CN116288450A - Method and device for preparing synthesis gas by reducing carbon dioxide assisted by flow battery - Google Patents

Abstract

The invention discloses a method and a device for preparing synthesis gas by reducing carbon dioxide assisted by a flow battery, wherein the method comprises the following steps: under the condition of charging, the flow battery generates an oxidized mediator A electrolyte in an anode chamber and a reduced mediator B electrolyte in a cathode chamber. Under the action of a catalyst, the electrolyte of the mediator A in an oxidation state reacts with water in a catalytic reactor I to generate oxygen and protons, and meanwhile, the mediator A is reduced from the oxidation state to a reduction state; protons pass through the membrane of the flow battery from the anode chamber to the cathode chamber of the flow battery, then the protons react with the reduced mediator B electrolyte under the action of a catalyst to generate synthesis gas, and the reduced mediator B is oxidized into an oxidized state. The invention realizes the conversion of carbon dioxide into synthesis gas, and the efficiency of converting carbon dioxide into synthesis gas is not lower than 90%.

Description

Translated fromChinese

一种液流电池辅助的二氧化碳还原制取合成气的方法及装置A method and device for producing synthesis gas by reduction of carbon dioxide assisted by a liquid flow battery

技术领域technical field

本发明涉及一种液流电池辅助的二氧化碳还原制取合成气的方法及装置，属于温室气体处理领域。The invention relates to a method and a device for producing synthesis gas by reduction of carbon dioxide assisted by a liquid flow battery, and belongs to the field of greenhouse gas treatment.

背景技术Background technique

二氧化碳是主要的温室气体，也是一种廉价易得的碳氧资源，研究二氧化碳的化学转化和利用具有重要意义。但由于二氧化碳具有热力学稳定性及动力学惰性，实现二氧化碳的有效转化一直是研究者致力解决的难题，也是绿色化学与催化领域具有挑战性的课题之一。Carbon dioxide is the main greenhouse gas, and it is also a cheap and easy-to-obtain carbon and oxygen resource. It is of great significance to study the chemical conversion and utilization of carbon dioxide. However, due to the thermodynamic stability and kinetic inertness of carbon dioxide, the effective conversion of carbon dioxide has always been a difficult problem for researchers to solve, and it is also one of the challenging topics in the field of green chemistry and catalysis.

目前，常用的二氧化碳催化转化方法有热催化方法、高温裂解法、光催化方法、电催化方法等，然而二次污染、高耗能、低收益严重制约了上述方法的发展。因此，在温和的反应条件下，发明一种有效绿色处理二氧化碳的方法和装置具有重要的意义。At present, commonly used carbon dioxide catalytic conversion methods include thermal catalytic method, pyrolysis method, photocatalytic method, electrocatalytic method, etc. However, secondary pollution, high energy consumption and low yield seriously restrict the development of the above methods. Therefore, it is of great significance to invent an effective and green method and device for carbon dioxide treatment under mild reaction conditions.

发明内容Contents of the invention

本发明的目的是提供了一种液流电池辅助的二氧化碳还原制取合成气的方法和装置，该方法能将二氧化碳还原为具有高附加值的氢气和一氧化碳即合成气，从而实现对含有二氧化碳气体的有效转化利用。该方法处理效率较高，效果显著。The object of the present invention is to provide a method and device for producing synthesis gas through the reduction of carbon dioxide assisted by a liquid flow battery. effective transformation and utilization. This method has high processing efficiency and remarkable effect.

为了实现上述目的，本发明的技术方案如下：In order to achieve the above object, the technical scheme of the present invention is as follows:

本发明一方面提供一种液流电池辅助的二氧化碳还原制取合成气的方法，所述方法包括以下步骤：One aspect of the present invention provides a method for producing synthesis gas by reduction of carbon dioxide assisted by a liquid flow battery, the method comprising the following steps:

液流电池在充电的情况下，阳极生成氧化态的媒介体A电解液，阴极生成还原态的媒介体B电解液；When the flow battery is being charged, the anode generates an oxidized mediator A electrolyte, and the cathode generates a reduced mediator B electrolyte;

将氧化态的媒介体A电解液由阳极室通入催化反应器I，在催化剂的作用下，氧化态的媒介体A电解液与水发生化学反应，生成氧气和质子，同时氧化态的媒介体A电解液被还原为还原态，接着，将质子和还原态的媒介体A电解液混合物返回至液流电池阳极室，通过电解反应，再次生成氧化态的媒介体A电解液，媒介体A电解液在催化反应器I和阳极室之间进行循环；Pass the oxidized mediator A electrolyte from the anode chamber into the catalytic reactor I, under the action of the catalyst, the oxidized mediator A electrolyte reacts with water to generate oxygen and protons, and at the same time the oxidized mediator A Electrolyte A is reduced to a reduced state. Then, the mixture of protons and the electrolyte of mediator A in the reduced state is returned to the anode chamber of the flow battery. Through the electrolytic reaction, the electrolyte of mediator A in the oxidized state is generated again, and the electrolyte of mediator A is electrolyzed. The liquid circulates between the catalytic reactor I and the anode chamber;

质子穿过液流电池隔膜到达阴极室，将还原态的媒介体B电解液由阴极室通入催化反应器II，在催化剂的作用下，质子、还原态的媒介体B电解液与二氧化碳发生反应，生成一氧化碳和氢气即合成气，同时还原态的媒介体B电解液被氧化为氧化态，接着，将氧化态的媒介体B电解液回流到液流电池阴极室，通过电解反应，再次生成还原态的媒介体B电解液，媒介体B电解液在催化反应器II和阴极室之间进行循环。The protons pass through the membrane of the flow battery to the cathode chamber, and the reduced electrolyte of mediator B is passed from the cathode chamber to the catalytic reactor II. Under the action of the catalyst, the protons, the electrolyte of the reduced mediator B and carbon dioxide react , to generate carbon monoxide and hydrogen, that is, synthesis gas, and at the same time, the electrolyte of the mediator B in the reduced state is oxidized to an oxidized state. Then, the electrolyte of the mediator B in the oxidized state is returned to the cathode chamber of the flow battery, and the reduced state is generated again through the electrolytic reaction. The medium B electrolyte in the state, the medium B electrolyte is circulated between the catalytic reactor II and the cathode chamber.

