阅读说明：本技术 基于新型人工光合作用实现太阳能能量转换、存储和利用的方法 (Method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis ) 是由 李长明 沈杨彬 胡俊蝶 于 2020-05-13 设计创作，主要内容包括：本发明公开了一种基于新型人工光合作用实现太阳能能量转换、存储和利用的方法,包括如下步骤：(1)将太阳能转换为化学能：聚光太阳能并加热反应器,在反应器内通入二氧化碳和水,在第一催化剂的作用下生成有机液体,存储得到的有机液体；(2)将化学能转换为电能：在聚光太阳能加热条件下,利用第二催化剂将所述有机液体催化生成氢气,并利用生成的氢气驱动燃料电池,产生电能。本发明的基于新型人工光合作用实现太阳能能量转换、存储和利用的方法,整个过程仅仅需要水和二氧化碳作为反应物,通过太阳能即可高效实现光热转换,便可以完成太阳能的转换、存储和利用,避免能量转换效率较低受卡诺循环限制的热机过程,是一种液态太阳能的高效转换方案。(The invention discloses a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which comprises the following steps: (1) conversion of solar energy into chemical energy: concentrating solar energy and heating a reactor, introducing carbon dioxide and water into the reactor, generating organic liquid under the action of a first catalyst, and storing the obtained organic liquid; (2) conversion of chemical energy into electrical energy: and under the heating condition of concentrating solar energy, catalyzing the organic liquid by using a second catalyst to generate hydrogen, and driving a fuel cell by using the generated hydrogen to generate electric energy. According to the method for realizing solar energy conversion, storage and utilization based on the novel artificial photosynthesis, only water and carbon dioxide are needed as reactants in the whole process, photo-thermal conversion can be efficiently realized through solar energy, conversion, storage and utilization of the solar energy can be completed, the heat engine process that the energy conversion efficiency is low and is limited by Carnot cycle is avoided, and the method is an efficient conversion scheme of liquid solar energy.)

1. A method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis is characterized by comprising the following steps:

(1) conversion of solar energy into chemical energy: the concentrated solar heating reactor is filled with carbon dioxide and water, and organic liquid is generated under the action of a first catalyst;

(2) conversion of chemical energy into electrical energy: and under the condition of concentrating solar energy heating, catalyzing the organic liquid by using a second catalyst to generate hydrogen, and driving a fuel cell by using the generated hydrogen to generate electric energy.

2. The method for solar energy conversion, storage and utilization based on novel artificial photosynthesis according to claim 1, wherein: in the step (1), the organic liquid generated is, but not limited to, methanol, formic acid or formaldehyde.

3. The method for solar energy conversion, storage and utilization based on novel artificial photosynthesis according to claim 1, wherein: the first catalyst includes, but is not limited to, one or a mixture of at least two of ceria, titania, and copper-zinc alloy.

4. The method for solar energy conversion, storage and utilization based on novel artificial photosynthesis according to claim 1, wherein: the second catalyst includes, but is not limited to, a metal oxide, a metal organic compound, and/or a supported monatomic catalyst.

5. The method for solar energy conversion, storage and utilization based on novel artificial photosynthesis, according to claim 4, wherein: the metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium.

6. The method for solar energy conversion, storage and utilization based on novel artificial photosynthesis, according to claim 4, wherein: the supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

7. Method for solar energy conversion, storage and utilization based on novel artificial photosynthesis according to any one of claims 1 to 6, characterized in that: and the organic liquid is subjected to catalytic reaction to produce a mixed gas containing hydrogen, carbon dioxide and carbon monoxide, and the hydrogen obtained by separating and purifying the mixed gas is introduced into an anode region of the proton exchange membrane-based fuel cell or other types of fuel cells or the mixed gas is directly introduced into the anode region of the fuel cell.

Technical Field

The invention belongs to the technical field of solar energy utilization, and particularly relates to a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis.

Background

At present, the utilization of solar energy to replace fossil fuel to provide fuel and energy for human beings is one of the important approaches for solving the current environmental problems. The direct conversion of solar energy to hydrogen or photolyzed/electrolyzed water by biomimetic photosynthesis is still in the research stage and has low efficiency. The energy conversion process of the concentrating solar heat machine-electric energy is limited by Carnot cycle, the energy conversion efficiency is not high, and the solar cell is not beneficial to the requirement of a mobile power supply at present and does not relate to the link of energy storage.

In 2011, the academy of california and swiss scientists developed a solar reactor, which uses a novel catalyst with low cost to concentrate the heat of the sun, and converts water and carbon dioxide into hydrogen and carbon monoxide by a thermochemical cycle method, and a large amount of hydrogen and carbon monoxide are combined together to form liquid fuel. The experimental equipment comprises two parts, wherein one part is a cylindrical container developed by California institute of technology, and the inner wall of the cylindrical container is filled with cerium dioxide; the second part is a solar collector which is currently arranged at the research institute of paul schhler, switzerland and is a set of huge curved mirrors which can collect sunlight in a large range.

