WO2022227146A1 - Composition and method for capturing and electrolyzing carbon dioxide - Google Patents

Composition and method for capturing and electrolyzing carbon dioxide Download PDF

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WO2022227146A1
WO2022227146A1 PCT/CN2021/095048 CN2021095048W WO2022227146A1 WO 2022227146 A1 WO2022227146 A1 WO 2022227146A1 CN 2021095048 W CN2021095048 W CN 2021095048W WO 2022227146 A1 WO2022227146 A1 WO 2022227146A1
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composition
ppm
capturing
present disclosure
anode
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French (fr)
Chinese (zh)
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加尔格萨希尔
李梦然
拉福德托马斯•爱德华
王国雄
鲁道夫维克多
王新东
李建新
吝章国
常金宝
李立业
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河钢集团有限公司
河钢股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a composition for capturing and electrolyzing CO2 , and more particularly, to a composition for capturing and electrolyzing CO2 and a method for capturing and electrolyzing CO2 .
  • CCS CO2 capture and storage
  • CCU CO2 capture and utilization
  • An object of the present disclosure is to provide a composition that can both capture CO 2 and serve as an electrolyte for CO 2 electrolysis.
  • compositions for capturing and electrolyzing CO 2 including, by mass percentage: 2wt%-60wt% of aminoalcohol compounds and 40wt%-98wt% of alcohols solvent,
  • the composition further comprises 50 ppm to 500 ppm of a chelating agent.
  • the aminoalcohol-based compound may include at least one of an ethanolamine-based compound and an aminocyclic alcohol-based compound.
  • the ethanolamine compound may include at least one of monoethanolamine, diethanolamine, and triethanolamine.
  • the aminocycloalcohol compound may include at least one of aminocyclopentanol, aminocyclohexanol, and aminocycloheptanol.
  • the ethanolamine compound may be monoethanolamine, and the purity of the monoethanolamine may be 99.5wt%-98wt%.
  • the alcohol-based solvent may include at least one of methanol, ethanol, propanol, and butanol.
  • the chelating agent may include ethylenediaminetetraacetic acid.
  • the composition may further include 1 ppm to 10,000 ppm of piperazine, based on the total weight of the composition.
  • the composition may further include at least one of propylene carbonate, dimethyl ether, polyethylene glycol, acetonitrile, and dimethylformamide.
  • a method of capturing and electrolyzing CO comprising the steps of contacting a gas mixture comprising CO with the composition described above to obtain a composition comprising CO and the a mixture of compositions; supplying a mixture comprising CO and the composition as an electrolyte to an electrolysis device, wherein the electrolysis device includes an anode, a cathode, and an ion-conducting membrane disposed between the anode and the cathode; and a pair of anodes And the cathode is energized, thereby electrolyzing CO 2 .
  • the cathode may include at least one of silver, nickel, cobalt, zinc, palladium, tin, bismuth, mercury, lead, and copper.
  • the cathode can be a metal foil, a porous metal, or a composite electrode in which the catalyst is supported on a porous carbon or polymer material.
  • the anode may include one of graphite, a noble metal catalyst-based dimensionally stable anode, a foam electrode, and a non-noble metal electrode.
  • the electrification step may be performed at a predetermined temperature (eg, normal temperature or low temperature) under the condition of stirring the electrolyte.
  • a predetermined temperature eg, normal temperature or low temperature
  • the composition for capturing and electrolyzing CO 2 according to the present disclosure can both capture CO 2 and act as an electrolyte to electrolyze CO 2 , and can improve the conversion efficiency of CO 2 . Furthermore, the composition for capturing and electrolyzing CO 2 according to the present disclosure can reduce the requirement for the purity of monoethanolamine. In addition, the compositions of the non-aqueous systems of the present disclosure can greatly improve the Faradaic efficiency of CO. Furthermore, the method for capturing and electrolyzing CO 2 according to the present disclosure can reduce the cost of controlling carbon dioxide emissions.
  • FIG. 1 is a flow chart illustrating a method for capturing and electrolyzing CO 2 according to an embodiment of the present disclosure.
  • FIG. 2 is a graph showing the Faradaic efficiencies of H 2 and CO after conversion of Examples 1 to 5.
  • FIG. 2 is a graph showing the Faradaic efficiencies of H 2 and CO after conversion of Examples 1 to 5.
  • FIG. 3 is a graph showing the Faradaic efficiency of H 2 after conversion for Reference Example 1, Example 6, and Example 7.
  • FIG. 3 is a graph showing the Faradaic efficiency of H 2 after conversion for Reference Example 1, Example 6, and Example 7.
  • FIG. 4 is a graph showing the Faradaic efficiency of the converted CO of Reference Example 1, Example 6, and Example 7.
  • FIG. 4 is a graph showing the Faradaic efficiency of the converted CO of Reference Example 1, Example 6, and Example 7.
  • Figure 5 is a graph showing the Faradaic efficiency of CO in compositions with the addition of varying amounts of EDTA.
  • the present invention provides a composition for capturing and electrolyzing CO 2 .
  • the composition comprises in mass percentage: 2wt%-60wt% of an amino alcohol compound and 40wt%-98wt% of an alcohol solvent, wherein, based on the
  • the composition also includes 50 ppm to 500 ppm of the chelating agent, based on the total weight of the composition.
  • the amino alcohol compound may refer to a compound including an amino group and a hydroxyl group, for example, a compound including a primary amine group, a secondary amine group, a tertiary amine group or a cyclic amine group and a hydroxyl group.
  • the aminoalcohol-based compound may include at least one of an ethanolamine-based compound and an aminocyclic alcohol-based compound.
  • the ethanolamine-based compound may include at least one of monoethanolamine, diethanolamine, and triethanolamine; however, embodiments of the present disclosure are not limited thereto.
  • the ethanolamine compound is monoethanolamine (MEA).
  • the purity of monoethanolamine has a great influence on the Faradaic efficiency of CO.
  • the purity of monoethanolamine can be 99.5wt%-98wt%.
  • the aminocycloalcohol compound may include at least one of aminocyclopentanol, aminocyclohexanol, and aminocycloheptanol; however, embodiments of the present disclosure are not limited thereto.
  • the content of the amino alcohol compound is in the range of 2wt%-60wt%, for example, 5wt%-55wt%, 10wt%-50wt%, 15wt%-45wt%, 20wt%-40wt%, Within the range of 25wt%-35wt%, or any range defined by the values given above, eg, 20wt%-35wt%, 35wt%-50wt%, or 15wt%-25wt%.
  • the content of the amino alcohol compound may be in the range of 26wt%-32wt%, more preferably, may be 30wt%.
  • the alcohol-based solvent may refer to an alcohol-based compound containing one or more hydroxyl groups.
  • the alcohol-based solvent may include at least one of methanol, ethanol, propanol (eg, isopropanol), and butanol; however, embodiments of the present disclosure are not limited thereto.
  • the alcohol solvent may include methanol.
  • the content of the alcohol solvent may be in the range of 40wt%-98wt%, for example, 40wt%-95wt%, 45wt%-90wt%, 50wt%-85wt%, 55wt%-80wt%, Within the range of 60wt%-75wt% or 65wt%-70wt%, or any range defined by the values given above, eg, 50wt%-80wt%, 55wt%-75wt% or 65wt%-75wt%.
  • the content of the alcohol solvent may be in the range of 68wt%-72wt%, more preferably, it may be 70wt%.
  • the composition does not include water as a solvent.
  • the composition when using the traditional method in the art using KHCO3 as a CO2 capture solvent, only 0.0056 mol CO2 can be captured per mole of this capture solvent in a 5 wt% K2CO3 aqueous solution.
  • the composition by using a mixture of an alcohol amine-based compound and a non-aqueous solvent alcohol-based compound as a solvent, the composition has a sufficiently high CO capture capability (eg, capable of capturing CO per 1 mole of the composition). 0.5mol-0.55mol CO 2 ), which is obviously better than the existing above-mentioned traditional methods.