优选地，所述液流电池的阳极室的媒介体A电解液中媒介体A选自Ce³⁺/Ce⁴⁺、Mn²⁺/Mn³⁺中的至少一种；所述媒介体A的摩尔浓度为1×10^-3～2mol/L。Preferably, the medium A in the electrolyte of the anode chamber of the flow battery is selected from at least one of Ce³⁺ /Ce⁴⁺ , Mn²⁺ /Mn³⁺ ; The molar concentration is 1×10^-3 ～2 mol/L.

优选地，所选液流电池的阴极室的媒介体B电解液中媒介体B选自H₆[P₂W₁₈O₆₂]/Li₆[P₂W₁₈O₆₂]、H₄SiW₁₂O₄₀/Na₄SiW₁₂O₄₀、Cr²⁺/Cr³⁺、乙二胺四乙酸铬(Cr(II)EDTA/Cr(III)EDTA)、丙二胺四乙酸铬(Cr(II)EPTA/Cr(III)EPTA)、V²⁺/V³⁺中的至少一种；所述媒介体B的摩尔浓度为1×10^-3～2mol/L。Preferably, the medium B in the electrolyte of the cathode chamber of the selected flow battery is selected from H₆ [P₂ W₁₈ O₆₂ ]/Li₆ [P₂ W₁₈ O₆₂ ], H₄ SiW₁₂ O₄₀ /Na₄ SiW₁₂ O₄₀ , Cr²⁺ /Cr³⁺ , chromium ethylenediaminetetraacetic acid (Cr(II)EDTA/Cr(III)EDTA), propylenediaminetetraacetic acid chromium (Cr(II)EPTA/ At least one of Cr(III)EPTA), V²⁺ /V³⁺ ; the molar concentration of the mediator B is 1×10^-3 -2 mol/L.

优选地，所述液流电池的电解液的pH值为2～8。Preferably, the electrolyte of the flow battery has a pH value of 2-8.

上述根据所采用液流电池阳极化学电解液中所含媒介体A的状态，形成对应的氧化态的媒介体A电解液和还原态的媒介体A电解液。According to the state of the mediator A contained in the anode chemical electrolyte of the flow battery used above, the corresponding electrolyte of the mediator A in the oxidized state and the electrolyte of the mediator A in the reduced state are formed.

以媒介体Ce³⁺/Ce⁴⁺为例说明，大量含有Ce³⁺的化学电解液为还原态电解液，Ce³⁺在阳极氧化后，生成大量含有Ce⁴⁺的溶液，称为氧化态电解液。液流电池阴极电解液中所含媒介体B的状态，形成对应的氧化态电解液和还原态电解液；以媒介体Cr(II)EDTA/Cr(III)EDTA为例说明，大量含有Cr(III)EDTA的化学电解液为氧化态的电解液，Cr(III)EDTA在阳极还原后，生成大量含有Cr(II)EDTA的溶液，称为还原态的电解液。Taking the medium Ce³⁺ /Ce⁴⁺ as an example, the chemical electrolyte containing a large amount of Ce³⁺ is a reduced state electrolyte. After Ce³⁺ is anodized, a large amount of Ce⁴⁺ is generated, which is called the oxidation state. electrolyte. The state of the mediator B contained in the catholyte of the flow battery forms the corresponding oxidized electrolyte and reduced electrolyte; taking the mediator Cr(II)EDTA/Cr(III)EDTA as an example, a large amount of Cr( III) The chemical electrolyte of EDTA is an electrolyte in an oxidized state. After Cr(III)EDTA is reduced at the anode, a large amount of Cr(II)EDTA-containing solution is generated, which is called a reduced electrolyte.

优选地，所述液流电池的隔膜为Nafion膜、多孔陶瓷隔膜、多孔聚烯烃膜、磺化聚苯砜膜中的一种。Preferably, the diaphragm of the liquid flow battery is one of Nafion membrane, porous ceramic diaphragm, porous polyolefin membrane, and sulfonated polyphenylsulfone membrane.

优选地，所述液流电池施加电压为1.35～3V。Preferably, the applied voltage of the flow battery is 1.35-3V.

优选地，所述电压为直流电压。Preferably, the voltage is a DC voltage.

优选地，所述催化反应器I中的催化剂包括RuO₂、IrO₂、MnO₃、MoO₂中的至少一种。Preferably, the catalyst in the catalytic reactor I includes at least one of RuO₂ , IrO₂ , MnO₃ , and MoO₂ .

优选地，所述催化反应器Ⅱ中的催化剂包括钴酞箐、钴卟啉、铜酞箐、铜卟啉、铁氮碳、镍氮碳、钴氮碳、Au、Ag中的至少一种。Preferably, the catalyst in the catalytic reactor II includes at least one of cobalt phthalocyanine, cobalt porphyrin, copper phthalocyanine, copper porphyrin, iron nitrogen carbon, nickel nitrogen carbon, cobalt nitrogen carbon, Au, and Ag.