Researchers at the university of Texas, USA, Arlington, 2016, Brian Dennis, et al found that in a photothermal chemical fluid reactor, carbon dioxide and water can be converted to liquid hydrocarbons and oxygen in one step at 180 ℃ to 200 ℃ and 6 atmospheres. They explain that concentrating light energy causes a photochemical reaction to produce high energy intermediates and heat, thereby initiating a thermochemical reaction that forms a carbon chain, which produces hydrocarbons in a single step process. They therefore use a parabolic mirror to concentrate sunlight onto the catalyst bed, providing heat and light excitation for the reaction. The excess heat can also be used to drive the operation of the associated solar fuel facility, including product separation, water purification, and the like.

Prashan Jain 2019, university of Enlboro-Champagne, Irbara, Illino, USA, found that carbon dioxide and water can be converted into liquid fuels by means of solar energy using novel artificial photosynthesis. Liquid fuels are ideal energy sources and are easier, safer and more economical to transport than fuels such as natural gas, hydrogen, etc. The wangdong team of the university of academy of sciences in china 2019, using a two-step method, realizes solar high-temperature thermochemical energy storage, and they found that carbon dioxide and water can be cracked to generate carbon monoxide and hydrogen under the isothermal condition of 900 ℃.

Disclosure of Invention

In view of the above, the present invention provides a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which realizes the conversion of solar energy → heat energy → chemical energy → electric energy, and converts solar energy into organic liquid, so as to realize not only energy conversion but also energy storage, thereby avoiding the heat engine process limited by carnot cycle due to low energy conversion efficiency, and thus, the method is a high efficiency conversion scheme for liquid solar energy.

In order to achieve the purpose, the invention provides the following technical scheme:

a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis comprises the following steps:

(1) conversion of solar energy into chemical energy: concentrating solar energy and heating a reactor, introducing carbon dioxide and water into the reactor, and generating organic liquid under the action of a first catalyst;

(2) conversion of chemical energy into electrical energy: and under the heating condition of concentrating solar energy, catalyzing the organic liquid by using a second catalyst to generate hydrogen, and driving a fuel cell by using the generated hydrogen to generate electric energy.

Further, in the step (1), the generated organic liquid is methanol, formic acid or formaldehyde.

Further, the first catalyst includes, but is not limited to, one or a mixture of at least two of cerium oxide, titanium dioxide and copper-zinc alloy.

Further, the second catalyst comprises a metal organic compound and/or a supported monatomic catalyst.

Further, the metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium.

Further, the supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

Further, the organic liquid is subjected to catalytic reaction to produce a mixed gas containing hydrogen, carbon dioxide and carbon monoxide, and the hydrogen obtained by separating and purifying the mixed gas is introduced into an anode region of the proton exchange membrane-based fuel cell or other types of fuel cells or the mixed gas is directly introduced into the anode region of the fuel cell.

The invention has the beneficial effects that:

the method for realizing solar energy conversion, storage and utilization based on the novel artificial photosynthesis firstly utilizes solar energy to convert carbon dioxide and water into organic liquid, not only converts the solar energy into chemical energy, but also facilitates the storage and transportation of the organic liquid; in the energy utilization process, the solar thermal energy is utilized to catalyze the organic liquid to decompose and generate hydrogen, the hydrogen can be utilized to directly drive the fuel cell to generate electric energy, the conversion from chemical energy to electric energy is realized, the whole process only needs water and carbon dioxide as reactants, the photo-thermal conversion can be efficiently realized through solar energy, the conversion, the storage and the utilization of the solar energy can be completed, the heat engine process limited by Carnot cycle and low energy conversion efficiency is avoided, meanwhile, the problem of greenhouse gas can be solved, and the liquid solar energy high-efficiency conversion scheme is provided.

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 the solar energy conversion process in the method for realizing solar energy conversion, storage and utilization based on the novel artificial photosynthesis;

FIG. 2 is a schematic diagram of a concentrated solar power plant and reactor;

FIG. 3 is a chemical structure diagram of a metal organic compound catalyst;

FIG. 4 is a chemical structural diagram of a second catalyst catalyzing the reforming of methanol and water in example 1;

FIG. 5 is a chemical structural diagram of a second catalyst for catalyzing a decomposition reaction of formic acid in example 2;

FIG. 6 is a chemical structural diagram of a second catalyst catalyzing a formaldehyde decomposition reaction in example 3.

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.

Fig. 1 is a schematic diagram of a solar energy conversion process in the method for realizing solar energy conversion, storage and utilization based on the novel artificial photosynthesis. The embodiment of the invention relates to a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which comprises the following steps:

(1) conversion of solar energy into chemical energy: concentrating solar energy, heating the reactor, introducing carbon dioxide and water into the reactor, generating organic liquid under the action of the first catalyst, and storing the obtained organic liquid. As shown in FIG. 2, solar energy heats the reactor under the action of the condenser, so that the reactor generates high temperature of 500-1200 ℃, carbon dioxide and water are input into the reactor, and organic liquid is generated under the action of the first catalyst, thereby realizing the conversion and storage of solar energy. Specifically, the generated organic liquid is methanol, formic acid or formaldehyde, and the first catalyst includes but is not limited to one or a mixture of at least two of cerium dioxide, titanium dioxide and copper-zinc alloy.

