A carbon dioxide absorbent and a method of preparing the same

Abstract

The application discloses a carbon dioxide absorbent and a preparation method thereof, and belongs to the technical field of adsorbents.The carbon dioxide absorbent takes a composite material as a carrier and takes a eutectic solvent as a load; raw materials of the composite material are graphene oxide and zirconium oxychloride; and raw materials of the eutectic solvent are 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid.The carbon dioxide absorbent prepared by using the method has high adsorption efficiency and high stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adsorbents, and particularly relates to a carbon dioxide adsorbent and a preparation method thereof. BACKGROUND

[0002] With the rapid development of human civilization technology, natural resources such as coal, oil, natural gas and other fossil fuels in the earth's crust are continuously exploited and utilized, resulting in a large amount of carbon dioxide being discharged into the atmosphere. As the main greenhouse gas at present, carbon dioxide is the main cause of a series of environmental problems such as sea level rise and glacier melting. In order to alleviate a series of problems caused by climate change on the environment, countries around the world have developed a series of carbon emission reduction measures, and one of the most effective measures is carbon dioxide capture. At present, the main carbon capture methods include absorption method, adsorption method and membrane separation method. Absorption separation is an important mass transfer process in chemical engineering technology, and is widely used in the separation of mixed gases. At present, absorption method is also used for decarburization in industry. There are mainly four kinds of solid adsorption materials applied in industry, including silica gel, activated carbon, active lead oxide and zeolite molecular sieve. Membrane separation technology is a newly emerging and rapidly developing carbon dioxide separation technology, which has the advantages of simple device, easy operation and low investment cost.

[0003] However, the existing method is not ideal for carbon dioxide capture, and the adsorption efficiency is low and the adsorption performance is unstable. Therefore, it is an urgent problem to be solved to provide a carbon dioxide adsorbent with high adsorption effect and strong stability. SUMMARY

[0004] In view of the problems existing in the prior art, the application provides a carbon dioxide adsorbent and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the application provides the following technical scheme:

[0006] Technical scheme one: a carbon dioxide adsorbent, wherein a composite material is used as a carrier, and a eutectic solvent is used as a load.

[0007] The raw material of the composite material is graphene oxide and zirconium oxychloride.

[0008] The raw material of the eutectic solvent is 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid.

[0009] Further, the mass ratio of the carrier to the load is 1:(8-10).

[0010] Further, the mass ratio of the graphene oxide to the zirconium oxychloride is 1:(0.03-0.08).

[0011] Further, the mass ratio of the 1-methyl-3-butane sulfonic acid imidazole to the p-toluene sulfonic acid is (2-5):1.

[0012] Technical solution two: the application also provides a preparation method of the carbon dioxide absorbent, comprising the following steps:

[0013] Mixing the graphene oxide dispersion liquid and the zirconium oxychloride solution, adjusting the pH to 9-12, and performing a hydrothermal reaction on the obtained mixture to obtain a composite material;

[0014] Mixing 1-methyl-3-butane sulfonic acid imidazole and p-toluenesulfonic acid, heating and stirring to obtain a eutectic solvent;

[0015] Adding the composite material into the eutectic solvent and performing ultrasonic treatment to obtain the carbon dioxide absorbent.

[0016] Further, the hydrothermal reaction temperature is 160-185 DEG C, and the time is 20-30 min.

[0017] Further, the heating and stirring temperature is 100-150 DEG C, the stirring speed is 450-600 rpm, and the time is 8-15 min.

[0018] Further, the ultrasonic treatment parameters are: power 200-350 W, and time 3-5 min.

[0019] Technical solution three: the application of the carbon dioxide absorbent in capturing carbon dioxide.

[0020] Compared with the prior art, the application has the following advantages and technical effects:

[0021] The application utilizes the layered structure of graphene oxide, composites the zirconium oxide with ion adsorption function with the same, obtains a composite as a carrier, simultaneously loads the high-activity eutectic solvent as an active center on the carrier, realizes further modification of the carrier, and obtains the carbon dioxide absorbent which can improve the adsorption efficiency of carbon dioxide.