本发明的另一方面还提供了上述液流电池辅助的二氧化碳还原制取合成气的方法所用的装置，所述装置包括液流电池、催化反应器I和催化反应器II。Another aspect of the present invention also provides a device used in the above-mentioned method for producing synthesis gas by reduction of carbon dioxide assisted by a flow battery, and the device includes a flow battery, a catalytic reactor I and a catalytic reactor II.

所述液流电池包括阳极室和阴极室；所述阳极室的出液口与所述催化反应器装置I的进液口管路连接；所述阳极室的进液口与所述催化反应器I的出液口管路连接；所述阴极室的出液口与所述催化反应器II的进液口管路连接；所述阴极室的进液口与所述催化反应器装置II的出液口管路连接。The liquid flow battery includes an anode chamber and a cathode chamber; the liquid outlet of the anode chamber is connected with the liquid inlet pipeline of the catalytic reactor device 1; the liquid inlet of the anode chamber is connected with the catalytic reactor The liquid outlet pipeline of I is connected; The liquid outlet of described cathode chamber is connected with the liquid inlet pipeline of described catalytic reactor II; The liquid inlet of described cathode chamber is connected with the outlet of described catalytic reactor device II Fluid line connection.

本发明中，氧化态的媒介体A电解液和还原态的媒介体B电解液在液流电池中产生的；水氧化产生氧气在催化反应器装置I中进行；二氧化碳还原产生合成气在催化反应器装置II中进行。In the present invention, the medium A electrolyte in the oxidized state and the medium B electrolyte in the reduced state are produced in the flow battery; the oxidation of water to generate oxygen is carried out in the catalytic reactor device I; the reduction of carbon dioxide to produce synthesis gas is carried out in the catalytic reaction carried out in Device Apparatus II.

通过上述方法，可以循环的将二氧化碳转化为合成气，二氧化碳转化合成气的效率不低于90％。Through the above method, carbon dioxide can be converted into synthesis gas in a circular manner, and the conversion efficiency of carbon dioxide into synthesis gas is not lower than 90%.

优选地，所述催化反应器I、催化反应器Ⅱ内沿纵向均间隔设置多层筛板；所述筛板上设置有催化剂，所述筛板为多孔陶瓷筛板，所述多孔陶瓷筛板的孔隙直径为10～500微米。Preferably, the catalytic reactor I and the catalytic reactor II are provided with multi-layer sieve plates evenly spaced along the longitudinal direction; the sieve plates are provided with catalysts, the sieve plates are porous ceramic sieve plates, and the porous ceramic sieve plates are The pore diameter is 10-500 microns.

优选地，所述装置还包括电源，所述电源分别与阴极和阳极电路连接。Preferably, the device further comprises a power supply connected to the cathode and anode circuits respectively.

通过采用该装置实现对阳极媒介体A电解液和阴极媒介体B电解液的闭路循环使用，同时对待处理气体中所含二氧化碳进行循环处理，提高处理效率，实现二氧化碳的转化利用。By adopting the device, the closed-circuit circulation of the electrolyte of the anode medium A and the electrolyte of the cathode medium B is realized, and at the same time, the carbon dioxide contained in the gas to be treated is recycled to improve the treatment efficiency and realize the conversion and utilization of carbon dioxide.

本发明的原理为：Principle of the present invention is:

液流电池阳极中获得的氧化态的媒介体A电解液被泵送到所述催化反应I与水接触反应得到氧气、质子和还原态的媒介体A电解液；其中，产生氧气被收集，质子和还原态的媒介体A电解液被泵送至所述阳极室完成循环。质子穿过液流电池隔膜到达阴极室，含有质子的还原态的媒介体B电解液被泵送到催化反应器II，还原态的媒介体B电解液与二氧化碳反应，得到合成气和氧化态的媒介体B电解液；其中，合成气被收集，氧化态的媒介体B电解液被泵送至所述的液流电池阴极室完成循环。The oxidized state mediator A electrolyte obtained in the anode of the flow battery is pumped to the catalytic reaction I to contact with water to obtain oxygen, protons and the reduced state mediator A electrolyte; wherein, the generated oxygen is collected, and the protons and reduced mediator A electrolyte is pumped to the anode chamber to complete the cycle. The protons pass through the flow battery diaphragm to the cathode chamber, and the reduced medium B electrolyte containing protons is pumped to the catalytic reactor II, where the reduced medium B electrolyte reacts with carbon dioxide to obtain synthesis gas and oxidized Medium B electrolyte; wherein, the synthesis gas is collected, and the oxidized medium B electrolyte is pumped to the cathode chamber of the liquid flow battery to complete the cycle.

本发明涉及一种液流电池辅助的二氧化碳还原制取合成气的方法及装置。在本发明中，将二氧化碳转化为合成气产品的方法分三步进行。第一步在液流电池内完成，液流电池的阳极室和阴极室采用质子膜隔离；在外加电压的作用，在阳极得到氧化态的媒介体A电解液，同时阴极得到还原态的媒介体B电解液。第二步在催化反应器I内进行，氧化态的媒介体A电解液被泵传送到催化反应器I内，在催化剂的作用下与水发生反应，生成氧气、质子和还原态的媒介体A电解液，氧气被收集，质子和还原态的媒介体A电解液再被泵传送到液流电池阳极室完成循环。第三步在催化反应器II内进行，质子和还原态的媒介体B电解液被泵传送到催化反应器II，在催化剂的作用下，催化二氧化碳还原生成合成气和氧化态的媒介体B电解液，氧化态的媒介体B电解液再被泵传送到液流电池阴极室完成循环。The invention relates to a method and a device for producing synthesis gas by reducing carbon dioxide assisted by a liquid flow battery. In the present invention, the method of converting carbon dioxide into a synthesis gas product is carried out in three steps. The first step is completed in the flow battery. The anode chamber and the cathode chamber of the flow battery are separated by a proton membrane; under the action of an applied voltage, the electrolyte of mediator A in an oxidized state is obtained at the anode, and the mediator in a reduced state is obtained at the cathode B electrolyte. The second step is carried out in the catalytic reactor I. The oxidized mediator A electrolyte is pumped into the catalytic reactor I, and reacts with water under the action of the catalyst to generate oxygen, protons and reduced mediator A. The electrolyte and oxygen are collected, and the protons and reduced mediator A electrolyte are pumped to the anode chamber of the flow battery to complete the cycle. The third step is carried out in the catalytic reactor II. The protons and the reduced state mediator B electrolyte are pumped to the catalytic reactor II. Under the action of the catalyst, the catalytic carbon dioxide is reduced to generate synthesis gas and the oxidized state mediator B is electrolyzed. The oxidized medium B electrolyte is pumped to the cathode chamber of the flow battery to complete the cycle.

