d. drying the resulting product at a temperature of 50-100°C for 8-24 hours.

[0049] Example 4 - The experimental result of cyclic carbonate synthetic ability of the catalyst by the co-catalyst

[0050] Table 1

[0051]

[0052] From the experimental result, it was found that, under the same conditions with carbon dioxide pressure of 20 bars at the temperature of 60°C for 6 hours, the cyclic carbonates could not be synthesized in the condition where there is only the catalyst and no co-catalyst, while in the conditions with the catalyst and co-catalysts - tetrabutyl ammonium bromide and ionic liquid - the cyclic carbonates could be synthesized with 41.86% and 48.19% yields, respectively.

[0053] It was found that using the ionic liquid as a co-catalyst yielded cyclic carbonates more than when using tetrabutyl ammonium bromide as a co-catalyst. Moreover, the ionic liquid can also be easily attached to the catalyst at a room temperature. Thus, the ionic liquid is a preferred option for use as the co-catalyst in attachment to the catalyst for the synthesis of cyclic carbonates.

[0054] Example 6 - The experimental result of cyclic carbonate synthetic ability of the catalyst with different amounts of ionic liquid attached to its surface

[0055] Table 2

[0056]

[0057]

[0058] From the experimental results, it was found that, under the same conditions with the carbon dioxide pressure of 20 bars at the temperature of 90°C for 24 hours and with centrifugation as a product harvesting method, the catalyst with 0.2%, 0.4% and 0.6% ionic liquid attached to its surface could synthesize cyclic carbonates with 53.91%, 75.25% and 59.84% yields, respectively, whereas the catalyst with 1% ionic liquid attached to its surface could not synthesize cyclic carbonates since the catalyst was too concentrated. The catalyst with 0.4% ionic liquid attached to its surface was the concentration that can synthesize the largest amount of cyclic carbonate.

[0059] Example 7 - The experimental result of the catalyst recyclability

[0060] Table 3

[0061]

[0062] From the experimental result, it was found that, under the same conditions with the carbon dioxide gas pressure of 20 bars at the temperature of 90°C for 24 hours and with centrifugation as a product harvesting method, the fresh catalyst can synthesize cyclic carbonates with 53.69% yield. And when the 1sttime-recycled catalyst was taken together with the fresh catalyst according to Sample 2 compared to the 1sttime-recycled catalyst alone according to Sample 3, it was found that the cyclic carbonate synthetic ability gives 49.49% and 54.33% yields, respectively. Thus, it can be concluded that the catalyst according to the present invention can be recycled and still maintain good efficacy in the synthesis of cyclic carbonates.

[0063] Any improvement or alteration to the present invention may be clearly understood and can be made by a person of ordinary skill in the art, and the same may fall within the scope and spirit of the present invention as appear in the attached claims.

[0064] BEST MODE OF THE INVENTION

[0065] Best mode of the invention is as described in the detailed description of the invention.

Claims

WHAT IS CLAIMED IS:

1. A process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates, the process comprising the steps of: a) preparing the catalyst from the metal-organic framework material by adding a sulfonic acid, a metal compound, and an inorganic acid at a temperature of 100-220°C under a pressure of 1-50 bars for 0.5-24 hours, then heating at a temperature of 150-220°C for 4-9 days, harvesting a product by centrifugation; b) preparing the catalyst from the metal-organic framework material by dissolving the product from step a) in an inorganic acid and drying it overnight at a temperature of 100-150°C in a vacuum condition; c) preparing an amino group-containing ionic liquid by adding a heterocyclic compound, a halogen group-containing amine compound, and an alcohol solution, causing a reaction by heating at a temperature of 50-100°C for 8-15 hours, and adjusting a pH to be in a range of 6.0-8.0; d) preparing the amino group-containing ionic liquid by centrifuging the prepared agent from step c), evaporating a resulting product, and washing with an ether compound; and e) linking an ionic liquid structure to a catalyst structure by adding the catalyst from step b) and adding the ionic liquid from step d), mixing at a temperature of 20-60°C for 1-10 hours, centrifuging and washing with an alcohol solution, drying at a temperature of 50-100°C for 8-24 hours.

2. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the sulfonic acid is selected from benzenesulfonic acid, methanesulfonic acid, toluenesulfonic acid, aminomethanesulfonic acid, laurylbenzenesulfonic acid, dioctylsulfonic acid, monosodium 2- sulfoterephthalic acid, or a mixture thereof.

3. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the metal compound is selected from chromium metal compound, aluminium metal compound, or a mixture thereof.

4. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the inorganic acidis selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, chloric acid, or a mixture thereof.

5. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the heterocyclic compound is selected from pyrimidine compound, imidazole compound, pyrazole compound, or a mixture thereof.

6. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the heterocyclic compound is imidazole compound.

7. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the halogen group-containing amine compound is selected from fluoroamine, chloroamine, bromoamine, iodoamine, or a mixture thereof.

8. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the halogen group-containing amine compound is bromoamine compound.

9. The process for preparing a catalyst from a metal-organic framework material for use in a catalytic synthesis of cyclic carbonates according to claim 1, wherein the alcohol solution is selected from alcohols having 1 to 4 carbon atoms, or a mixture thereof.

10. A catalyst from a recyclable metal-organic framework material prepared by the process according to any one of claims 1 to 9.

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