[0022] The carrier material in the application can realize physical adsorption, and the carbon dioxide absorbent loaded with the eutectic solvent can realize chemical adsorption, and the effect of "double adsorption" is better.

[0023] The method provided by the application is simple and easy to operate, has high adsorption efficiency and strong stability. DETAILED DESCRIPTION

[0024] The various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the application.

[0025] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of a parameter, unless otherwise stated, the inclusion of either extremity of the range is to be understood as if both are stated. For example, "from 1 to 10" should be interpreted as meaning "from 1 to 10 as well as 1 to 10".

[0026] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe in full the methods and / or materials which are described herein. In case of conflict, the content of the present specification will control.

[0027] Many modifications and variations of the present application described in the specific embodiments of the application can be made by those skilled in the art without departing from the spirit or scope of the application. Other implementations of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application. The specification and examples given are exemplary only.

[0028] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean including, but not limited to.

[0029] The present application provides a preparation method of a carbon dioxide absorbent, comprising the following steps:

[0030] (1) mixing a graphene oxide dispersion solution and a zirconium oxychloride solution, adjusting the pH to 9-12, and performing a hydrothermal reaction on the obtained mixture to obtain a composite material;

[0031] (2) mixing 1-methyl-3-butane sulfonic acid imidazole and p-toluenesulfonic acid, and heating and stirring to obtain a deep eutectic solvent;

[0032] (3) adding the composite material into the deep eutectic solvent, and performing ultrasonic treatment to obtain a carbon dioxide absorbent.

[0033] In some preferred embodiments of the present application, in step (1), the mass ratio of graphene oxide and zirconium oxychloride is 1:(0.03-0.08). The hydrothermal reaction temperature is 160-185℃, and the time is 20-30 min.

[0034] In step (2) of some preferred embodiments of the present application, the mass ratio of the 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid is (2-5) : 1. The heating and stirring temperature is 100-150℃, the stirring speed is 450-600rpm, and the time is 8-15min.

[0035] In step (3) of some preferred embodiments of the present application, the mass ratio of the composite material and the eutectic solvent is 1:(8-10). The ultrasonic treatment parameters are: power 200-350W, time 3-5min.

[0036] In the present application, “room temperature” refers to 25±2℃ unless otherwise specified.

[0037] In the examples, if the specific experimental steps or conditions are not specified, the operation or conditions can be carried out according to the conventional experimental steps described in the literature in the art. If the reagents or instruments used are not specified by the manufacturer, they are conventional reagents that can be obtained by purchase.

[0038] The following examples are further illustrations of the technical solutions of the present application.

[0039] Example 1

[0040] A preparation method of a carbon dioxide absorbent, comprising the following steps:

[0041] (1) ultrasonically disperse 2g of graphene oxide in 20mL of deionized water to obtain a graphene oxide dispersion; dissolve zirconium oxychloride in 20mL of deionized water to obtain a zirconium oxychloride solution; mix the graphene oxide dispersion and the zirconium oxychloride solution (wherein the mass ratio of graphene oxide and zirconium oxychloride is 1:0.05), adjust the pH to 10, and obtain a mixture; the mixture is hydrothermally reacted at 170℃ for 25min, and after solid-liquid separation and drying, a composite material is obtained;

[0042] (2) mix 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid according to a mass ratio of 3:1, stir at 500rpm at 120℃ for 12min to obtain a eutectic solvent;

[0043] (3) mix the composite material and the eutectic solvent according to a mass ratio of 1:9, ultrasonically treat at 300W for 4min, and dry to obtain a carbon dioxide absorbent.

