Method for preparing methane by reforming small molecular alcohol through high-energy electron beam irradiation

Abstract

The invention discloses a method for preparing methane by reforming small molecular alcohol through high-energy electron beam irradiation, and belongs to the technical field of environmental catalysis. According to the method, methane is prepared by reforming small molecular alcohol through high-energy electron beam irradiation. Compared with a traditional biological method, high-energy electron beam irradiation is adopted, substances are irradiated by electron rays accelerated in a high-voltage electric field, molecules of various substances are ionized and excited through interaction of high-energy electrons and the substances, and therefore chemical reactions are initiated. The method disclosed by the invention has a better irradiation methane preparation effect, and the problems of long reaction period (15-30 days), high energy consumption of a preparation process, large carbon emission and the like in the prior art are solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental catalysis, and particularly relates to a method for preparing methane by reforming small molecule alcohols by high-energy electron beam irradiation. Background Art

[0002] The rapid development of industrialization and urbanization and the continuous growth of the population have become the key factors leading to the energy crisis and serious environmental pollution. In order to meet the rising energy demand, the mining activities of fossil fuels are becoming increasingly frequent, which not only causes many environmental problems such as greenhouse gas emissions, but also exacerbates the trend of global warming. Clean and sustainable energy is regarded as the most effective resource to solve the current global energy crisis and environmental problems. Therefore, the development of clean and sustainable energy is the top priority of modern research. Among many strategies, methane (CH4), as a clean energy with high calorific value and low pollution, only generates carbon dioxide and water after combustion, and the particulate matter emission is almost zero, which is an important carrier for realizing energy decarbonization. With the acceleration of the global energy transition, producing methane through green technologies and replacing traditional fossil fuels such as coal and oil has become the key path to reduce greenhouse gas emissions and build a circular economy.

[0003] At present, most of the methods for producing methane mainly use anaerobic digestion as the core technology, using microorganisms to decompose organic matter (such as agricultural waste, food waste, etc.) under anaerobic conditions, and generating biogas (methane content 50% - 70%) through four stages: hydrolysis, acidification, acetic acid production, and methane production. This technology has the advantages of waste resource utilization and low carbon emissions, but there are problems such as long reaction cycle (15 - 30 days) and low methane purity. In addition, landfill gas recovery collects methane (accounting for 40% - 60%) generated by the natural fermentation of organic waste in landfills, which has both emission reduction and energy recovery benefits, but is limited by collection efficiency and site conditions. There is also the use of thermochemical methods to produce methane. Coal or biomass is gasified to generate syngas (CO + H2), and then through catalytic methanation reactions such as nickel-based catalysts (CO + 3H2 → CH4 + H2O), high-purity synthetic natural gas (SNG, CH4 > 95%) is produced. This type of method is technically mature but has high carbon emissions and relies on fossil energy. Natural gas extraction: directly extract methane (purity 70% - 95%) from natural gas fields, and use it after dehydration, desulfurization, etc. The cost is low but there is a risk of methane leakage (strong greenhouse effect); steam reforming of hydrocarbons: generate syngas by high-temperature reforming of natural gas or light hydrocarbons, and then recover methane by methanation, with high energy consumption and large carbon emissions. Summary of the Invention

[0004] In view of the above technical problems, the present invention provides a method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation. Compared with the traditional photocatalytic methane production and biological methane production, the present invention has better methane production effect by irradiation to overcome the deficiencies in the above-mentioned prior art. And compared with the traditional biological method, the present invention uses high-energy electron beam irradiation, which is to irradiate substances with electron rays accelerated in a high-voltage electric field, and ionize and excite molecules of various substances through the interaction between high-energy electrons and substances, thereby triggering chemical reactions.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention:

[0007] A method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation, comprising the following steps:

[0008] Irradiate the alcohol solution with a high-energy electron beam to prepare methane.

[0009] Beneficial effects: The present invention irradiates the solution with electron rays accelerated in a high-voltage electric field, ionizes and excites molecules of various substances through the interaction between high-energy electrons and substances, and utilizes the interaction between electrons and substances. Among them, electrons act on the small molecule alcohol solution to generate ionization or excitation, release orbital electrons, form free radicals and change the original molecular structure. Free radicals or other activated groups can form new molecular forms, that is, while breaking chemical bonds, new chemical reactions are accompanied, such as organic matter decomposition or atomic dislocation. Therefore, the present invention uses high-energy electron beam irradiation to treat the solution, makes high-energy electrons react with molecules and atoms in the solution, and then generates methane efficiently through the interaction between the high-energy electron beam and the solution.

[0010] Optionally, the alcohol in the alcohol solution is a small molecule alcohol;

[0011] The power of the high-energy electron beam is 0 - 20 kW, where the power is not 0; preferably 20 kW.