  • the CO Faradaic Efficiency (FE) of the compositions according to the present disclosure is as high as 72%.
  • the purity of alkanolamines is extremely high, specifically, taking monoethanolamine (MEA) as an example, under the same conditions, the Faradaic efficiency of CO (FE) of the MEA with the purity greater than 99.5% ) is significantly higher than the Faradaic efficiency of CO for the example of MEA with 98% purity.
  • MEA monoethanolamine
  • the present inventor proposes to add a chelating agent to the mixture of the alcohol amine compound and the alcohol solvent.
  • the chelating agent may include ethylenediaminetetraacetic acid.
  • the content of the chelating agent is in the range of 50ppm-500ppm, for example, 70ppm-470ppm, 90ppm-450ppm, 110ppm-430ppm, 130ppm-410ppm, 150ppm-390ppm, 170ppm-370ppm, 190ppm- 350 ppm, 210 ppm-330 ppm, 230 ppm-310 ppm, 250 ppm-330 ppm, 270 ppm-310 ppm, or any range defined by the numerical values given above, for example, 130 ppm-250 ppm, 170 ppm-310 ppm, or 150 ppm-500 ppm.
  • the chelating agent can also prevent the electrode from being degraded during the electrolysis of CO 2 , while also ensuring stable operation of the electrochemical reaction.
  • the composition may further include piperazine.
  • Piperazine is able to accelerate the CO2 absorption rate without sacrificing CO2 conversion selectivity.
  • the amount of piperazine may be in the range of 1 ppm-10000 ppm, for example, 100 ppm-9900 ppm, 300 ppm-9700 ppm, 500 ppm-9700 ppm, 700 ppm-9500 ppm, 900 ppm-9300 ppm, 1000 ppm-9000 ppm, 2000 ppm-8000 ppm, Within the range of 3000 ppm-7000 ppm, 4000 ppm-6000 ppm, or any range defined by the numerical values given above, eg, 6000 ppm-10000 ppm or 7000 ppm-9000 ppm.
  • composition according to an embodiment of the present disclosure may further include other non-aqueous organic solvents other than the alcoholic solvent.
  • the composition may further include at least one of propylene carbonate, dimethyl ether, polyethylene glycol, acetonitrile, and dimethylformamide; however, embodiments of the present disclosure are not limited thereto.
  • compositions according to embodiments of the present disclosure may further include additives for increasing ionic conductivity.
  • the additive may be an inorganic salt, eg, sodium chloride, potassium chloride, and the like.
  • compositions according to embodiments of the present disclosure may be applied to processes that emit CO in various industries (eg, industrial processes that generate heat or power from carbon-rich fuels such as coal or natural gas) or use carbon-based The process of producing other chemicals (such as methane) using reducing agents (such as steelmaking) or carbon feedstocks.
  • industries eg, industrial processes that generate heat or power from carbon-rich fuels such as coal or natural gas
  • carbon-based e.g., carbon-based The process of producing other chemicals (such as methane) using reducing agents (such as steelmaking) or carbon feedstocks.
  • a method for capturing and electrolyzing CO 2 according to an embodiment of the present disclosure will be described in detail below with reference to FIG. 1 .
  • the method comprises: contacting a gas mixture comprising CO 2 with a composition according to the above description (step S1 ), whereby the composition is capable of absorbing and capturing CO 2 in the gas mixture to obtain a mixture comprising CO 2 and the composition;
  • the mixture comprising CO 2 and the composition is supplied as an electrolyte into the electrolysis device (step S2 ); and the anode and the cathode are energized, thereby electrolyzing CO 2 (step S3 ).
  • the gas mixture including CO 2 may refer to an exhaust gas stream (eg, blast furnace gas or flue gas, etc.); however, embodiments of the present disclosure are not limited thereto.
  • the composition in step S1 is the same as the composition described above, and thus the description thereof will be omitted.
  • step S1 the composition according to an embodiment of the present disclosure may be placed in a gas absorption unit first, and then a gas mixture (eg, flue gas, etc.) including CO 2 is supplied into the gas absorption unit, so that the composition including CO 2 The gas mixture is contacted with the composition, thereby capturing CO 2 in the gas mixture and obtaining a CO 2 rich fluid.
  • a gas mixture eg, flue gas, etc.
  • B is any basic substance present in the composition such as MEA or methanol etc.
  • the electrolysis device may be any suitable electrolysis device commonly used in the art.
  • the electrolysis device includes an anode, a cathode, and an ion-conducting membrane disposed between the anode and the cathode.
  • the cathode may include at least one of silver, nickel, cobalt, zinc, palladium, tin, bismuth, mercury, lead, and copper;
  • the anode may include one of graphite, noble metal-based dimensionally stable anodes, foam electrodes, and non-precious metal electrodes .
  • the dimensionally stable anode based on noble metal can be, for example, a titanium plate or porous titanium material with noble metals such as IrO 2 and RuO 2 supported on the surface; Metallic porous nickel or titanium material.
  • step S2 the CO2 -enriched fluid obtained by step S1 is pumped into the electrolysis device as electrolyte. Furthermore, it is also possible to feed the gas mixture comprising CO directly into the electrolyzer if the electrolyzer has additional compartments for gas transport and a porous cathode structure for gas diffusion.
  • step S3 the anode and the cathode are energized at a predetermined temperature (eg, normal temperature or low temperature) under the condition of stirring the electrolyte, thereby electrolyzing CO 2 .
  • a predetermined temperature eg, normal temperature or low temperature
  • CO 2 can be electrolyzed under the condition that the cathode potential (V vs. RHE) is -1.084 to -0.784.
  • CO 2 can be converted to value-added chemicals such as CO, CH 4 , formic acid or other products, etc., depending on the type of electrode.
  • metal-based electrodes such as silver, nickel, cobalt, zinc, or palladium help convert CO to CO ; metal-based electrodes such as tin, bismuth, mercury, or lead help convert CO to formic acid salts or formic acid, etc.; copper-based electrodes help convert CO2 into hydrocarbons such as methane, ethylene, methanol, and ethanol, etc.
  • the electrolyte becomes a CO2 -lean fluid, so the electrolyte in the electrolysis unit can be recycled to capture CO2 again.
  • the capture and conversion of CO 2 emissions achieved by the compositions of embodiments of the present disclosure offset more than 90% of the cost of conventional CO 2 capture (eg, >$60 per ton of CO 2 captured using conventional means). For example, reducing the total carbon dioxide emissions of a steel mill by only 10%, the technology critical to this disclosure could save more than $2.4 billion in carbon dioxide emissions control costs per year.
  • composition and method for capturing and electrolyzing CO 2 of the present invention will be described in detail below with reference to examples and FIGS. 2 to 5 .
  • Example 2 (potential of -1.084V), Example 3 was examined in the same manner as Example 1, except that the Faradaic efficiency of CO2 conversion to H2 and CO products was measured at the potential shown in reference to Figure 2
  • the Faradaic efficiencies of the CO products of Example 4 (potential of -0.984V), Example 4 (potential of -0.884V) and Example 5 (potential of -0.784V) are shown in FIG. 2 .
  • the composition of the present disclosure as an electrolyte has significantly improved CO conversion efficiency at different potentials, but has a greater impact on the Faradaic efficiency of CO at different potentials, and the Faradaic efficiency of CO products is up to 72% .
  • the electrolytic cell is an H-type electrolytic cell, the cathode is silver foil, and the anode is a graphite electrode.
  • Reference Example 2 was prepared in the same manner as that of Reference Example 1, except that the corresponding components were added at the contents given in Table 1. The results are shown in Table 1.
  • Examples 6 and 7 were prepared in the same manner as in Reference Example 1, except that the corresponding components were added in the contents given in Table 1. The results are shown in Table 1.