[0044] Example 2

[0045] A preparation method of a carbon dioxide absorbent, comprising the following steps:

[0046] (1) 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide to zirconium oxychloride was 1:0.03), the pH was adjusted to 12, and the obtained mixture was hydrothermally reacted at 160°C for 30 min to obtain a composite material;

[0047] (2) 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid were mixed at a mass ratio of 5:1, stirred at 150°C at a stirring speed of 450 rpm for 15 min to obtain a deep eutectic solvent;

[0048] (3) The composite material and the deep eutectic solvent were mixed at a mass ratio of 1:10, ultrasonically treated at 350 W for 3 min, and dried to obtain a carbon dioxide absorbent.

[0049] Example 3

[0050] A preparation method of a carbon dioxide absorbent, comprising the following steps:

[0051] (1) 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide to zirconium oxychloride was 1:0.08), the pH was adjusted to 9, and the obtained mixture was hydrothermally reacted at 185°C for 20 min to obtain a composite material;

[0052] (2) 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid were mixed at a mass ratio of 2:1, stirred at 120°C at a stirring speed of 500 rpm for 12 min to obtain a deep eutectic solvent;

[0053] (3) The composite material and the deep eutectic solvent were mixed at a mass ratio of 1:8, ultrasonically treated at 200 W for 5 min, and dried to obtain a carbon dioxide absorbent.

[0054] Comparative Example 1

[0055] A preparation method of a carbon dioxide absorbent, comprising the following steps:

[0056] 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide to zirconium oxychloride was 1:0.05), the pH was adjusted to 10, and the obtained mixture was hydrothermally reacted at 170°C for 25 min to obtain a composite material.

[0057] Comparative Example 2

[0058] The same as Example 1, except that the composite material in step (1) is replaced by graphene oxide, i.e., graphene oxide is used as a carrier. The specific steps are as follows:

[0059] (1) 1-methyl-3-butane sulfonic acid imidazole and p-toluenesulfonic acid are mixed according to a mass ratio of 3:1, stirred at 500 rpm at 120°C for 12 min to obtain a deep eutectic solvent;

[0060] (2) Graphene oxide and the deep eutectic solvent are mixed according to a mass ratio of 1:9, ultrasonically treated at 300 W for 4 min, and dried to obtain a carbon dioxide absorbent.

[0061] Comparative Example 3

[0062] The same as Example 1, except that the deep eutectic solvent is replaced, and the specific steps are as follows:

[0063] (1) 2 g of graphene oxide is ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride is dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution are mixed (wherein the mass ratio of graphene oxide and zirconium oxychloride is 1:0.05), the pH is adjusted to 10, and the obtained mixture is hydrothermally reacted at 170°C for 25 min. After solid-liquid separation and drying, a composite material is obtained;

[0064] (2) Choline chloride and N,N-dimethylethanolamine are mixed according to a molar ratio of 1:1, stirred at 500 rpm at 120°C for 12 min to obtain a deep eutectic solvent;

[0065] (3) The composite material and the deep eutectic solvent are mixed according to a mass ratio of 1:9, ultrasonically treated at 300 W for 4 min, and dried to obtain a carbon dioxide absorbent.

[0066] Comparative Example 4

[0067] The same as Example 1, except that in step (1), the composition ratio of the composite material is changed, and the specific steps are as follows:

[0068] (1) 2 g of graphene oxide is ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride is dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution are mixed (wherein the mass ratio of graphene oxide and zirconium oxychloride is 0.3:1), the pH is adjusted to 10, and the obtained mixture is hydrothermally reacted at 170°C for 25 min. After solid-liquid separation and drying, a composite material is obtained;

[0069] (2) 1-methyl-3-butanesulfonic acid imidazole and p-toluenesulfonic acid were mixed at a mass ratio of 3:1, stirred at 120°C at a stirring speed of 500 rpm for 12 min to obtain the deep eutectic solvent;

[0070] (3) The composite material was mixed with the deep eutectic solvent at a mass ratio of 1:9, ultrasonically treated at 300 W for 4 min, and dried to obtain the carbon dioxide absorbent.

