阅读说明：本技术 太阳能仿生催化的液态燃料的合成方法 (Synthetic method of liquid fuel by solar biomimetic catalysis ) 是由 李长明 吴小帅 于 2020-05-13 设计创作，主要内容包括：本发明公开了仿生太阳能液态燃料的合成方法,利用太阳能将二氧化碳和水在光催化剂及生物催化剂的协同作用下高效转化为液态燃料的联合技术；通过将化反应和微生物电合成两种反应体系进行优势互补,利用太阳能装置实现二氧化碳向液态燃料的高效转化,最后将液态燃料通过燃料电池的使用将合成的液态燃料转化为电能和CO-(2),实现碳的有效循环,有望解决所面临的能源危机及温室效应等环境问题,实现清洁能源的可持续发展。(The invention discloses a synthetic method of bionic solar liquid fuel, which utilizes a combined technology that solar energy is utilized to efficiently convert carbon dioxide and water into liquid fuel under the synergistic action of a photocatalyst and a biocatalyst; the advantages of two reaction systems of chemical reaction and microbial electrosynthesis are complemented, and the solar device is utilized to realize the high-efficiency conversion of carbon dioxide to liquid fuelFinally, the liquid fuel is converted into electric energy and CO by using the fuel cell 2 The method realizes effective circulation of carbon, is expected to solve the environmental problems of energy crisis, greenhouse effect and the like, and realizes sustainable development of clean energy.)

1. The synthesis method of the solar biomimetic catalytic liquid fuel is characterized by comprising the following steps: combined photocatalytic and microbial electrosynthesis of CO₂And is converted into liquid fuel.

2. The method for synthesizing the solar biomimetic catalytic liquid fuel according to claim 1, characterized in that: the method comprises the steps of fixing carbon dioxide into an intermediate product by using a photocatalyst I, and then selecting the biocatalyst I capable of using the intermediate product to convert the intermediate product into liquid fuel through microbial electrosynthesis;

or CO is synthesized by bioelectricity by utilizing a biocatalyst II₂And then the intermediate product is further converted into liquid fuel, but not limited to methanol or acetic acid, by using a photocatalyst II.

3. The method for synthesizing the bionic solar liquid fuel according to claim 2, characterized by comprising the following steps: the intermediate products are CO, formaldehyde and CH₄One or more of (a).

4. The method for synthesizing the bionic solar liquid fuel according to claim 2, characterized by comprising the following steps: the liquid fuel is methanol, ethanol or esters.

5. The method for synthesizing the bionic solar liquid fuel according to claim 2, characterized by comprising the following steps: the biocatalyst I can react with CO, formaldehyde and CH₄One or more of a microorganism, a biological enzyme, or a biomimetic enzyme that converts to methanol or ethanol; the biocatalyst II is capable of reacting CO₂Conversion into CO, formaldehyde, CH₄Or a biomimetic enzyme, or a combination thereof.

6. The method for synthesizing the bionic solar liquid fuel according to claim 5, wherein the method comprises the following steps: the biocatalyst I comprises but is not limited to methane oxidizing bacteria, methanol dehydrogenase, aldose reductase and the like; the biocatalyst II comprises but is not limited to methanogen or acetogen; such acetogens include, but are not limited to, Sporosma spp, Moorella thermoacetica, and methanogens include, but are not limited to, Methanococcus equi (Methanococcus), Methanosarcina (Methano-sarcina), Methanobacterium ruminatum (Methanobacterium), and the like.

7. The method for synthesizing the bionic solar liquid fuel according to claim 2, characterized by comprising the following steps: the photocatalyst I can reduce carbon dioxide to generate CO, formaldehyde and CH₄Etc. which is, but not limited to, a precious or non-precious metal modified vanadium-based compound, Ti-based compound, or graphite phase carbon nitride;

the photocatalyst II can be used for reacting CO, formaldehyde and CH at room temperature₄And the like into liquid fuels such as methanol or ethanol, and the catalytic material is a vanadium compound, a Ti-based compound or graphite-phase carbon nitride modified by noble metal or non-noble metal.

8. The method for synthesizing the bionic solar liquid fuel according to claim 7, wherein the method comprises the following steps: the noble metal is but not limited to one or more of Pt, Ag, Pd or Au; the non-noble metal includes, but is not limited to, one or more of Cu, Mg, Co, or Ni.