  • Ep represents the maximum positive potential during the test
  • En represents the maximum negative potential during the test
  • RHE irreversible hydrogen electrode
  • FE value represents the average value in the potential range
  • DEA is diethanolamine.
  • Reference Examples 3 to 10 were prepared in the same manner as Reference Example 1 except that the corresponding components were added in the contents given in Table 2, and CO 2 was electrolyzed under the conditions of Table 2 . The results are shown in Table 2.
  • Examples 8 to 24 were prepared in the same manner as in Reference Example 1, except that the corresponding components were added in the contents given in Table 2, and CO 2 was electrolyzed under the conditions of Table 2 . The results are shown in Table 2.
  • composition for capturing and electrolyzing CO 2 can both capture CO 2 and act as an electrolyte to electrolyze CO 2 , and the CO 2 conversion efficiency is significantly improved.
  • compositions of the non-aqueous systems of the present disclosure can greatly improve the Faradaic efficiency of CO.
  • the method for capturing and electrolyzing CO 2 according to the present invention can reduce the cost of controlling carbon dioxide emissions.

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Abstract

Disclosed in the present invention are a composition and method for capturing and electrolyzing carbon dioxide. The composition comprises the following components in percentage by mass: 2-60 wt% of an aminoalcohol compound and 40-98 wt% of an alcohol solvent, wherein the composition further comprises 50-500 ppm of a chelating agent on the basis of the total weight of the composition. The composition for capturing and electrolyzing CO2 according to the present invention is capable of capturing CO2, and also can serve as an electrolyte to carry out CO2 electrolysis. In addition, the composition of a non-aqueous system of the present invention can greatly improve CO Faraday efficiency. Furthermore, the method for capturing and electrolyzing CO2 according to the present invention can reduce the cost of controlling carbon dioxide emissions.

Description

用于捕获并电解二氧化碳的组合物以及方法Compositions and methods for capturing and electrolyzing carbon dioxide 技术领域technical field
本发明涉及一种用于捕获并电解CO 2的组合物，更具体地，涉及一种用于捕获并电解CO 2的组合物及一种捕获并电解CO 2的方法。 The present invention relates to a composition for capturing and electrolyzing CO2 , and more particularly, to a composition for capturing and electrolyzing CO2 and a method for capturing and electrolyzing CO2 .
背景技术Background technique
减少碳排放量是全球范围内的挑战性问题，但同时也带来了巨大的市场机会。2013年，全球二氧化碳排放总量超过320亿吨，其中28％来自中国。作为制造业中最大的能源消耗行业，钢铁行业排放的二氧化碳超过总排放量的5％(约4.5亿吨CO 2)。例如，在典型的基于高炉路线的钢厂中，产生一吨钢需要排放大约两吨CO 2。 Reducing carbon emissions is a challenging issue on a global scale, but it also presents a huge market opportunity. In 2013, the total global carbon dioxide emissions exceeded 32 billion tons, of which 28% came from China. As the largest energy-consuming industry in manufacturing, the steel industry emits more than 5% of total carbon dioxide emissions (about 450 million tons of CO 2 ). For example, in a typical blast furnace route based steel plant, approximately two tons of CO2 are emitted to produce one ton of steel.
使用现有的气液吸收技术从废气或高炉煤气中分离CO 2会在CO 2捕集与封存(CCS)工艺或CO 2捕集与利用(CCU)工艺中带来巨大的经济成本和能源损失。捕获和存储解决方案需要合适的地质储层来存储CO 2，并且储层必须靠近生产现场从而使成本最少化。具有现场捕集CO 2并直接转化为其它化学品的CCU工艺有潜力提供低成本、有效的方式来抵消生产工厂减少CO 2排放的部分成本。关键的挑战是开发一种既可以捕获CO 2又可以用作CO 2电解的电解质的溶剂。 Separation of CO2 from flue gas or blast furnace gas using existing gas-liquid absorption technologies would incur huge economic costs and energy losses in CO2 capture and storage (CCS) processes or CO2 capture and utilization (CCU) processes . Capture and storage solutions require suitable geological reservoirs to store CO2 , and the reservoirs must be close to the production site to minimize costs. A CCU process with on-site capture of CO2 and direct conversion to other chemicals has the potential to provide a low-cost, efficient way to offset some of the cost of reducing CO2 emissions from production plants. The key challenge is to develop a solvent that can both capture CO and serve as an electrolyte for CO electrolysis.
发明内容SUMMARY OF THE INVENTION
本公开的目的在于提供一种既可以捕获CO 2又可以用作CO 2电解的电解质的组合物。 An object of the present disclosure is to provide a composition that can both capture CO 2 and serve as an electrolyte for CO 2 electrolysis.
本公开的目的在于提供一种降低碳密集制造过程和/或动力或热产生过程的CO 2排放的技术。 It is an object of the present disclosure to provide a technique for reducing CO 2 emissions from carbon-intensive manufacturing processes and/or power or heat generation processes.
根据本公开的一方面，提供一种用于捕获并电解CO 2的组合物，所述组合物按质量百分比计包括：2wt％-60wt％的氨基醇类化合物和40wt％-98wt％的醇类溶剂， According to an aspect of the present disclosure, there is provided a composition for capturing and electrolyzing CO 2 , the composition including, by mass percentage: 2wt%-60wt% of aminoalcohol compounds and 40wt%-98wt% of alcohols solvent,
其中，基于所述组合物的总重量，所述组合物还包括50ppm-500ppm的 螯合剂。Wherein, based on the total weight of the composition, the composition further comprises 50 ppm to 500 ppm of a chelating agent.
根据本公开的实施例，氨基醇类化合物可以包括乙醇胺类化合物和氨基环醇类化合物中的至少一种。According to an embodiment of the present disclosure, the aminoalcohol-based compound may include at least one of an ethanolamine-based compound and an aminocyclic alcohol-based compound.
根据本公开的实施例，乙醇胺类化合物可以包括单乙醇胺、二乙醇胺和三乙醇胺中的至少一种。According to an embodiment of the present disclosure, the ethanolamine compound may include at least one of monoethanolamine, diethanolamine, and triethanolamine.
根据本公开的实施例，氨基环醇类化合物可以包括氨基环戊醇、氨基环己醇和氨基环庚醇中的至少一种。According to an embodiment of the present disclosure, the aminocycloalcohol compound may include at least one of aminocyclopentanol, aminocyclohexanol, and aminocycloheptanol.
根据本公开的实施例，乙醇胺类化合物可以为单乙醇胺，单乙醇胺的纯度可以为99.5wt％-98wt％。According to an embodiment of the present disclosure, the ethanolamine compound may be monoethanolamine, and the purity of the monoethanolamine may be 99.5wt%-98wt%.
根据本公开的实施例，醇类溶剂可以包括甲醇、乙醇、丙醇和丁醇中的至少一种。According to an embodiment of the present disclosure, the alcohol-based solvent may include at least one of methanol, ethanol, propanol, and butanol.
根据本公开的实施例，螯合剂可以包括乙二胺四乙酸。According to embodiments of the present disclosure, the chelating agent may include ethylenediaminetetraacetic acid.
根据本公开的实施例，基于组合物的总重量，组合物还可以包括1ppm-10000ppm的哌嗪。According to embodiments of the present disclosure, the composition may further include 1 ppm to 10,000 ppm of piperazine, based on the total weight of the composition.
根据本公开的实施例，组合物还可以包括碳酸亚丙酯、二甲醚、聚乙二醇、乙腈和二甲基甲酰胺中的至少一种。According to an embodiment of the present disclosure, the composition may further include at least one of propylene carbonate, dimethyl ether, polyethylene glycol, acetonitrile, and dimethylformamide.