[0071] Comparative Example 5

[0072] The same as Example 1, except that the composition ratio of the deep eutectic solvent was changed. The specific steps are as follows:

[0073] (1) 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide and zirconium oxychloride was 1:0.05), the pH was adjusted to 10, and the obtained mixture was hydrothermally reacted at 170°C for 25 min. After solid-liquid separation and drying, a composite material was obtained;

[0074] (2) 1-methyl-3-butanesulfonic acid imidazole and p-toluenesulfonic acid were mixed at a mass ratio of 8:1, stirred at 120°C at a stirring speed of 500 rpm for 12 min to obtain the deep eutectic solvent;

[0075] (3) The composite material was mixed with the deep eutectic solvent at a mass ratio of 1:9, ultrasonically treated at 300 W for 4 min, and dried to obtain the carbon dioxide absorbent.

[0076] Comparative Example 6

[0077] The same as Example 1, except that the composition ratio of the composite material and the deep eutectic solvent was changed. The specific steps are as follows:

[0078] (1) 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide and zirconium oxychloride was 1:0.05), the pH was adjusted to 10, and the obtained mixture was hydrothermally reacted at 170°C for 25 min. After solid-liquid separation and drying, a composite material was obtained;

[0079] (2) 1-methyl-3-butanesulfonic acid imidazole and p-toluenesulfonic acid were mixed at a mass ratio of 3:1, stirred at 120°C at a stirring speed of 500 rpm for 12 min to obtain the deep eutectic solvent;

[0080] (3) The composite material and the deep eutectic solvent were mixed at a mass ratio of 1:9, ultrasonic treatment was carried out at 300 W for 4 min, and drying was performed to obtain the carbon dioxide absorbent.

[0081] Comparative Example 7

[0082] The same as Example 1, except that the composition of the deep eutectic solvent was changed. The specific steps are as follows:

[0083] (1) 2 g of graphene oxide was ultrasonically dispersed in 20 mL of deionized water to obtain a graphene oxide dispersion; zirconium oxychloride was dissolved in 20 mL of deionized water to obtain a zirconium oxychloride solution; the graphene oxide dispersion and the zirconium oxychloride solution were mixed (wherein the mass ratio of graphene oxide and zirconium oxychloride was 1:0.05), the pH was adjusted to 10, and the obtained mixture was hydrothermally reacted at 170°C for 25 min. After solid-liquid separation and drying, a composite material was obtained;

[0084] (2) 1-butyl-2,3-dimethylimidazole and p-toluenesulfonic acid were mixed at a mass ratio of 3:1, stirred at 500 rpm for 12 min at 120°C to obtain a deep eutectic solvent;

[0085] (3) The composite material and the deep eutectic solvent were mixed at a mass ratio of 1:9, ultrasonic treatment was carried out at 300 W for 4 min, and drying was performed to obtain the carbon dioxide absorbent.

[0086] Performance test

[0087] The carbon dioxide absorbents prepared in Examples 1-3 and Comparative Examples 1-7 were tested for performance. The test method included the following steps: 20 mg of the carbon dioxide absorbent supported by quartz wool was placed in the constant temperature heating zone of a fixed bed reactor, CO2(50 mL / min) gas was introduced to adsorb it under room temperature conditions, and an online gas analyzer was used for testing. After the carbon dioxide absorbent was saturated (the adsorption time was 30 min), the carbon dioxide adsorption amount was calculated. The carbon dioxide absorbent after saturation was calcined at 800°C for 0.5-0.75 h, and then reused. The saturated adsorption amount of the first use and the saturated adsorption amount after 10 times of reuse were recorded. The test results are shown in Table 1.