(2) Conversion of chemical energy into electrical energy: and under the heating condition of concentrating solar energy, catalyzing the organic liquid by using a second catalyst to generate hydrogen, and driving a fuel cell by using the generated hydrogen to generate electric energy. Specifically, the second catalyst comprises a metal, a metal oxide, a metal organic compound and/or a supported monatomic catalyst. The metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium. The supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

Further, the organic liquid is subjected to catalytic reaction to produce a mixed gas containing hydrogen, carbon dioxide and carbon monoxide, and the hydrogen obtained by separating and purifying the mixed gas is introduced into an anode region of the proton exchange membrane-based fuel cell or other types of fuel cells or the mixed gas is directly introduced into the anode region of the fuel cell.

Methanol, formic acid and formaldehyde can be used for storing hydrogen atoms and generating hydrogen and carbon dioxide under the action of a second catalyst. The reaction equation is as follows:

reaction 1: CH (CH)₃OH+H₂O→3H₂+CO₂

Reaction 2: HCHO + H₂O→2H₂+CO₂

Reaction 3: HCOOH → H₂+CO₂

For reaction 1, the second catalyst may be catalyzed using organoiridium, organoruthenium, organorhodium, zirconium nitride supported monatomic platinum catalyst, zirconium nitride supported monatomic iridium catalyst, zirconium nitride supported monatomic rhodium catalyst.

For reaction 2, the second catalyst can be accomplished using an organoruthenium or zirconium nitride supported monoatomic ruthenium catalyst.

For reaction 3, the second catalyst may be catalyzed using organoiridium and organorhodium.

The organometallic compounds described herein (organoiridium, organoruthenium and organorhodium) are essentially organometallic catalysts having the chemical structure shown in figure 3 and coordinated with a nitrogen-containing heterocycle.

Because the catalyst has higher activity and selectivity, the generated hydrogen can be directly used in a hydrogen-oxygen fuel cell to realize the conversion of chemical energy into electric energy.

The following further describes a specific embodiment of the present embodiment with reference to specific examples.

Example 1

The embodiment of the invention relates to a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which comprises the following steps:

(1) the concentrating solar energy device shown in fig. 2 is used, the concentrating solar energy is used for heating a reactor, water and carbon dioxide are introduced into the reactor after the temperature of the reactor reaches 800 ℃, and a mixture of cerium dioxide, titanium dioxide and nano copper and zinc is used as a first catalyst to catalyze the reaction of the carbon dioxide and the water to generate methanol and oxygen. Methanol is liquid and can be directly collected by a condensing device.

(2) The reactor was heated to 150 ℃ using a concentrating solar power unit as shown in fig. 2. And (3) introducing water and methanol into the reactor, and using the compound with the structure shown in the figure 4 as a second catalyst to catalyze the reforming of the methanol and the water to generate hydrogen and carbon dioxide. No CO is generated in the reaction process.

In the embodiment, the mixture of carbon dioxide and hydrogen generated by the reforming reaction of methanol and water can be directly input into a proton exchange membrane fuel cell or other types of fuel cells to generate electric energy.

Example 2

The embodiment of the invention relates to a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which comprises the following steps:

(1) by using the concentrating solar device shown in fig. 2, concentrating solar energy is used for heating a reactor, water and carbon dioxide are introduced into the reactor after the temperature of the reactor reaches 800 ℃, and titanium dioxide is used as a first catalyst to catalyze the reaction of the carbon dioxide and the water to generate formic acid and oxygen. Formic acid is a liquid that can be collected directly with a condensing unit.

(2) The reactor was heated to 90 ℃ using a concentrating solar power unit as shown in fig. 2. Water and formic acid are introduced into the reactor, and a compound with a structure shown in figure 5 is used as a second catalyst to catalyze the decomposition of formic acid to generate hydrogen and carbon dioxide. No CO is generated in the reaction process.

In the embodiment, the mixture of carbon dioxide and hydrogen generated by the decomposition of formic acid can be directly input into the proton exchange membrane fuel cell to generate current.

Example 3

The embodiment of the invention relates to a method for realizing solar energy conversion, storage and utilization based on novel artificial photosynthesis, which comprises the following steps:

(1) using the concentrating solar device shown in fig. 2, concentrating solar energy is used to heat a reactor, after the temperature of the reactor reaches 800 ℃, water and carbon dioxide are introduced into the reactor, ceria is used as a first catalyst to catalyze the reaction of carbon dioxide and water, and formaldehyde and oxygen are generated. The aqueous formaldehyde solution is liquid and can be directly collected by a condensing device.

(2) The reactor was heated to 90 ℃ using a concentrating solar power unit as shown in fig. 2. Introducing a formaldehyde aqueous solution into the reactor, and catalyzing the decomposition of the formaldehyde aqueous solution to generate hydrogen and carbon dioxide by using a compound with a structure shown in figure 6 as a second catalyst. No CO is generated in the reaction process.

The mixture of carbon dioxide and hydrogen generated by formaldehyde decomposition can be directly input into a proton exchange membrane fuel cell or other types of fuel cells to generate electric energy.

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.