根据本公开的另一方面，提供一种捕获并电解CO 2的方法，所述方法包括如下步骤：使包括CO 2的气体混合物与以上所述的组合物接触，以得到包括CO 2和所述组合物的混合物；将包括CO 2和所述组合物的混合物作为电解质供应到电解装置中，其中，所述电解装置包括阳极、阴极以及设置在阳极与阴极之间的离子传导膜；以及对阳极和阴极通电，从而电解CO 2。 According to another aspect of the present disclosure, there is provided a method of capturing and electrolyzing CO , the method comprising the steps of contacting a gas mixture comprising CO with the composition described above to obtain a composition comprising CO and the a mixture of compositions; supplying a mixture comprising CO and the composition as an electrolyte to an electrolysis device, wherein the electrolysis device includes an anode, a cathode, and an ion-conducting membrane disposed between the anode and the cathode; and a pair of anodes And the cathode is energized, thereby electrolyzing CO 2 .
根据本公开的实施例，阴极可以包括银、镍、钴、锌、钯、锡、铋、汞、铅和铜中的至少一种。阴极可以是金属箔、多孔金属或者可以是催化剂负载于多孔的碳或者高分子材料上的复合电极。According to an embodiment of the present disclosure, the cathode may include at least one of silver, nickel, cobalt, zinc, palladium, tin, bismuth, mercury, lead, and copper. The cathode can be a metal foil, a porous metal, or a composite electrode in which the catalyst is supported on a porous carbon or polymer material.
根据本公开的实施例，阳极可以包括石墨、基于贵金属催化剂的形稳阳极、泡沫电极和非贵金属电极中的一种。According to an embodiment of the present disclosure, the anode may include one of graphite, a noble metal catalyst-based dimensionally stable anode, a foam electrode, and a non-noble metal electrode.
根据本公开的实施例，可以以预定温度(例如常温或者低温)在搅拌电解质的条件下执行通电步骤。According to an embodiment of the present disclosure, the electrification step may be performed at a predetermined temperature (eg, normal temperature or low temperature) under the condition of stirring the electrolyte.
根据本公开的用于捕获并电解CO 2的组合物既能够捕获CO 2也能够作为电解质使CO 2电解，并且能够提高CO 2的转化效率。此外，根据本公开的用于捕获并电解CO 2的组合物能够降低对单乙醇胺的纯度的要求。此外，本公 开的非水体系的组合物能够大大提高CO的法拉第效率。此外，根据本公开的用于捕获并电解CO 2的方法能够降低控制二氧化碳排放的成本。 The composition for capturing and electrolyzing CO 2 according to the present disclosure can both capture CO 2 and act as an electrolyte to electrolyze CO 2 , and can improve the conversion efficiency of CO 2 . Furthermore, the composition for capturing and electrolyzing CO 2 according to the present disclosure can reduce the requirement for the purity of monoethanolamine. In addition, the compositions of the non-aqueous systems of the present disclosure can greatly improve the Faradaic efficiency of CO. Furthermore, the method for capturing and electrolyzing CO 2 according to the present disclosure can reduce the cost of controlling carbon dioxide emissions.
附图说明Description of drawings
通过结合附图对示例性实施例的描述，发明构思的上述和/或其它特征和方面将变得清楚和易于理解。The above and/or other features and aspects of the inventive concept will become apparent and readily understood from the description of the exemplary embodiments taken in conjunction with the accompanying drawings.
图1是示出根据本公开的实施例的用于捕获并电解CO 2的方法的流程图。 1 is a flow chart illustrating a method for capturing and electrolyzing CO 2 according to an embodiment of the present disclosure.
图2是示出示例1至示例5的转化后的H 2和CO的法拉第效率的曲线图。 FIG. 2 is a graph showing the Faradaic efficiencies of H 2 and CO after conversion of Examples 1 to 5. FIG.
图3是示出参考示例1、示例6和示例7的转化后的H 2的法拉第效率的曲线图。 FIG. 3 is a graph showing the Faradaic efficiency of H 2 after conversion for Reference Example 1, Example 6, and Example 7. FIG.
图4是示出参考示例1、示例6和示例7的转化后的CO的法拉第效率的曲线图。FIG. 4 is a graph showing the Faradaic efficiency of the converted CO of Reference Example 1, Example 6, and Example 7. FIG.
图5是示出在加入不同量的EDTA的组合物的CO的法拉第效率的曲线图。Figure 5 is a graph showing the Faradaic efficiency of CO in compositions with the addition of varying amounts of EDTA.
具体实施方式Detailed ways
下面将通过参照附图来描述实施例，以解释本发明。然而，本发明可以以多种不同的形式来实施，不应该被理解为局限于在此提出的示例性实施例。提供这些实施例使本发明的公开将是彻底的和完整的，并将本发明的范围充分地传达给本领域的技术人员。The embodiments will be described below in order to explain the present invention by referring to the figures. The present invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
本发明提供一种用于捕获并电解CO 2的组合物，该组合物按质量百分比计包括：2wt％-60wt％的氨基醇类化合物和40wt％-98wt％的醇类溶剂，其中，基于该组合物的总重量，组合物还包括50ppm-500ppm的螯合剂。 The present invention provides a composition for capturing and electrolyzing CO 2 . The composition comprises in mass percentage: 2wt%-60wt% of an amino alcohol compound and 40wt%-98wt% of an alcohol solvent, wherein, based on the The composition also includes 50 ppm to 500 ppm of the chelating agent, based on the total weight of the composition.
在本公开的实施例中，氨基醇类化合物可以指包括氨基和羟基的化合物，例如，包括伯胺基团、仲胺基团、叔胺基团或环胺基团以及羟基的化合物。具体地，根据本公开的实施例，氨基醇类化合物可以包括乙醇胺类化合物和氨基环醇类化合物中的至少一种。In the embodiments of the present disclosure, the amino alcohol compound may refer to a compound including an amino group and a hydroxyl group, for example, a compound including a primary amine group, a secondary amine group, a tertiary amine group or a cyclic amine group and a hydroxyl group. Specifically, according to an embodiment of the present disclosure, the aminoalcohol-based compound may include at least one of an ethanolamine-based compound and an aminocyclic alcohol-based compound.
根据本公开的实施例，乙醇胺类化合物可以包括单乙醇胺、二乙醇胺和三乙醇胺中的至少一种；然而，本公开的实施例不限于此。优选地，乙醇胺类化合物是单乙醇胺(MEA)。According to embodiments of the present disclosure, the ethanolamine-based compound may include at least one of monoethanolamine, diethanolamine, and triethanolamine; however, embodiments of the present disclosure are not limited thereto. Preferably, the ethanolamine compound is monoethanolamine (MEA).
单乙醇胺的纯度对CO的法拉第效率影响较大，优选地，单乙醇胺的纯 度可以为99.5wt％-98wt％。The purity of monoethanolamine has a great influence on the Faradaic efficiency of CO. Preferably, the purity of monoethanolamine can be 99.5wt%-98wt%.
根据本公开的实施例，氨基环醇类化合物可以包括氨基环戊醇、氨基环己醇和氨基环庚醇中的至少一种；然而，本公开的实施例不限于此。According to embodiments of the present disclosure, the aminocycloalcohol compound may include at least one of aminocyclopentanol, aminocyclohexanol, and aminocycloheptanol; however, embodiments of the present disclosure are not limited thereto.
在本公开的实施例中，氨基醇类化合物的含量在2wt％-60wt％的范围内，例如，5wt％-55wt％、10wt％-50wt％、15wt％-45wt％、20wt％-40wt％、25wt％-35wt％的范围内，或上述给出的数值限定的任意范围内，例如，20wt％-35wt％、35wt％-50wt％或15wt％-25wt％内。优选地，氨基醇类化合物的含量可以为26wt％-32wt％的范围内，更优选地，可以为30wt％。In the embodiments of the present disclosure, the content of the amino alcohol compound is in the range of 2wt%-60wt%, for example, 5wt%-55wt%, 10wt%-50wt%, 15wt%-45wt%, 20wt%-40wt%, Within the range of 25wt%-35wt%, or any range defined by the values given above, eg, 20wt%-35wt%, 35wt%-50wt%, or 15wt%-25wt%. Preferably, the content of the amino alcohol compound may be in the range of 26wt%-32wt%, more preferably, may be 30wt%.