9. The method for synthesizing the bionic solar liquid fuel according to claim 6, wherein the method comprises the following steps: the photocatalyst I comprises but is not limited to BiVO by a high-temperature method and a deposition method₄The surface of the substrate material is doped with but not limited to a catalytic material of non-noble metal atoms such as Cu, Mg, Co or Ni; the photocatalyst II comprises but is not limited to Cu, Pt, Pb and other doped polymer carbon nitride materials or silicon oxide supported transition metal phosphide and the like.

Technical Field

The invention relates to the technical field of renewable clean energy utilization, in particular to a combined technology for efficiently converting carbon dioxide and water into liquid fuel by utilizing solar energy under the synergistic action of a photocatalyst and a biocatalyst.

Background

With the gradual increase of global environmental pollution and energy shortage, it is the focus of research at present to seek efficient clean energy to replace the existing fossil energy. The large consumption of traditional fossil energy such as coal, petroleum and natural gas not only causes the energy reserves to be sharply reduced, but also causes serious environmental pollution problems, especially CO₂The global ecological balance is seriously threatened by the emission of greenhouse gases. How to reduce the content in the atmosphere, relieve the greenhouse effect and convert the greenhouse effect into clean energy, and realize the efficient utilization of renewable energy has attracted extensive attention. In recent years, CO has been produced by homogeneous and heterogeneous catalytic hydrogenation, inorganic photoelectrocatalysis, and pyrolysis₂The "carbon capture and utilization" technology for activation has made great progress, and CO is realized₂Will convert organic substances such as methane, methanol and longer carbon chain alcohols and fatty acid ester polymers. CO 2₂The biological fixation method can realize CO under mild conditions₂Compared with an inorganic catalytic method, the microbial electrosynthesis method has more advantages, wherein the microbial electrosynthesis method is the focus of current research, and the microbial electrosynthesis method is used for producing organic matters such as methane, formic acid, acetic acid, butyric acid and the like. However, for the microbial electrical synthesis method, the current synthesis efficiency is far from sufficient for large-scale popularization and application in industrial production, and the main difficulties are low metabolism rate of the microbial carbon fixation pathway and low microbial extracellular electron transfer efficiency. In order to promote the development and the practical application of the microbial electrosynthesis carbon sequestration approach and achieve the industrialized production requirement, besides the genetic approach of microorganism modification and the design of efficient electrode materials, the optimization of the reactor design and the combined utilization of a plurality of energy production approaches to improve the conversion efficiency are more effective approaches.

Solar energy is the most clear and accepted energy source, and the solar energy is mainly utilized in the forms of photovoltaic, photothermal, green plants and the like. The photocatalytic organic synthesis can realize the conversion of organic matters under normal pressure by utilizing solar energy, is widely applied to organic synthesis reactions from amine to imine organic matters, alcohol to aldehyde organic matters and the like, and has good product selectivity. However, the catalytic conversion rate of the organic synthesis is low, and the organic synthesis with high efficiency still has great challenges. Recently, the application scene of visible sunlight is greatly expanded by the proposal of the concept of 'liquid sunlight', the purpose of which is to extract renewable green liquid fuel from sunlight, carbon dioxide and water and convert the renewable green liquid fuel into storable and usable energy, but a plurality of technical bottlenecks need to be broken through when the 'liquid sunlight' is industrially popularized and applied in a large scale. At present, the photocatalytic reaction and microbial electrosynthesis are reported to realize the conversion and reuse of carbon dioxide, and the carbon dioxide is hopefully converted into the available liquid fuel while the concentration of the carbon dioxide in the atmosphere is reduced, but the conversion efficiency is low at present and the method is applied to the industry on a large scale. In conclusion, the advantages of the two reaction systems are complemented, the solar device is utilized to realize the high-efficiency conversion of the carbon dioxide to the liquid fuel, the environmental problems of energy crisis, greenhouse effect and the like are expected to be solved, and the sustainable development of clean energy is realized.