[0088] Table 1 Experimental data of different carbon dioxide absorbents

[0089]

[0090] As can be seen from Table 1, the carbon dioxide absorbent prepared by the method of the embodiment of the present application has high carbon dioxide adsorption efficiency and strong stability. The carbon dioxide absorbent prepared by Comparative Example 1 has no eutectic solvent loaded, and as can be seen from Table 1, the adsorption effect of the carbon dioxide absorbent prepared by Comparative Example 1 is significantly lower than that of Example 1, and the saturated adsorption amount after ten repetitions also has a large decrease. It can be seen that the loading of the eutectic solvent is crucial for improving the adsorption effect. In Comparative Example 2, the composite material is replaced by graphene oxide, and as can be seen from Table 1, although the adsorption effect of the absorbent of Comparative Example 2 on carbon dioxide is improved compared with Comparative Example 1, it is still not satisfactory compared with Example 1. This shows that the composite material carrier is better than the single graphene oxide carrier for carbon dioxide adsorption effect, which may be due to the participation of zirconium oxychloride increasing the adsorption sites of the composite material carrier. Comparative Examples 3 and 7 change the type of eutectic solvent, and as can be seen from Table 1, the combination of choline chloride and N,N-dimethylethanolamine is slightly worse than the combination of 1-methyl-3-butane sulfonic acid imidazole and p-toluenesulfonic acid; Comparative Example 4 changes the composition ratio of the composite material compared with Example 1, and the adsorption effect of the prepared carbon dioxide absorbent is lower than that of Example 1, which shows that the composition ratio of graphene oxide and zirconium oxychloride must be within a suitable range, and too large or too small is not conducive to the improvement of the adsorption effect; Comparative Example 5 changes the composition ratio of the eutectic solvent compared with Example 1, and as can be seen from Table 1, the adsorption effect of carbon dioxide decreases obviously, which shows that the composition ratio of the eutectic solvent is important for improving the adsorption effect; Comparative Example 6 increases the loading amount of the eutectic solvent compared with Example 1, and although the first adsorption effect decreases not obviously, the saturated adsorption amount has a large decrease after ten repetitions, which shows that the loading amount of the eutectic solvent is too large, which may cause desorption during repeated use.

[0091] The above merely provides the preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any changes or replacements easily thought of by those skilled in the art within the technical range disclosed by the present application should be covered in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A carbon dioxide absorbent, characterized by, The composite material is used as a carrier, and the low eutectic solvent is used as a load; The raw material of the composite material is graphene oxide and zirconium oxychloride; The raw material of the low eutectic solvent is 1-methyl-3-butane sulfonic acid imidazole and p-toluene sulfonic acid; The mass ratio of the carrier to the load is 1: (8-10); The mass ratio of the graphene oxide to the zirconium oxychloride is 1: (0.03-0.08); The mass ratio of the 1-methyl-3-butane sulfonic acid imidazole to the p-toluene sulfonic acid is (2-5):

1.

2. A method for producing the carbon dioxide absorbent according to claim 1, characterized by, The method comprises the following steps: The graphene oxide dispersion liquid and the zirconium oxychloride solution are mixed, the pH is adjusted to 9-12, the obtained mixture is subjected to a hydrothermal reaction, and a composite material is obtained; The 1-methyl-3-butane sulfonic acid imidazole and the p-toluene sulfonic acid are mixed, heated and stirred, and a low eutectic solvent is obtained; The composite material is added into the low eutectic solvent, ultrasonic treatment is performed, and drying is performed, and a carbon dioxide absorbent is obtained.

3. The method of claim 2, wherein the carbon dioxide absorbent is prepared by the steps of: The temperature of the hydrothermal reaction is 160-185℃, and the time is 20-30 min.

4. The method of claim 2, wherein the carbon dioxide absorbent is prepared by the steps of: The temperature of the heating and stirring is 100-150℃, the stirring speed is 450-600 rpm, and the time is 8-15 min.

5. The method of claim 2, wherein the carbon dioxide absorbent is prepared by the steps of: The ultrasonic treatment parameters are as follows: power 200-350 W, and time 3-5 min.

6. The carbon dioxide absorbent according to claim 1 is applied to capture carbon dioxide.

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