在本公开的实施例中，醇类溶剂可以指含有一个或更多个羟基的醇类化合物。In the embodiments of the present disclosure, the alcohol-based solvent may refer to an alcohol-based compound containing one or more hydroxyl groups.
根据本公开的实施例，醇类溶剂可以包括甲醇、乙醇、丙醇(例如异丙醇)和丁醇中的至少一种；然而，本公开的实施例不限于此。在本公开的实施例中，优选地，醇类溶剂可以包括甲醇。According to embodiments of the present disclosure, the alcohol-based solvent may include at least one of methanol, ethanol, propanol (eg, isopropanol), and butanol; however, embodiments of the present disclosure are not limited thereto. In the embodiment of the present disclosure, preferably, the alcohol solvent may include methanol.
在本公开的实施例中，醇类溶剂的含量可在40wt％-98wt％的范围内，例如，40wt％-95wt％、45wt％-90wt％、50wt％-85wt％、55wt％-80wt％、60wt％-75wt％或65wt％-70wt％的范围内，或上述给出的数值限定的任意范围内，例如，50wt％-80wt％、55wt％-75wt％或65wt％-75wt％内。优选地，醇类溶剂的含量可以为68wt％-72wt％的范围内，更优选地，可以为70wt％。In an embodiment of the present disclosure, the content of the alcohol solvent may be in the range of 40wt%-98wt%, for example, 40wt%-95wt%, 45wt%-90wt%, 50wt%-85wt%, 55wt%-80wt%, Within the range of 60wt%-75wt% or 65wt%-70wt%, or any range defined by the values given above, eg, 50wt%-80wt%, 55wt%-75wt% or 65wt%-75wt%. Preferably, the content of the alcohol solvent may be in the range of 68wt%-72wt%, more preferably, it may be 70wt%.
此外，在本公开的实施例中，该组合物不包括水作为溶剂。Furthermore, in embodiments of the present disclosure, the composition does not include water as a solvent.
在本领域中，当使用本领域的利用KHCO 3作为CO 2捕获溶剂的传统方法时，在5wt％的K 2CO 3水溶液中，每摩尔该捕获溶剂仅能够捕获0.0056mol CO 2。然而，在本公开的实施例中，通过使用醇胺类化合物与非水溶剂的醇类化合物作为溶剂的混合物，该组合物具有足够高的CO 2捕获能力(例如，每1摩尔组合物能够捕获0.5mol-0.55mol CO 2)，其明显优于现有的上述传统方法。 In the art, when using the traditional method in the art using KHCO3 as a CO2 capture solvent, only 0.0056 mol CO2 can be captured per mole of this capture solvent in a 5 wt% K2CO3 aqueous solution. However, in the embodiments of the present disclosure, by using a mixture of an alcohol amine-based compound and a non-aqueous solvent alcohol-based compound as a solvent, the composition has a sufficiently high CO capture capability (eg, capable of capturing CO per 1 mole of the composition). 0.5mol-0.55mol CO 2 ), which is obviously better than the existing above-mentioned traditional methods.
此外，根据本公开的组合物的CO法拉第效率(FE)高达72％。Furthermore, the CO Faradaic Efficiency (FE) of the compositions according to the present disclosure is as high as 72%.
在CO 2的电解期间，对醇胺类化合物的纯度要求极高，具体地，以单乙醇胺(MEA)为例，在相同条件下，纯度大于99.5％的MEA的示例的CO的法拉第效率(FE)明显高于纯度为98％的MEA的示例的CO的法拉第效率。 During the electrolysis of CO , the purity of alkanolamines is extremely high, specifically, taking monoethanolamine (MEA) as an example, under the same conditions, the Faradaic efficiency of CO (FE) of the MEA with the purity greater than 99.5% ) is significantly higher than the Faradaic efficiency of CO for the example of MEA with 98% purity.
为了降低对醇胺类化合物的纯度要求，本发明人提出，在醇胺类化合物与醇类溶剂的混合物中加入螯合剂。In order to reduce the requirement for the purity of the alcohol amine compound, the present inventor proposes to add a chelating agent to the mixture of the alcohol amine compound and the alcohol solvent.
在本公开的实施例中，螯合剂可以包括乙二胺四乙酸。此外，基于该组合物的总重量，螯合剂的含量为50ppm-500ppm的范围内，例如，70ppm-470ppm、90ppm-450ppm、110ppm-430ppm、130ppm-410ppm、150ppm-390ppm、170ppm-370ppm、190ppm-350ppm、210ppm-330ppm、230ppm-310ppm、250ppm-330ppm、270ppm-310ppm的范围内，或上述给出的数值限定的任意范围内，例如，130ppm-250ppm、170ppm-310ppm或150ppm-500ppm内。In embodiments of the present disclosure, the chelating agent may include ethylenediaminetetraacetic acid. In addition, based on the total weight of the composition, the content of the chelating agent is in the range of 50ppm-500ppm, for example, 70ppm-470ppm, 90ppm-450ppm, 110ppm-430ppm, 130ppm-410ppm, 150ppm-390ppm, 170ppm-370ppm, 190ppm- 350 ppm, 210 ppm-330 ppm, 230 ppm-310 ppm, 250 ppm-330 ppm, 270 ppm-310 ppm, or any range defined by the numerical values given above, for example, 130 ppm-250 ppm, 170 ppm-310 ppm, or 150 ppm-500 ppm.
在本公开的实施例中，螯合剂还能够防止在电解CO 2期间电极被降解，同时还能够确保电化学反应的稳定运行。 In the embodiments of the present disclosure, the chelating agent can also prevent the electrode from being degraded during the electrolysis of CO 2 , while also ensuring stable operation of the electrochemical reaction.
此外，根据本公开的实施例，组合物还可以包括哌嗪。哌嗪能够加速CO 2的吸收速率，但不会牺牲CO 2的转化选择性。 Additionally, according to embodiments of the present disclosure, the composition may further include piperazine. Piperazine is able to accelerate the CO2 absorption rate without sacrificing CO2 conversion selectivity.
基于组合物的总重量，哌嗪的含量可以在1ppm-10000ppm的范围内，例如，100ppm-9900ppm、300ppm-9700ppm、500ppm-9700ppm、700ppm-9500ppm、900ppm-9300ppm、1000ppm-9000ppm、2000ppm-8000ppm、3000ppm-7000ppm、4000ppm-6000ppm的范围内，或上述给出的数值限定的任意范围内，例如，6000ppm-10000ppm或7000ppm-9000ppm内。Based on the total weight of the composition, the amount of piperazine may be in the range of 1 ppm-10000 ppm, for example, 100 ppm-9900 ppm, 300 ppm-9700 ppm, 500 ppm-9700 ppm, 700 ppm-9500 ppm, 900 ppm-9300 ppm, 1000 ppm-9000 ppm, 2000 ppm-8000 ppm, Within the range of 3000 ppm-7000 ppm, 4000 ppm-6000 ppm, or any range defined by the numerical values given above, eg, 6000 ppm-10000 ppm or 7000 ppm-9000 ppm.
此外，根据本公开的实施例的组合物还可以包括除了醇类溶剂之外的其它非水有机溶剂。例如，组合物还可以包括碳酸亚丙酯、二甲醚、聚乙二醇、乙腈和二甲基甲酰胺中的至少一种；然而，本公开的实施例不限于此。In addition, the composition according to an embodiment of the present disclosure may further include other non-aqueous organic solvents other than the alcoholic solvent. For example, the composition may further include at least one of propylene carbonate, dimethyl ether, polyethylene glycol, acetonitrile, and dimethylformamide; however, embodiments of the present disclosure are not limited thereto.