Disclosure of Invention

The invention carries out advantage complementation on two reaction systems of photocatalyst and bioelectricity synthesis, utilizes the solar device to realize the high-efficiency conversion of carbon dioxide to liquid fuel, and then converts the synthesized liquid fuel into electric energy and CO by using the fuel cell₂And effective circulation of carbon is realized (the principle is shown in figure 1).

To achieve the above purpose, the synthesis process of liquid fuel is designed into two routes (see fig. 2):

(1) the first route is as follows: the carbon dioxide is catalyzed by a photocatalyst to firstly generate CO, formaldehyde and CH₄And the like. In the reaction, different photocatalysts are selected to obtain different main products, such as BiVO₄And zinc oxide catalyst mainly containing CO₂The reduction to methane and Ti-based compounds can mainly reduce CO₂Catalytic reduction to formic acid, etc.; then aiming at different intermediate products, reasonably selecting a microorganism/biological enzyme/biomimetic enzyme catalyst to further catalyze the intermediate products to generate the alphaLiquid fuel end products such as alcohols and ethanol;

(2) the second route is as follows: firstly, adopting a bioelectricity synthesis method to selectively convert the CO, the formaldehyde and the CH by utilizing a microorganism/biological enzyme/bionic enzyme catalyst₄Etc., for example, Clostridium (Clostridium) can be used as a multifunctional acid producing bacterium, acetogenic bacteria (Sporosuma spp. and Moorella thermoacetica) can convert CO₂Fixed as acetic acid, etc.; and then the mixture is converted into liquid fuel final products such as ethanol and the like by selecting a photocatalyst.

The specific scheme is as follows:

method for synthesizing bionic solar liquid fuel by combining photocatalytic reaction and microbial electrosynthesis to synthesize CO₂And is converted into liquid fuel.

The specific method of the combined utilization is to utilize a photocatalyst I to fix carbon dioxide as an intermediate product, and then select a biocatalyst I capable of utilizing the intermediate product to convert the intermediate product into liquid fuel through microbial electrosynthesis;

or CO is synthesized by bioelectricity by utilizing a biocatalyst II₂Conversion into CO, formaldehyde, CH₄And then CO, formaldehyde and CH are treated by a photocatalyst II₄And so on into liquid fuels.

As a preferred technical scheme of the invention, the intermediate products are CO, formaldehyde and CH₄And formic acid.

In a preferred embodiment of the present invention, the liquid fuel is methanol, ethanol, or the like.

As a preferable technical scheme of the invention, the biocatalyst I can be used for dissolving CO, formaldehyde and CH₄One or more of a microorganism, a biological enzyme, or a biomimetic enzyme that converts to methanol and ethanol; the biocatalyst II is capable of reacting CO₂Conversion into CO, formaldehyde, CH₄Etc., or a biological enzyme, or a biomimetic enzyme.

As a preferred technical scheme of the invention, the biocatalyst I comprises but is not limited to methane-oxidizing bacteria, methanol dehydrogenase, aldose reductase and the like; the biocatalyst II comprises but is not limited to methanogen or acetogen; such acetogens include, but are not limited to, Sporosma spp, Moorella thermoacetica, and methanogens include, but are not limited to, Methanococcus equi (Methanococcus), Methanosarcina (Methano-sarcina), Methanobacterium ruminatum (Methanobacterium), and the like.

As a preferable technical scheme of the invention, the photocatalyst I can reduce carbon dioxide to generate CO, formaldehyde and CH₄The catalytic material is a vanadium compound, a Ti-based compound or graphite-phase carbon nitride modified by noble metal or non-noble metal;

the photocatalyst II can be used for reacting CO, formaldehyde and CH at room temperature₄And the like, and the catalytic material is a vanadium compound, a Ti-based compound or graphite-phase carbon nitride modified by noble metal or non-noble metal.

As a preferable technical scheme of the invention, the noble metal is one or more of Pt, Ag, Pd or Au; the non-noble metal is one or more of Cu, Mg, Co or Ni.

As a preferred technical scheme of the invention, the photocatalyst I comprises but is not limited to BiVO (BiVO) prepared by a high-temperature method and a deposition method₄The surface of the substrate material is doped with a catalytic material of non-noble metal atoms such as Cu, Mg, Co or Ni; the photocatalyst II comprises but is not limited to Cu, Pt, Pb and other doped polymer carbon nitride materials or silicon oxide supported transition metal phosphide and the like.