本发明中，“液流电池阳极室”，是指包括液流电池装置的阳极区域、容纳于该阳极区域内的电解液以及插入电解液中的阳极。“液流电池阴极室”，是指包括液流电池装置的阴极区域、容纳于该阴极区域内的电解液以及插入电解液中的阴极。“阳极媒介体A电解液”，是指特定含有氧化还原状态媒介体A的溶液，“阴极媒介体B电解液”，是指含有特定氧化还原媒介体B溶液。In the present invention, "the anode compartment of the flow battery" refers to the anode area of the flow battery device, the electrolyte contained in the anode area, and the anode inserted into the electrolyte. "Cathode compartment of a flow battery" refers to the cathode area of the flow battery device, the electrolyte contained in the cathode area, and the cathode inserted into the electrolyte. "Anode mediator A electrolyte" refers to a solution containing specific redox mediator A, and "cathode mediator B electrolyte" refers to a solution containing specific redox mediator B.

本发明的有益效果为：The beneficial effects of the present invention are:

(1)本发明所提供的液流电池辅助的二氧化碳还原制取合成气的方法，在液流电池阳极产生氧化态的媒介体A电解液，将所得氧化态的媒介体A电解液用于水的氧化，生成氧气，在液流电池阴极产生还原态的媒介体B电解液，质子和还原态的媒介体B电解液在催化剂的作用下生成合成气。通过此方法实现二氧化碳到合成气的转化，二氧化碳转化合成气的效率不低于90％。(1) The method for producing synthesis gas by reduction of carbon dioxide assisted by the flow battery provided by the present invention generates an oxidized mediator A electrolyte at the anode of the liquid flow battery, and uses the obtained oxidized mediator A electrolyte in water Oxygen is generated by the oxidation of the flow battery, and the reduced mediator B electrolyte is produced at the cathode of the flow battery, and the protons and the reduced mediator B electrolyte generate synthesis gas under the action of the catalyst. The conversion of carbon dioxide into synthesis gas is realized by this method, and the conversion efficiency of carbon dioxide into synthesis gas is not lower than 90%.

(2)本发明所提供的液流电池辅助的二氧化碳还原制取合成气循环转化处理装置，包括串联循环使用的液流电池、催化反应器I和催化反应器II，三者通过气路和液路相连接，从而实现对含二氧化碳气体的资源化利用。(2) The flow battery-assisted carbon dioxide reduction and synthesis gas circulation conversion treatment device provided by the present invention includes a flow battery, a catalytic reactor I and a catalytic reactor II used in series, and the three pass through the gas path and the liquid Roads are connected to realize resource utilization of carbon dioxide-containing gas.

附图说明Description of drawings

图1为本发明液流电池辅助的二氧化碳还原制取合成气的方法反应过程示意图；Fig. 1 is a schematic diagram of the reaction process of the method for producing synthesis gas by reduction of carbon dioxide assisted by a liquid flow battery in the present invention;

图2为本发明液流电池辅助的二氧化碳还原制取合成气的方法使用的装置示意图；Fig. 2 is a schematic diagram of the device used in the method for producing synthesis gas by reduction of carbon dioxide assisted by a flow battery in the present invention;

图中：100、液流电池，200、催化反应器I，300、催化反应器II，400、筛板，500、电源，600、阳极室，700、阴极室，800、隔膜。In the figure: 100, liquid flow battery, 200, catalytic reactor I, 300, catalytic reactor II, 400, sieve plate, 500, power supply, 600, anode chamber, 700, cathode chamber, 800, diaphragm.

具体实施方式Detailed ways

下面结合实施例详述本发明，但本发明并不局限于这些实施例。The present invention is described in detail below in conjunction with examples, but the present invention is not limited to these examples.

如无特别说明，本发明的实施例中的原料均通过商业途径购买。Unless otherwise specified, the raw materials in the examples of the present invention were purchased through commercial channels.