另外，根据本公开的实施例的组合物还可以包括用于增加离子电导率的添加剂。该添加剂可以为无机盐，例如，氯化钠、氯化钾等。Additionally, compositions according to embodiments of the present disclosure may further include additives for increasing ionic conductivity. The additive may be an inorganic salt, eg, sodium chloride, potassium chloride, and the like.
根据本公开的实施例的组合物可以应用于各种工业中的排放CO 2的过程(例如，从富含碳的燃料(如煤或天然气)中产生热量或动力的工业过程)或者使用碳基还原剂(例如炼钢)或碳原料来生产其他化学品(例如甲烷)的过程。 Compositions according to embodiments of the present disclosure may be applied to processes that emit CO in various industries (eg, industrial processes that generate heat or power from carbon-rich fuels such as coal or natural gas) or use carbon-based The process of producing other chemicals (such as methane) using reducing agents (such as steelmaking) or carbon feedstocks.
下面将参照图1详细描述根据本公开的实施例的用于捕获并电解CO 2的方法。 A method for capturing and electrolyzing CO 2 according to an embodiment of the present disclosure will be described in detail below with reference to FIG. 1 .
该方法包括：使包括CO 2的气体混合物与根据以上描述的组合物接触(步骤S1)，从而组合物能够吸收并捕获气体混合物中的CO 2，以得到包括CO 2和该组合物的混合物；将包括CO 2和组合物的混合物作为电解质供应到电解装置中(步骤S2)；以及对阳极和阴极通电，从而电解CO 2(步骤S3)。 The method comprises: contacting a gas mixture comprising CO 2 with a composition according to the above description (step S1 ), whereby the composition is capable of absorbing and capturing CO 2 in the gas mixture to obtain a mixture comprising CO 2 and the composition; The mixture comprising CO 2 and the composition is supplied as an electrolyte into the electrolysis device (step S2 ); and the anode and the cathode are energized, thereby electrolyzing CO 2 (step S3 ).
在步骤S1中，包括CO 2的气体混合物可以指废气流(例如，高炉煤气或烟道气等)；然而，本公开的实施例不限于此。此外，步骤S1中的组合物与上面描述的组合物相同，因此将省略其描述。 In step S1 , the gas mixture including CO 2 may refer to an exhaust gas stream (eg, blast furnace gas or flue gas, etc.); however, embodiments of the present disclosure are not limited thereto. In addition, the composition in step S1 is the same as the composition described above, and thus the description thereof will be omitted.
在步骤S1中，首先可以将根据本公开的实施例的组合物置于气体吸收单元中，然后将包括CO 2的气体混合物(例如烟道气等)供应到气体吸收单元中，从而使包括CO 2的气体混合物与组合物接触，从而捕获气体混合物中的CO 2，并得到富含CO 2的流体。 In step S1, the composition according to an embodiment of the present disclosure may be placed in a gas absorption unit first, and then a gas mixture (eg, flue gas, etc.) including CO 2 is supplied into the gas absorption unit, so that the composition including CO 2 The gas mixture is contacted with the composition, thereby capturing CO 2 in the gas mixture and obtaining a CO 2 rich fluid.
为了便于理解，以化学反应方程式(1)和化学反应方程式(2)示出了MEA捕获CO 2的过程。 For ease of understanding, the process of capturing CO 2 by the MEA is shown in chemical reaction equation (1) and chemical reaction equation (2).
CO 2+MEA＝MEA +COO -                            (1) CO 2 +MEA = MEA + COO - (1)
MEA +COO -+B＝MEACOO -+BH +                      (2) MEA + COO - +B=MEACOO - +BH + (2)
其中，B是存在于组合物中的任何碱性物质，例如MEA或甲醇等。where B is any basic substance present in the composition such as MEA or methanol etc.
在步骤S2中，电解装置可以是本领域中常用的任何适合的电解装置。具体地，电解装置包括阳极、阴极以及设置在阳极与阴极之间的离子传导膜。阴极可以包括银、镍、钴、锌、钯、锡、铋、汞、铅和铜中的至少一种；阳极可以包括石墨、基于贵金属的形稳阳极、泡沫电极和非贵金属电极中的一种。在本公开的实施例中，基于贵金属的形稳阳极例如可以是表面负载IrO 2和RuO 2等贵金属的钛板或多孔钛材料；非贵金属电极例如可以是负载有基于镍、铁、钴等过渡金属的多孔镍或钛材料。 In step S2, the electrolysis device may be any suitable electrolysis device commonly used in the art. Specifically, the electrolysis device includes an anode, a cathode, and an ion-conducting membrane disposed between the anode and the cathode. The cathode may include at least one of silver, nickel, cobalt, zinc, palladium, tin, bismuth, mercury, lead, and copper; the anode may include one of graphite, noble metal-based dimensionally stable anodes, foam electrodes, and non-precious metal electrodes . In the embodiments of the present disclosure, the dimensionally stable anode based on noble metal can be, for example, a titanium plate or porous titanium material with noble metals such as IrO 2 and RuO 2 supported on the surface; Metallic porous nickel or titanium material.
在步骤S2中，将通过步骤S1得到的富含CO 2流体作为电解质被泵送到电解装置中。此外，如果电解装置具有用于气体传输的附加隔室和用于气体扩散的多孔阴极结构，则也可以将包括CO 2气体混合物直接供给到电解装置中。 In step S2, the CO2 -enriched fluid obtained by step S1 is pumped into the electrolysis device as electrolyte. Furthermore, it is also possible to feed the gas mixture comprising CO directly into the electrolyzer if the electrolyzer has additional compartments for gas transport and a porous cathode structure for gas diffusion.
在步骤S3中，在预定温度(例如常温或者低温)下在搅拌电解质的条件下对阳极和阴极通电，从而电解CO 2。具体地，可以在阴极电势(V vs.RHE)为-1.084至-0.784的条件下电解CO 2。 In step S3, the anode and the cathode are energized at a predetermined temperature (eg, normal temperature or low temperature) under the condition of stirring the electrolyte, thereby electrolyzing CO 2 . Specifically, CO 2 can be electrolyzed under the condition that the cathode potential (V vs. RHE) is -1.084 to -0.784.
在本公开的实施例中，根据电极的类型能够将CO 2转化为增值化学品，例如，CO、CH 4、甲酸或其它产物等。例如，诸如银、镍、钴、锌或钯等的金属基电极有助于将CO 2转化为CO；诸如锡、铋、汞或铅等的金属基电极有助于将CO 2转换为甲酸盐或甲酸等；铜基电极有助于将CO 2转化为碳氢化合物，例如甲烷、乙烯、甲醇和乙醇等。 In embodiments of the present disclosure, CO 2 can be converted to value-added chemicals such as CO, CH 4 , formic acid or other products, etc., depending on the type of electrode. For example, metal-based electrodes such as silver, nickel, cobalt, zinc, or palladium help convert CO to CO ; metal-based electrodes such as tin, bismuth, mercury, or lead help convert CO to formic acid salts or formic acid, etc.; copper-based electrodes help convert CO2 into hydrocarbons such as methane, ethylene, methanol, and ethanol, etc.
此外，在电解操作过程中，电解质变成贫CO 2流体，因此可以循环回收电解装置中的电解质，以再次利用其捕获CO 2。 In addition, during the electrolysis operation, the electrolyte becomes a CO2 -lean fluid, so the electrolyte in the electrolysis unit can be recycled to capture CO2 again.