[0012] Further, the small molecule alcohol includes at least one of methanol, ethanol, n-propanol or isopropanol.

[0013] Furthermore, the small molecule alcohol is isopropanol.

[0014] Further, the content of alcohol in the alcohol solution is 1 - 3 vol.%. Preferably 3 vol.%.

[0015] Optionally, the conditions in the irradiation treatment process are: irradiate to 120 KGy in the form of 0 - 15 KGy / round, where the irradiation form is not 0; preferably 15 KGy / round.

[0016] Furthermore, the irradiation rate during the irradiation process is 0 - 18 KGy / s, where the irradiation rate is not 0; preferably it is 18 KGy / s.

[0017] Beneficial effects: The present invention defines the parameter conditions during the irradiation treatment, such as 15 K / round, and the irradiation rate of 18 KGy / s. This is because a higher irradiation power dose will cause the reaction vessel bottle body to rupture; too low a dose will result in a slower reaction rate. Therefore, under the irradiation parameter conditions defined in the present invention, both the reaction rate can be ensured and the continuous progress of the reaction can be guaranteed.

[0018] Furthermore, the irradiation treatment process is carried out at room temperature and normal pressure.

[0019] Optionally, the method for preparing methane by irradiating and reforming small molecule alcohols with high-energy electron beams includes the following steps:

[0020] Irradiate an aqueous solution of 3 vol.% isopropanol with high-energy electron beams in the form of 15 KGy / round until 120 KGy to prepare methane.

[0021] Furthermore, the concentration of the methane is 885.2 mmol / L.

[0022] The second technical solution of the present invention:

[0023] The application of the above method for preparing methane by irradiating and reforming small molecule alcohols with high-energy electron beams in the field of methane preparation.

[0024] Compared with the prior art, the present invention has the following advantages and technical effects:

[0025] 1) The present invention uses high-energy electron beam irradiation to reform small molecule alcohol solutions to produce CH4, which has the advantages of relatively simple operation, low cost, and can be implemented in large quantities, etc.;

[0026] 2) The present invention uses high-energy electron beam irradiation to reform small molecule alcohol solutions to produce CH4, showing excellent CH4 production efficiency. And during the preparation process of the present invention, the yield of small molecule alcohols reduced to CH4 increases with the increase of the irradiation dose, and the purity of methane also increases with the progress of the reaction until the small molecule alcohols are completely consumed. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0028] Figure 1 It is the effect diagram of methane production by the aqueous solution EB-IPA-1 of 1% concentration isopropanol prepared in Example 1 under electron beam irradiation;

[0029] Figure 2 It is the effect diagram of methane production by the aqueous solution EB-IPA-2 with a concentration of 2% isopropyl alcohol prepared in Example 2 under electron beam irradiation;

[0030] Figure 3 It is the effect diagram of methane production by the aqueous solution EB-IPA-3 with a concentration of 3% isopropyl alcohol prepared in Example 3 under electron beam irradiation;

[0031] Figure 4 It is the effect diagram of methane production by the aqueous solution EB-H2O prepared in Comparative Example 1 under electron beam irradiation;

[0032] Figure 5 It is the comparative diagram of methane production effects of EB-IPA-1, EB-IPA-2, EB-IPA-3 prepared in Examples 1-3 and the aqueous solution EB-H2O prepared in Comparative Example 1 under 120 KGy electron beam irradiation;

[0033] Figure 6 It is the comparative diagram of methane production effects of isopropyl alcohol EB-IPA prepared in Example 1 and EB-H2O, EB-MeOH, EB-EtOH prepared in Comparative Example 1 and Examples 4 and 5 under 120 KGy electron beam irradiation. Detailed implementation manners

[0034] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0035] It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0036] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0037] Without departing from the scope or spirit of the present invention, various modifications and variations can be made to the specific embodiments of the description of the present invention, which will be obvious to those skilled in the art. Other embodiments obtained from the description of the present invention will be obvious to those skilled in the art. The description and examples of the present invention are merely exemplary.

[0038] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0039] An embodiment of the present invention discloses a method for reforming small molecule alcohols into methane by high-energy electron beam irradiation, specifically as follows:

[0040] Irradiate the small molecule alcohol solution with a high-energy electron beam, and then measure the content of methane gas by a gas chromatograph.

[0041] In some alternative embodiments, the alcohol in the small molecule alcohol solution is at least one of methanol, ethanol, and isopropanol.

[0042] In some alternative embodiments, the method includes the following steps:

[0043] Add the alcohol to the aqueous solution, and stir to mix evenly to obtain a mixed solution;

[0044] Irradiate the mixed solution with a high-energy electron beam, and measure the content of the gas by a gas chromatograph.