实施例1Example 1

参见图1和图2，本实施例中阳极和阴极的媒介体的产生是在液流电池100中进行的；水的氧化是在催化反应器I 200内进行；二氧化碳的还原在催化反应器II 300中进行。液流电池100内设有阴极室700与阳极室600。阴极室700与阳极室600之间由Nafion 117隔膜800隔开。催化反应器I 200内沿其纵向相互间隔设有8层石多孔陶瓷筛板400，筛板400孔隙直径为10微米，多孔陶瓷筛板400上固定IrO₂析氧催化剂。催化反应器II 300内沿其纵向相互间隔设有6层石多孔陶瓷筛板400，筛板400孔隙直径为20微米，多孔陶瓷筛板400上固定钴酞箐催化剂。Referring to Fig. 1 and Fig. 2, the generation of the intermediary body of anode and cathode in the present embodiment is carried out inliquid flow battery 100; The oxidation of water is carried out in catalytic reactor I 200; The reduction of carbon dioxide is carried out in catalytic reactor II 300. Theflow battery 100 is provided with acathode chamber 700 and ananode chamber 600 . Thecathode chamber 700 and theanode chamber 600 are separated by a Nafion 117diaphragm 800 . The catalytic reactor I 200 is provided with 8 layers of stone porousceramic sieve plates 400 along its longitudinal interval, thesieve plates 400 have a pore diameter of 10 microns, and the porousceramic sieve plates 400 are fixed with_IrO2 oxygen evolution catalyst. The catalytic reactor II 300 is provided with 6 layers of stone porousceramic sieve plates 400 at intervals along its longitudinal direction. The pore diameter of thesieve plates 400 is 20 microns, and the cobalt phthalocyanine catalyst is fixed on the porousceramic sieve plates 400 .

在阳极室600加入含0.5mol/L的Ce₂(SO₄)₃溶液作为阳极媒介体A电解液。阴极室700加入含1mol/L的VCl₃溶液作为阴极媒介体B电解液。使用盐酸和NaOH溶液调节电解液pH为2.0。阴极和阳极均为石墨电极，石墨电极分别插入阴极化学电解液和阳极化学电解液中。阴极和阳极的纵截面尺寸为5cm×5cm的正方形。A solution containing 0.5 mol/L Ce₂ (SO₄ )₃ is added into theanode chamber 600 as the anode medium A electrolyte. Thecathode chamber 700 is filled with a VCl₃ solution containing 1 mol/L as the cathode medium B electrolyte. The pH of the electrolyte was adjusted to 2.0 using hydrochloric acid and NaOH solution. Both the cathode and the anode are graphite electrodes, and the graphite electrodes are respectively inserted into the cathodic chemical electrolyte and the anode chemical electrolyte. The longitudinal cross-sectional size of the cathode and anode is a square of 5 cm x 5 cm.

外加恒压源通过导线分别连接阴极和阳极，同时电流表串联入电路中。本实施例中反应恒压源施加2.0V直流电压。施加电压后，观测到反应体系电流为120mA。An external constant voltage source is connected to the cathode and anode respectively through wires, and an ammeter is connected in series to the circuit. In this embodiment, the reaction constant voltage source applies a 2.0V DC voltage. After applying the voltage, a current of 120 mA was observed in the reaction system.

反应开始后，阳极化学电解液的颜色逐渐加深，阴极化学电解液的颜色逐渐变浅。反应15h后，阳极室600得到氧化态的媒介体A Ce(SO₄)₂电解液，将氧化态的媒介体A Ce(SO₄)₂电解液引入催化反应器I 200，室温下，在IrO₂的催化作用下，大量氧气析出，收集测定，同时Ce(SO₄)₂被还原生成Ce₂(SO₄)₃。阳极室600中泵入催化反应产生0.5mol/L的Ce₂(SO₄)₃溶液继续反应，实现媒介体Ce(SO₄)₂在阳极室600和催化反应器I 200之间的循环。阴极室700得到媒介体0.5M VCl₂的还原态电解液，将还原态的媒介体VCl₂电解液引入催化反应器II 300内，室温下，在钴酞箐的催化作用下，二氧化碳被还原，产生大量合成气析出，收集测定，同时VCl₂被氧化为VCl₃。阴极室700中泵入催化反应产生的VCl₃溶液溶液继续反应。After the reaction starts, the color of the anode chemical electrolyte gradually deepens, and the color of the cathodic chemical electrolyte gradually becomes lighter. After reacting for 15 hours, theanode chamber 600 obtained the oxidized mediator A Ce(SO₄ )₂ electrolyte, and introduced the oxidized mediator A Ce(SO₄ )₂ electrolyte into the catalytic reactor I 200, at room temperature, in the IrO Under the catalytic action of₂ , a large amount of oxygen is released, collected and measured, and Ce(SO₄ )₂ is reduced to Ce₂ (SO₄ )₃ at the same time. Theanode chamber 600 is pumped into theanode chamber 600 to produce a 0.5 mol/L Ce₂ (SO₄ )₃ solution to continue the reaction, so as to realize the circulation of the medium Ce(SO₄ )₂ between theanode chamber 600 and thecatalytic reactor I 200 . Thecathode chamber 700 obtains a reduced state electrolyte solution of 0.5M VCl₂ as a medium, and introduces the reduced state medium VCl₂ electrolyte into the catalytic reactor II 300. At room temperature, under the catalysis of cobalt phthalocyanine, carbon dioxide is reduced, A large amount of synthesis gas is produced, collected and measured, and VCl₂ is oxidized to VCl₃ at the same time. The_VCl solution produced by the catalytic reaction is pumped into thecathode chamber 700 to continue the reaction.

整个过程中，氢气产生200L、一氧化碳产生490L，氧气产生700L，二氧化碳转化合成气的效率92％。During the whole process, 200L of hydrogen, 490L of carbon monoxide, and 700L of oxygen are produced, and the efficiency of converting carbon dioxide into synthesis gas is 92%.

实施例2Example 2

与实施例1不同之处在于：The difference from Example 1 is:

液流电池的隔膜为磺化聚苯砜膜，在阳极室600，以1.0mol/L MnCl₂的盐酸溶液为阳极化学电解液。电解液的pH为3。催化反应器I 200的催化剂为RuO₂；催化反应器II 300筛板400孔隙直径为200微米。催化反应器II 300的催化剂为镍氮碳。二氧化碳转化合成气的效率93％。The diaphragm of the flow battery is a sulfonated polyphenylsulfone membrane, and in theanode chamber 600, a 1.0 mol/L MnCl₂ hydrochloric acid solution is used as the anode chemical electrolyte. The pH of the electrolyte solution is 3. The catalyst of catalytic reactor I 200 is RuO₂ ; thesieve plate 400 of catalytic reactor II 300 has a pore diameter of 200 microns. The catalyst for catalytic reactor II 300 is nickel nitrogen carbon. The efficiency of converting carbon dioxide into synthesis gas is 93%.