此外，通过本公开的实施例的组合物实现的CO 2排放的捕获和转化抵消了传统捕获CO 2成本(例如，利用传统方式捕获每吨CO 2>60美元)的90％以上的成本。例如，仅将钢厂的二氧化碳排放总量减少10％，以本公开为关键的这项技术每年就能够节省超过24亿美元的二氧化碳排放控制成本。 In addition, the capture and conversion of CO 2 emissions achieved by the compositions of embodiments of the present disclosure offset more than 90% of the cost of conventional CO 2 capture (eg, >$60 per ton of CO 2 captured using conventional means). For example, reducing the total carbon dioxide emissions of a steel mill by only 10%, the technology critical to this disclosure could save more than $2.4 billion in carbon dioxide emissions control costs per year.
下面将结合示例以及图2至图5对本发明的用于捕获并电解CO 2的组合物以及方法进行详细的描述。 The composition and method for capturing and electrolyzing CO 2 of the present invention will be described in detail below with reference to examples and FIGS. 2 to 5 .
1、不同电势下对转化后的CO的法拉第效率的影响1. The effect of different potentials on the Faradaic efficiency of converted CO
示例1Example 1
将30wt％单乙醇胺(纯度为99.5％)溶于70wt％甲醇中，从而得到组合物；利用该组合物对CO 2进行捕获，以得到富含CO 2流体，其pH为8.5；将富含CO 2流体供应到H型三电极体系电解槽中，在-1.184V的电势下测量CO 2转化成H 2和CO产物的法拉第效率，其结果示出在图2中。在电解槽中，阳极室和阴极室被离子传导膜隔开，阴极电极为多晶银箔，阳极电极为石墨，参比电极为Ag|AgCl。 30 wt% monoethanolamine (99.5% purity) was dissolved in 70 wt% methanol to obtain a composition; CO2 was captured using the composition to obtain a CO2 -rich fluid with a pH of 8.5; the CO2-rich fluid was 2 Fluid was supplied to an H-type three-electrode system electrolyzer, and the Faradaic efficiency of CO2 conversion to H2 and CO products was measured at a potential of -1.184 V, the results of which are shown in Figure 2. In the electrolytic cell, the anode and cathode compartments are separated by an ion-conducting membrane, the cathode electrode is polycrystalline silver foil, the anode electrode is graphite, and the reference electrode is Ag|AgCl.
示例2至示例5Example 2 to Example 5
除了在参照图2中示出的电势下测量CO 2转化成H 2和CO产物的法拉第效率之外，以与示例1的方式相同的方式来考察示例2(电势为-1.084V)、示例3(电势为-0.984V)、示例4(电势为-0.884V)和示例5(电势为-0.784V)的CO产物的法拉第效率，其结果示出在图2中。 Example 2 (potential of -1.084V), Example 3 was examined in the same manner as Example 1, except that the Faradaic efficiency of CO2 conversion to H2 and CO products was measured at the potential shown in reference to Figure 2 The Faradaic efficiencies of the CO products of Example 4 (potential of -0.984V), Example 4 (potential of -0.884V) and Example 5 (potential of -0.784V) are shown in FIG. 2 .
从图2可以看出，本公开的组合物作为电解质在不同电势下CO 2的转化效率明显提高，但是在不同的电势下对CO的法拉第效率影响较大，CO产物的法拉第效率最高达72％。 As can be seen from Figure 2, the composition of the present disclosure as an electrolyte has significantly improved CO conversion efficiency at different potentials, but has a greater impact on the Faradaic efficiency of CO at different potentials, and the Faradaic efficiency of CO products is up to 72% .
2、组合物中的添加剂对转化后的CO的法拉第效率的影响2. The effect of additives in the composition on the Faradaic efficiency of the converted CO
参考示例1Reference Example 1
将30wt％纯度大于99.5％的MEA溶于70wt％甲醇中，以得到组合物。利用该组合物对CO 2进行捕获，以得到富含CO 2流体；将富含CO 2流体供应到电解槽中，然后测量CO 2转化成H 2和CO产物的法拉第效率，其结果示出在表1中。电解槽为H型电解槽，阴极为银箔，阳极为石墨电极。 30 wt% MEA with a purity greater than 99.5% was dissolved in 70 wt% methanol to obtain a composition. The composition is used to capture CO2 to obtain a CO2 -enriched fluid; the CO2 -enriched fluid is supplied to an electrolyser, and the Faradaic efficiency of CO2 conversion to H2 and CO products is measured, and the results are shown in in FIG. 1. The electrolytic cell is an H-type electrolytic cell, the cathode is silver foil, and the anode is a graphite electrode.
参考示例2Reference example 2
除了按照表1中给出的含量添加相应的组分之外，以与参考示例1的方式相同的方式来制备参考示例2。结果示于表1中。Reference Example 2 was prepared in the same manner as that of Reference Example 1, except that the corresponding components were added at the contents given in Table 1. The results are shown in Table 1.
示例6和示例7Example 6 and Example 7
除了按照表1中给出的含量添加相应的组分之外，以与参考示例1的方式相同的方式来制备示例6和示例7。结果示于表1中。Examples 6 and 7 were prepared in the same manner as in Reference Example 1, except that the corresponding components were added in the contents given in Table 1. The results are shown in Table 1.
表1Table 1
Figure PCTCN2021095048-appb-000001
Figure PCTCN2021095048-appb-000001
注：Ep表示测试期间的最大正电位，En表示测试期间的最大负电位，RHE(可逆氢电极)表示参考电位，FE值表示电位范围内的平均值，DEA为二乙醇胺。Note: Ep represents the maximum positive potential during the test, En represents the maximum negative potential during the test, RHE (reversible hydrogen electrode) represents the reference potential, FE value represents the average value in the potential range, and DEA is diethanolamine.
从参考示例1和参考示例2能够看出，从FE(CO)的角度看，对MEA的纯度要求高。从参考示例2和示例6能够看出，加入EDTA之后，示例的CO 2转化效率显著改善，能够降低对MEA纯度的要求。 It can be seen from Reference Example 1 and Reference Example 2 that, from the perspective of FE(CO), the purity requirements for MEA are high. It can be seen from Reference Example 2 and Example 6 that after adding EDTA, the CO 2 conversion efficiency of the examples is significantly improved, which can reduce the requirement for MEA purity.
此外，为了更直观地考察参考示例1、示例6和示例7在不同电势下转化后的H 2和CO产物的法拉第效率，如图3和图4所示，以曲线图的方式示出了H 2和CO产物的法拉第效率。 In addition, in order to more intuitively examine the Faradaic efficiencies of H and CO products after conversion of Reference Example 1, Example 6 and Example 7 at different potentials, as shown in Figures 3 and 4, H is shown in a graph 2 and Faradaic efficiencies of CO products.
参照表1、图3和图4，纯度为98％的MEA的参考示例2显示出约38％ 的FE(CO)，其远低于纯度为99.5％的MEA的参考示例1。然而，通过添加150ppm的EDTA后，纯度为98％的MEA的示例6表现出显着的改善，实现了约60％的FE(CO)。此外，加入哌嗪后，在基本不损失CO 2转化选择性的同时能够加速CO 2的吸收速率。 Referring to Table 1, Figure 3 and Figure 4, Reference Example 2 of MEA with 98% purity showed about 38% FE(CO), which was much lower than Reference Example 1 of MEA with 99.5% purity. However, by adding 150 ppm of EDTA, Example 6 of the MEA with a purity of 98% showed a significant improvement, achieving an FE(CO) of about 60%. In addition, the addition of piperazine can accelerate the CO absorption rate without substantially losing CO conversion selectivity.
2、组合物中的添加剂对氨基醇类化合物的纯度的影响2. The influence of additives in the composition on the purity of amino alcohol compounds
参考示例3至参考示例10Reference Example 3 to Reference Example 10
除了按照表2中给出的含量添加相应的组分之外，以与参考示例1的方式相同的方式来制备参考示例3至参考示例10，并按照表2的条件电解CO 2。结果示于表2中。 Reference Examples 3 to 10 were prepared in the same manner as Reference Example 1 except that the corresponding components were added in the contents given in Table 2, and CO 2 was electrolyzed under the conditions of Table 2 . The results are shown in Table 2.