The invention has the beneficial effects that: the invention discloses a synthetic method of bionic solar liquid fuel, which comprises the technical field of complementary utilization of various renewable clean energy sources, in particular to a multiple combination technology for efficiently converting carbon dioxide and water into liquid fuel by utilizing solar energy under the synergistic action of a photocatalyst and a biological enzyme catalyst. The invention aims to complement the advantages of two reaction systems of photocatalysis reaction and microbial electrosynthesis and realize the high-efficiency conversion of carbon dioxide to liquid fuel by utilizing a solar device. Firstly, designing and synthesizing a proper photocatalyst which can be suitable for realizing the rapid reaction of organic synthesis under the high-energy catalysis of concentrating solar energy; secondly, screening a microbial catalyst in the microbial electrosynthesis reaction, and selectively and efficiently converting carbon dioxide into organic matters such as methane, formaldehyde, formic acid and the like, or further converting the formic acid, the formaldehyde and the like into ethanol and ester organic matters; and finally, the photocatalyst and the microbial catalyst are effectively combined, the reaction sequence is adjusted according to the photocatalyst and the microbial catalyst, and the rapid fixed conversion of carbon dioxide and the efficient production of liquid fuel are realized with the help of solar energy.

Drawings

In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:

FIG. 1 is a schematic diagram of a cycle of the present invention for achieving the fixed conversion of carbon dioxide into liquid fuel and then into electrical energy via a fuel cell; carbon dioxide and water are efficiently converted into liquid fuels such as ethanol and the like under the action of a photocatalyst and a biocatalyst, and the generated liquid fuels can be directly used as clean energy sources to be utilized by a fuel cell, so that the rapid circulation of solar energy, chemical energy and electric energy is realized.

FIG. 2 is a schematic diagram of a liquid fuel synthesis process design.

Detailed Description

The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.

Example 1

With BiVO₄The material which is used as a substrate material and is prepared by doping non-noble metal atoms such as Ni, Mg, Cu and the like on the surface of the material by adopting a high-temperature method and a deposition method is used as a photocatalyst so as to adjust the electronic structure on the surface of the substrate material to improve the photoelectric catalytic performance of the substrate material, and the photocatalyst is further used for converting carbon dioxide into methane under the irradiation of sunlight, so that the fixed conversion of the carbon dioxide at normal temperature and the conversion of solar energy into chemical energy are realized; then, methane oxidation flora is selected to specifically convert the obtained methane into ethanol, and the sustainable production of liquid fuel is realized.

Example 2

With H₂/CO₂As a substrate, methanogens of the hydrogen-forming type are microbial catalysts which reduce carbon dioxide to methane under anaerobic conditions at ambient temperature, or are capable of converting CO to methane using acetogens (Sporosma spp. and Moorella thermoacetica)₂Conversion to acetic acid, etc.; and then, a Cu-doped polymer carbon nitride material or silicon oxide loaded transition metal phosphide is used as a photocatalyst material, methane or acetic acid obtained by microbial electrosynthesis is converted into liquid fuels such as ethanol, and the like.

In the embodiment of the invention, through the selection of the photocatalyst and the biocatalyst and the adjustment of the reaction sequence, the parameter adjustment comprises the following steps: (1) solar light intensity: the tolerance of the photocatalyst to the intensity of sunlight ranges from one sunlight to ten sunlight; (2) the reactor temperature: the temperature of the reaction system will gradually rise under the influence of illumination factors, and the whole reaction system needs to be controlled in the range of highest activity of the biological enzyme/bionic enzyme catalyst (generally 30-37 ℃) by a cooling device; (3) poisoning effect of intermediate on catalyst: the increase of the concentration of the intermediate product and the final product has certain influence on the activity of the catalyst, and in order to ensure the continuation of the catalytic reaction, the liquid fuel final product needs to be collected in real time through a receiving device.

The catalyst has high activity and selectivity in the process of converting carbon dioxide into liquid fuel, can effectively reduce the generation of byproducts, and the generated liquid fuel can be directly utilized by a fuel cell, so that the rapid cycle conversion from solar energy to chemical energy and then to electric energy is realized.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.