[0045] In some alternative embodiments, the volume ratio of alcohol to water is 0.1 mL∶9.9 mL.

[0046] In some alternative embodiments, during high-energy electron beam irradiation, it is irradiated to 120 KGy in the form of 15 KGy / round.

[0047] In some alternative embodiments, the conditions for electron beam irradiation are room temperature and normal pressure.

[0048] The present invention also discloses the application of the above method in the production of methane from alcohols.

[0049] In the present invention, the "room temperature" mentioned herein, unless otherwise specified, refers to 20 - 30 °C, and the normal pressure is one atmospheric pressure.

[0050] All raw materials used in the present invention are obtained by purchasing on the market.

[0051] For each example and each comparative example of the present invention, the specific operation steps for testing the performance of the prepared mixed solution to irradiate and produce methane under the drive of a high-energy electron beam are as follows:

[0052] Take 1 mL of gas using a syringe and inject it into a gas chromatograph. Repeat this three times and take the average value. Detect the production of methane gas using gas chromatography, and thereby calculate the effect of methane production by high-energy electron beam irradiation.

[0053] The technical solution of the present invention will be further described below through examples.

[0054] Example 1

[0055] A method for producing methane by irradiating an isopropanol solution with a high-energy electron beam includes the following steps:

[0056] 1) Measure 0.1 mL of isopropanol and add it to 9.9 mL of pure water. Stir evenly to obtain a mixed solution, and add it to a 20 mL sealed glass bottle; label it as EB-IPA-1;

[0057] 2) Irradiate the glass bottle with a high-energy electron beam, irradiate it to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0058] 3) Use a syringe to collect 1 mL of the gas part after the high-energy electron beam irradiation in step 2);

[0059] 4) Use a gas chromatograph to analyze and measure the gas collected in step 3):

[0060] The effect diagram of methane production by EB-IPA-1 under the condition of high-energy electron beam irradiation in Example 1 is shown in Figure 1 , it can be seen from the figure that as the irradiation dose increases, the content of methane gradually rises. Finally, the methane production amount at an irradiation dose of 120 KGy reaches 188.6 μmol / L, indicating that EB-IPA-1 prepared in Example 1 has a good effect of methane production by irradiation.

[0061] Example 2

[0062] A method for producing methane by irradiating an isopropanol solution with a high-energy electron beam includes the following steps:

[0063] 1) Measure 0.2 mL of isopropanol and add it to 9.8 mL of pure water. Stir evenly to obtain a mixed solution, and add it to a 20 mL sealed glass bottle; label it as EB-IPA-2;

[0064] 2) Irradiate the glass bottle with a high-energy electron beam, irradiate it to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0065] 3) Use a syringe to collect 1 mL of the gas part after the high-energy electron beam irradiation in step 2);

[0066] 4) Analyze and measure the gas collected in step 3) using a gas chromatograph.

[0067] The methane production effect diagram of EB-IPA-2 prepared in Example 2 under the condition of high-energy electron beam irradiation is shown in Figure 2 , it can be seen from the figure that as the irradiation dose increases, the content of methane gradually increases. Finally, the methane production at an irradiation dose of 120 KGy reaches 453.9 μmol / L, indicating that EB-IPA-2 prepared in Example 2 has a good effect on methane production by irradiation.

[0068] Example 3

[0069] A method for producing methane by irradiating isopropanol solution with high-energy electron beam, including the following steps:

[0070] 1) Measure 0.3 mL of isopropanol and add it to 9.7 mL of pure water, stir evenly, and add the obtained mixed solution to a 20 mL sealed glass bottle; labeled as EB-IPA-3;

[0071] 2) Irradiate the glass bottle with high-energy electron beam, irradiate to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0072] 3) Use a syringe to collect 1 mL of the gas part after high-energy electron beam irradiation in step 2);

[0073] 4) Analyze and measure the gas collected in step 3) using a gas chromatograph.

[0074] The methane production effect diagram of EB-IPA-3 prepared in Example 3 under the condition of high-energy electron beam irradiation is shown in Figure 3 , it can be seen from the figure that as the irradiation dose increases, the content of methane gradually increases. Finally, the methane production at an irradiation dose of 120 KGy reaches 885.2 μmol / L, indicating that EB-IPA-3 prepared in Example 3 has a good effect on methane production by irradiation.

[0075] Example 4

[0076] A method for producing methane by irradiating methanol solution with high-energy electron beam, including the following steps:

[0077] 1) Measure 0.1 mL of methanol and add it to 9.9 mL of pure water, stir evenly, and add the obtained mixed solution to a 20 mL sealed glass bottle, labeled as EB-MeOH;

[0078] 2) Irradiate the glass bottle with high-energy electron beam, irradiate to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0079] 3) Use a syringe to collect 1 mL of the gas portion after the high-energy electron beam irradiation in step 2).