实施例3Example 3

与实施例1不同之处在于：The difference from Example 1 is:

液流电池的隔膜800为多孔聚烯烃膜。在阴极室700，0.4mol/L丙二胺四乙酸铬(Cr(II)EPTA)的溶液为阴极化学电解液。催化剂pH值为7催化反应器I筛板400孔隙直径为300微米。催化反应器I 200的催化剂为RuO₂；催化反应器II 300筛板400孔隙直径为100微米。催化反应器II 300的催化剂为Ag纳米粒子。施加电压为3.0V，二氧化碳转化合成气的效率91％。Theseparator 800 of the flow battery is a porous polyolefin membrane. In thecathode chamber 700, a solution of 0.4 mol/L chromium propylenediamine tetraacetate (Cr(II)EPTA) is the cathodic chemical electrolyte. The pH value of the catalyst is 7. Thesieve plate 400 of the catalytic reactor I has a pore diameter of 300 microns. The catalyst in the catalytic reactor I 200 is RuO₂ ; thesieve plate 400 in the catalytic reactor II 300 has a pore diameter of 100 microns. The catalyst for catalytic reactor II 300 is Ag nanoparticles. With an applied voltage of 3.0V, the efficiency of converting carbon dioxide into syngas is 91%.

实施例4Example 4

与实施例1不同之处在于：The difference from Example 1 is:

阳极化学电解液的组分为1×10^-3mol/L Ce₂(SO₄)₃溶液。在阴极室700，以1×10^-3mol/L H₄SiW₁₂O₄₀溶液为阴极化学电解液。在阳极和阴极间施加的电压为1.35V。催化反应器I 200筛板400孔隙直径为10微米。催化反应器I 200的催化剂为MnO₃；催化反应器II 300筛板400孔隙直径为10微米。催化反应器II 300的催化剂为铜卟啉。二氧化碳转化合成气的效率93％。The composition of the anodic chemical electrolyte is 1×10^-3 mol/L Ce₂ (SO₄ )₃ solution. In thecathode chamber 700, a 1×^{10 −3mol} /L H₄ SiW₁₂ O₄₀ solution is used as the cathodic chemical electrolyte. The voltage applied between the anode and the cathode was 1.35V.Catalytic Reactor I 200sieve plate 400 has a pore diameter of 10 microns. The catalyst in the catalytic reactor I 200 is MnO₃ ; thesieve plate 400 in the catalytic reactor II 300 has a pore diameter of 10 microns. The catalyst for catalytic reactor II 300 is copper porphyrin. The efficiency of converting carbon dioxide into synthesis gas is 93%.

实施例5Example 5

与实施例1不同之处在于：The difference from Example 1 is:

阳极化学电解液的组分为2mol/L Ce₂(SO₄)₃溶液。在阴极室700，以2mol/LLi₆[P₂W₁₈O₆₂]的溶液为阴极化学电解液。在阳极和阴极间施加的电压为3V。催化反应器I 200筛板400孔隙直径为150微米，催化反应器II 300筛板400孔隙直径为100微米。二氧化碳转化合成气的效率96％。The composition of the anodic chemical electrolyte is 2mol/L Ce₂ (SO₄ )₃ solution. In thecathode chamber 700, a solution of 2 mol/L Li₆ [P₂ W₁₈ O₆₂ ] is used as the cathodic chemical electrolyte. The voltage applied between the anode and the cathode was 3V.Catalytic Reactor I 200 sieve 400 has a pore diameter of 150 microns andCatalytic Reactor II 300sieve 400 has a pore diameter of 100 microns. The efficiency of converting carbon dioxide into synthesis gas is 96%.