示例8至示例24Example 8 to Example 24
除了按照表2中给出的含量添加相应的组分之外，以与参考示例1的方式相同的方式来制备示例8至示例24，并按照表2的条件电解CO 2。结果示于表2中。 Examples 8 to 24 were prepared in the same manner as in Reference Example 1, except that the corresponding components were added in the contents given in Table 2, and CO 2 was electrolyzed under the conditions of Table 2 . The results are shown in Table 2.
此外，为了更直观地体现EDTA对氨基醇类化合物的纯度的影响，在30wt％的MEA和70wt％的甲醇的基础上加入不同量的EDTA后，以银箔为阴极，石墨为阳极，在不同电势下考察CO的法拉第效率。In addition, in order to more intuitively reflect the effect of EDTA on the purity of amino alcohol compounds, after adding different amounts of EDTA on the basis of 30wt% MEA and 70wt% methanol, silver foil was used as the cathode and graphite was used as the anode. The Faradaic efficiency of CO was investigated under electric potential.
表2Table 2
Figure PCTCN2021095048-appb-000002
Figure PCTCN2021095048-appb-000002
Figure PCTCN2021095048-appb-000003
Figure PCTCN2021095048-appb-000003
Figure PCTCN2021095048-appb-000004
Figure PCTCN2021095048-appb-000004
参照表2和图5，通过加入EDTA后，即使使用纯度低的MEA也能够得到高的FE(CO)，从而能够利用纯度低的MEA来捕获并电解CO 2。 Referring to Table 2 and FIG. 5 , by adding EDTA, high FE(CO) can be obtained even if a low-purity MEA is used, and CO 2 can be captured and electrolyzed by a low-purity MEA.
综上，根据本公开的用于捕获并电解CO 2的组合物既能够捕获CO 2也能够作为电解质使CO 2电解，而且CO 2转化效率显著提高。 In conclusion, the composition for capturing and electrolyzing CO 2 according to the present disclosure can both capture CO 2 and act as an electrolyte to electrolyze CO 2 , and the CO 2 conversion efficiency is significantly improved.
此外，本公开的非水体系的组合物能够大大提高CO的法拉第效率。In addition, the compositions of the non-aqueous systems of the present disclosure can greatly improve the Faradaic efficiency of CO.
此外，根据本发明的用于捕获并电解CO 2的方法能够降低控制二氧化碳排放的成本。 Furthermore, the method for capturing and electrolyzing CO 2 according to the present invention can reduce the cost of controlling carbon dioxide emissions.
虽然已经参照本发明的示例性实施例具体地示出并描述了本发明，但是本领域普通技术人员将理解，在不脱离如权利要求和它们的等同物所限定的 本发明的精神和范围的情况下，可以在此做出形式和细节上的各种改变。应当仅仅在描述性的意义上而不是出于限制的目的来考虑实施例。因此，本发明的范围不是由本发明的具体实施方式来限定，而是由权利要求书来限定，该范围内的所有差异将被解释为包括在本发明中。While the invention has been particularly shown and described with reference to the exemplary embodiments of the invention, it will be understood by those of ordinary skill in the art that the invention can be Where appropriate, various changes in form and detail may be made herein. The embodiments should be considered in a descriptive sense only and not for purposes of limitation. Therefore, the scope of the invention is defined not by the detailed description of the invention but by the appended claims, and all differences within the scope will be construed as being included in the present invention.

Claims (11)

  1. 一种用于捕获并电解CO 2的组合物，所述组合物按质量百分比计包括：2wt％-60wt％的氨基醇类化合物和40wt％-98wt％的醇类溶剂， A composition for capturing and electrolyzing CO 2 , the composition comprises by mass percentage: 2wt%-60wt% of an amino alcohol compound and 40wt%-98wt% of an alcohol solvent,
    其中，基于所述组合物的总重量，所述组合物还包括50ppm-500ppm的螯合剂。Wherein, based on the total weight of the composition, the composition further comprises 50 ppm-500 ppm of a chelating agent.
  2. 根据权利要求1所述的组合物，其中，所述氨基醇类化合物包括乙醇胺类化合物和氨基环醇类化合物中的至少一种。The composition according to claim 1, wherein the amino alcohol compound comprises at least one of an ethanolamine compound and an amino cyclic alcohol compound.
  3. 根据权利要求2所述的组合物，其中，所述乙醇胺类化合物包括单乙醇胺、二乙醇胺和三乙醇胺中的至少一种；The composition according to claim 2, wherein the ethanolamine compound comprises at least one of monoethanolamine, diethanolamine and triethanolamine;
    氨基环醇类化合物包括氨基环戊醇、氨基环己醇和氨基环庚醇中的至少一种。The aminocycloalcohol compounds include at least one of aminocyclopentanol, aminocyclohexanol and aminocycloheptanol.
  4. 根据权利要求3所述的组合物，其中，所述乙醇胺类化合物为单乙醇胺，所述单乙醇胺的纯度为99.5wt％-98wt％。The composition according to claim 3, wherein the ethanolamine compound is monoethanolamine, and the purity of the monoethanolamine is 99.5wt%-98wt%.
  5. 根据权利要求1或3所述的组合物，其中，所述醇类溶剂包括甲醇、乙醇、丙醇和丁醇中的至少一种。The composition according to claim 1 or 3, wherein the alcoholic solvent comprises at least one of methanol, ethanol, propanol and butanol.
  6. 根据权利要求1所述的组合物，其中，所述螯合剂包括乙二胺四乙酸。The composition of claim 1, wherein the chelating agent comprises ethylenediaminetetraacetic acid.
  7. 根据权利要求1所述的组合物，基于所述组合物的总重量，所述组合物还包括1ppm-10000ppm的哌嗪。The composition of claim 1, further comprising 1 ppm to 10000 ppm piperazine, based on the total weight of the composition.
  8. 一种用于捕获并电解CO 2的方法，所述方法包括如下步骤： A method for capturing and electrolyzing CO , the method comprising the steps of:
    使包括CO 2的气体混合物与根据权利要求1至7中任一项所述的组合物接触，以得到包括CO 2和所述组合物的混合物； contacting a gas mixture comprising CO with a composition according to any one of claims 1 to 7 to obtain a mixture comprising CO and the composition;
    将包括CO 2和所述组合物的混合物作为电解质供应到电解装置中，其中，所述电解装置包括阳极、阴极以及设置在阳极与阴极之间的离子传导膜；以及 supplying a mixture comprising CO and the composition as an electrolyte into an electrolysis device, wherein the electrolysis device includes an anode, a cathode, and an ion-conducting membrane disposed between the anode and the cathode; and
    对阳极和阴极通电，从而电解CO 2。 The anode and cathode are energized to electrolyze CO 2 .
  9. 根据权利要求8所述的方法，其中，所述阴极包括银、镍、钴、锌、钯、锡、铋、汞、铅和铜中的至少一种。The method of claim 8, wherein the cathode comprises at least one of silver, nickel, cobalt, zinc, palladium, tin, bismuth, mercury, lead, and copper.
  10. 根据权利要求8所述的方法，其中，所述阳极包括石墨、基于贵金属的形稳阳极、泡沫电极和非贵金属电极中的一种。9. The method of claim 8, wherein the anode comprises one of graphite, a noble metal-based dimensionally stable anode, a foam electrode, and a non-noble metal electrode.
  11. 根据权利要求8所述的方法，其中，以预定温度在搅拌电解质的条 件下执行通电步骤。The method of claim 8, wherein the step of energizing is performed with stirring the electrolyte at a predetermined temperature.
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