[0080] 4) Use a gas chromatograph to analyze and measure the gas collected in step 3).

[0081] The methane production effect diagram of EB-MeOH prepared in Example 4 under the condition of high-energy electron beam irradiation is shown in Figure 6 , it can be seen from the figure that the methane production reaches 82.46 μmol / L after the final irradiation dose reaches 120 KGy, indicating that the prepared EB-MeOH has a good effect on methane production by irradiation.

[0082] Example 5

[0083] A method for producing methane by irradiating an ethanol solution with a high-energy electron beam, comprising the following steps:

[0084] 1) Measure 0.1 mL of ethanol and add it to 10 mL of pure water, stir evenly, and add the resulting mixed solution to a 20 mL sealed glass bottle, labeled as EB-EtOH;

[0085] 2) Irradiate the glass bottle with a high-energy electron beam, irradiate it to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0086] 3) Use a syringe to collect 1 mL of the gas portion after the high-energy electron beam irradiation in step 2);

[0087] 4) Use a gas chromatograph to analyze and measure the gas collected in step 3).

[0088] The methane production effect diagram of EB-EtOH prepared in Example 5 under the condition of high-energy electron beam irradiation is shown in Figure 6 , it can be seen from the figure that the methane production reaches 123.74 μmol / L after the final irradiation dose reaches 120 KGy, indicating that the prepared EB-EtOH has a good effect on methane production by irradiation.

[0089] Comparative Example 1

[0090] A method for producing methane by irradiating a pure aqueous solution with a high-energy electron beam, comprising the following steps:

[0091] 1) Measure 10 mL of pure water and add it to a 20 mL sealed glass bottle; label it as EB-H2O;

[0092] 2) Irradiate the glass bottle with a high-energy electron beam, irradiate it to 120 KGy in the form of 15 KGy / round, and the irradiation rate is 18 KGy / s;

[0093] 3) Use a syringe to collect 1 mL of the gas portion after the high-energy electron beam irradiation in step 2);

[0094] 4) Use a gas chromatograph to analyze and measure the gas collected in step 3).

[0095] The effect diagram of methane production by the EB-H2O prepared in Comparative Example 1 under the condition of high-energy electron beam irradiation is shown in Figure 4 , it can be seen from the figure that as the irradiation dose increases, the content of methane increases slowly, and the methane production amount after the irradiation dose finally reaches 120 KGy is 15.06 μmol / L. This is attributed to the reaction of CO2 in the air with H2O to generate methane, indicating that the EB-H2O prepared in Comparative Example 1 does not have the effect of methane production by irradiation.

[0096] Summary:

[0097] (1) The high-energy electron beam irradiation reforming of small molecule alcohol solution in the present invention has a good effect of methane production;

[0098] (2) Among different small molecule alcohol solutions, isopropanol has obvious advantages in the performance of methane production under the action of high-energy electron beam.

[0099] (3) As the content of isopropanol and the irradiation dose increase, the methane production amount per unit time also increases.

[0100] The above is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation, characterized in that, It includes the following steps: Irradiate an alcohol solution with a high-energy electron beam to prepare methane.

2. The method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation according to claim 1, wherein, The alcohol in the alcohol solution is a small molecule alcohol; The power of the high-energy electron beam is 0 - 20 kW, where the power is not 0.

3. A method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation according to claim 2, characterized in that, The small molecule alcohol includes at least one of methanol, ethanol, and isopropyl alcohol.

4. A method for preparing methane by irradiating and reforming small molecule alcohols with high-energy electron beams according to claim 3, characterized in that, The small molecule alcohol is isopropyl alcohol.

5. A method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation according to claim 1, characterized in that, The content of the alcohol in the alcohol solution is 1 - 3 vol.%.

6. A method for preparing methane by irradiating and reforming small molecule alcohols with high-energy electron beams according to claim 1, characterized in that The conditions during the irradiation treatment are: irradiate in the form of 0 - 15 KGy / round, where the irradiation form is not 0.

7. A method for preparing methane by reforming small molecule alcohols using high-energy electron beam irradiation according to claim 6, characterized in that, The irradiation rate during the irradiation treatment is 0 - 18 KGy / s, where the irradiation rate is not 0.

8. A method for preparing methane by irradiating and reforming small molecule alcohols with high-energy electron beams according to claim 1, characterized in that, The method for preparing methane by irradiating and reforming small molecule alcohols with a high-energy electron beam includes the following steps: Irradiate a 3 vol.% aqueous solution of isopropyl alcohol with a high-energy electron beam in the form of 15 KGy / round to 120 KGy to prepare methane.

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