实施例6Example 6

参见图2，使用以下装置进行二氧化碳还原制取合成气，该装置包括：液流电池100、催化反应器I 200和催化反应器II 300；液流电池100包括阳极室600和阴极室700，阳极室600生成氧化态的媒介体A电解液，阴极室700生成还原态的媒介体B电解液；液流电池阳极室600与催化反应器I 200的进液口管路连接。氧化态的媒介体A电解液被泵入催化反应器I。氧化态的媒介体A电解液自上而下的通过吸收装置200，并在催化反应器I 200中，在催化剂的作用下与水进行反应，生成氧气。催化反应器I 200的顶部设有出气口，反应产生的氧气向上运动通过多层筛板400后，从出气口离开。反应后的阳极媒介体A电解液在催化反应器I 200的底部出液口离开后，其中所含媒介体A为还原态，通过泵进入电化学阳极室中作为电解液再次循环使用。含有质子的阴极媒介体B电解液通过泵进入催化反应器II300。还原态的媒介体B电解液自上而下的通过催化反应器Ⅱ300，在催化反应器Ⅱ300筛板400上固定催化剂作用下，与来自催化反应器II 300进样口的二氧化碳反应，生成氢气和一氧化碳。氢气和一氧化碳通过出气口流出催化反应器II 300。反应后的阴极媒介体B电解液在催化反应器II 300的底部出液口离开，其中所含氧化态的阴极媒介体B电解液，通过泵进入阴极室700中作为电解液再次循环使用。整个处理过程仅需液流电池装置100、催化反应器I 200和催化反应器II 300连用即可实现二氧化碳气体的有效转化，设备简单成本低廉。同时处理效率较高。Referring to Fig. 2, the following device is used to reduce carbon dioxide to produce synthesis gas, which device includes:liquid flow battery 100, catalytic reactor I 200 and catalytic reactor II 300;liquid flow battery 100 includesanode chamber 600 andcathode chamber 700, anode Thechamber 600 generates the electrolyte of the mediator A in the oxidized state, and thecathode chamber 700 generates the electrolyte of the mediator B in the reduced state; theanode chamber 600 of the flow battery is connected with the liquid inlet pipeline of thecatalytic reactor I 200 . The mediator A electrolyte in the oxidized state is pumped into the catalytic reactor I. The oxidized medium A electrolyte passes through theabsorption device 200 from top to bottom, and reacts with water under the action of a catalyst in the catalytic reactor I 200 to generate oxygen. The top of the catalytic reactor I 200 is provided with a gas outlet, and the oxygen generated by the reaction moves upwards through themulti-layer sieve plate 400 and leaves from the gas outlet. After the reacted anode mediator A electrolyte leaves the liquid outlet at the bottom of the catalytic reactor I 200, the mediator A contained therein is in a reduced state, and enters the electrochemical anode chamber through a pump to be recycled as electrolyte again. The cathodic medium B electrolyte containing protons is pumped into catalytic reactor II 300 . The electrolyte solution of mediator B in the reduced state passes through the catalytic reactor II 300 from top to bottom, and reacts with the carbon dioxide from the inlet of the catalytic reactor II 300 to generate hydrogen and carbon monoxide. Hydrogen and carbon monoxide flow out of the catalytic reactor II 300 through the gas outlet. The reacted cathodic medium B electrolyte exits at the bottom liquid outlet of the catalytic reactor II 300, and the oxidized cathodic medium B electrolyte contained therein is pumped into thecathode chamber 700 to be recycled as electrolyte again. The entire treatment process only requires the joint use of the liquidflow battery device 100, the catalytic reactor I 200 and the catalytic reactor II 300 to realize the effective conversion of carbon dioxide gas, and the equipment is simple and low in cost. At the same time, the processing efficiency is high.

实施例1～5所用参数及二氧化碳转化率列于表1中。The parameters used in Examples 1-5 and the conversion rate of carbon dioxide are listed in Table 1.

表1实施例1～5所用参数及二氧化碳转化率Parameters and carbon dioxide conversion rate used in table 1 embodiment 1～5

注释：其中a:二氧化碳转化率按：

F为法拉第常数，96485库伦每摩尔。Note: where a: carbon dioxide conversion rate according to:

F is Faraday's constant, 96485 coulombs per mole.

由上实施例1～5可知，采用本发明提供的方法及装置，可以实现二氧化碳到合成气的转化，从而实现对二氧化碳资源化利用。From the above examples 1 to 5, it can be seen that the conversion of carbon dioxide into synthesis gas can be realized by adopting the method and device provided by the present invention, so as to realize resource utilization of carbon dioxide.

以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few embodiments of the present invention, and do not limit the present invention in any form. Although the present invention is disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any skilled person familiar with the profession, Without departing from the scope of the technical solution of the present invention, some changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (10)

Translated fromChinese

1.一种液流电池辅助的二氧化碳还原制取合成气的方法，其特征在于，包括以下步骤：1. A method for producing synthesis gas by reduction of carbon dioxide assisted by a liquid flow battery, characterized in that, comprising the following steps:液流电池在充电的情况下，阳极生成氧化态的媒介体A电解液，阴极生成还原态的媒介体B电解液；When the flow battery is being charged, the anode generates an oxidized mediator A electrolyte, and the cathode generates a reduced mediator B electrolyte;将氧化态的媒介体A电解液由阳极室通入催化反应器I，在催化剂的作用下，氧化态的媒介体A电解液与水发生化学反应，生成氧气和质子，同时氧化态的媒介体A电解液被还原为还原态，接着，将质子和还原态的媒介体A的电解液混合物返回至液流电池阳极室，通过电解反应，再次生成氧化态的媒介体A电解液，媒介体A电解液在催化反应器I和阳极室之间进行循环；Pass the oxidized mediator A electrolyte from the anode chamber into the catalytic reactor I, under the action of the catalyst, the oxidized mediator A electrolyte reacts with water to generate oxygen and protons, and at the same time the oxidized mediator A The A electrolyte is reduced to a reduced state, and then the electrolyte mixture of the proton and the reduced mediator A is returned to the anode chamber of the flow battery, and the oxidized mediator A electrolyte is generated again through the electrolytic reaction, and the mediator A The electrolyte circulates between the catalytic reactor I and the anode chamber;质子穿过液流电池隔膜到达阴极室，将还原态的媒介体B的电解液由阴极室通入催化反应器II，在催化剂的作用下，质子和还原态的媒介体B的电解液与二氧化碳发生反应，生成一氧化碳和氢气即合成气，同时还原态的媒介体B电解液被氧化为氧化态，接着，将氧化态的媒介体B的电解液回流到液流电池阴极室，通过电解反应，再次生成还原态的媒介体B电解液，媒介体B电解液在催化反应器II和阴极室之间进行循环。The protons pass through the flow battery diaphragm to the cathode chamber, and the electrolyte of the reduced medium B is passed from the cathode chamber into the catalytic reactor II. Under the action of the catalyst, the protons and the electrolyte of the reduced medium B are combined with carbon dioxide A reaction occurs to generate carbon monoxide and hydrogen, that is, synthesis gas. At the same time, the electrolyte of the mediator B in the reduced state is oxidized to an oxidized state. Then, the electrolyte of the mediator B in the oxidized state is returned to the cathode chamber of the flow battery, and through the electrolytic reaction, A reduced state of the mediator B electrolyte is generated again, and the mediator B electrolyte is circulated between the catalytic reactor II and the cathode compartment.2.根据权利要求1所述的方法，其特征在于，所述液流电池的阳极室的媒介体A电解液中媒介体A选自Ce³⁺/Ce⁴⁺、Mn²⁺/Mn³⁺中的至少一种；2. The method according to claim 1, wherein the medium A in the electrolyte of the anode compartment of the flow battery is selected from Ce³⁺ /Ce⁴⁺ , Mn²⁺ /Mn³⁺ at least one of;所述媒介体A的摩尔浓度为1×10^-3～2mol/L。The molar concentration of the vehicle A is 1×10^-3 -2 mol/L.3.根据权利要求1所述的方法，其特征在于，所选液流电池的阴极室的媒介体B电解液中媒介体B选自H₆[P₂W₁₈O₆₂]/Li₆[P₂W₁₈O₆₂]、H₄SiW₁₂O₄₀/Na₄SiW₁₂O₄₀、Cr²⁺/Cr³⁺、乙二胺四乙酸铬(Cr(II)EDTA/Cr(III)EDTA)、丙二胺四乙酸铬(Cr(II)EPTA/Cr(III)EPTA)、V²⁺/V³⁺中的至少一种；3. The method according to claim 1, characterized in that the medium B in the electrolyte of the cathode compartment of the selected flow battery is selected from the group consisting of H₆ [P₂ W₁₈ O₆₂ ]/Li₆ [P₂ W₁₈ O₆₂ ], H₄ SiW₁₂ O₄₀ /Na₄ SiW₁₂ O₄₀ , Cr²⁺ /Cr³⁺ , chromium ethylenediaminetetraacetic acid (Cr(II)EDTA/Cr(III)EDTA), propane At least one of chromium diamine tetraacetate (Cr(II)EPTA/Cr(III)EPTA), V²⁺ /V³⁺ ;所述媒介体B的摩尔浓度为1×10^-3～2mol/L。The molar concentration of the vehicle B is 1×10^-3 -2 mol/L.4.根据权利要求1所述的方法，其特征在于，所述催化反应器I中的催化剂包括RuO₂、IrO₂、MnO₃、MoO₂中的至少一种。4. The method according to claim 1, characterized in that the catalyst in the catalytic reactor I comprises at least one of_RuO2 ,_IrO2 ,_MnO3 ,_MoO2 .5.根据权利要求1所述的方法，其特征在于，所述催化反应器Ⅱ中的催化剂包括钴酞箐、钴卟啉、铜酞箐、铜卟啉、铁氮碳、镍氮碳、钴氮碳、Au、Ag中的至少一种。5. The method according to claim 1, wherein the catalyst in the catalytic reactor II comprises cobalt phthalocyanine, cobalt porphyrin, copper phthalocyanine, copper porphyrin, iron nitrogen carbon, nickel nitrogen carbon, cobalt At least one of nitrogen carbon, Au, Ag.6.根据权利要求1所述的方法，其特征在于，所述液流电池的电解液的pH值为2～8。6 . The method according to claim 1 , wherein the electrolyte of the flow battery has a pH value of 2-8.7.根据权利要求1所述的方法，其特征在于，所述液流电池的隔膜为Nafion膜、多孔陶瓷隔膜、多孔聚烯烃膜、磺化聚苯砜膜中的一种。7. The method according to claim 1, wherein the diaphragm of the liquid flow battery is one of a Nafion membrane, a porous ceramic diaphragm, a porous polyolefin membrane, and a sulfonated polyphenylsulfone membrane.8.根据权利要求1所述的方法，其特征在于，所述液流电池施加电压为1.35～3V。8. The method according to claim 1, wherein the applied voltage of the flow battery is 1.35-3V.9.一种如权利要求1～8中任一项所述的液流电池辅助的二氧化碳还原制取合成气的方法所用的装置，其特征在于，所述装置包括液流电池、催化反应器I和催化反应器II；9. A device used in the method for producing synthesis gas by the assisted carbon dioxide reduction of a flow battery as claimed in any one of claims 1 to 8, characterized in that the device comprises a flow battery, a catalytic reactor 1 and Catalytic Reactor II;所述液流电池包括阳极室和阴极室；所述阳极室的出液口与催化反应器I的进液口管路连接；所述阳极室的进液口与催化反应器I的出液口管路连接；所述阴极室的出液口与催化反应器II的进液口管路连接；所述阴极室的进液口与催化反应器II的出液口管路连接。The liquid flow battery includes an anode chamber and a cathode chamber; the liquid outlet of the anode chamber is connected with the liquid inlet pipeline of the catalytic reactor 1; the liquid inlet of the anode chamber is connected with the liquid outlet of the catalytic reactor 1 pipeline connection; the liquid outlet of the cathode chamber is connected with the liquid inlet pipeline of the catalytic reactor II; the liquid inlet of the cathode chamber is connected with the liquid outlet pipeline of the catalytic reactor II.10.根据权利要求9所述的装置，其特征在于，所述催化反应器I、催化反应器Ⅱ内沿纵向均间隔设置多层筛板；所述筛板上设置有催化剂，所述筛板为多孔陶瓷筛板，所述多孔陶瓷筛板的孔隙直径为10～500微米。10. The device according to claim 9, characterized in that, in the catalytic reactor I and the catalytic reactor II, multilayer sieve plates are evenly spaced vertically; the sieve plate is provided with a catalyst, and the sieve plate It is a porous ceramic sieve plate, and the pore diameter of the porous ceramic sieve plate is 10-500 microns.

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