WO2025201488A1 - 碳捕集吸收剂中铁离子的去除方法及装置 - Google Patents

碳捕集吸收剂中铁离子的去除方法及装置

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Publication number
WO2025201488A1
WO2025201488A1 PCT/CN2025/085489 CN2025085489W WO2025201488A1 WO 2025201488 A1 WO2025201488 A1 WO 2025201488A1 CN 2025085489 W CN2025085489 W CN 2025085489W WO 2025201488 A1 WO2025201488 A1 WO 2025201488A1
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WO
WIPO (PCT)
Prior art keywords
iron ions
absorption liquid
removal container
liquid
carbon capture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2025/085489
Other languages
English (en)
French (fr)
Inventor
孙北奇
魏忠平
邱林年
杨大鹏
杨发田
刘汉明
王焕君
范紫桉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huaneng Longdong Energy Co Ltd Zhengning Power Plant
Huaneng Clean Energy Research Institute
Original Assignee
Huaneng Longdong Energy Co Ltd Zhengning Power Plant
Huaneng Clean Energy Research Institute
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Publication date
Application filed by Huaneng Longdong Energy Co Ltd Zhengning Power Plant, Huaneng Clean Energy Research Institute filed Critical Huaneng Longdong Energy Co Ltd Zhengning Power Plant
Publication of WO2025201488A1 publication Critical patent/WO2025201488A1/zh
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/10—Magnetic separation acting directly on the substance being separated with cylindrical material carriers
    • B03C1/14—Magnetic separation acting directly on the substance being separated with cylindrical material carriers with non-movable magnets

Definitions

  • the present invention relates to the technical field of carbon capture, and in particular to a method and device for removing iron ions from a carbon capture absorbent.
  • the present invention aims to at least partially address one of the technical problems in the related art.
  • embodiments of the present invention provide a method for removing iron ions from a carbon capture absorbent, which can remove iron ions from the absorbent and improve the performance of the absorbent.
  • the embodiment of the present invention further provides a device for removing iron ions from a carbon capture absorbent.
  • the rate of adding the reducing agent is determined according to the concentration of the ferric ions in the absorption liquid and the flow rate parameter of the absorption liquid, so that part of the ferric ions is reduced to ferrous ions;
  • the precipitate was discharged.
  • the method for removing iron ions from a carbon capture absorbent can remove iron ions from the absorbent and improve the performance of the absorbent.
  • determining the rate of adding the reducing agent according to the concentration of the trivalent iron ions in the absorption liquid and the flow rate parameter of the absorption liquid includes:
  • the area of the pipe cross section at the flow velocity measurement location is calculated as A;
  • the concentration of the ferric iron ions in the absorption liquid is measured to be ;
  • the rate of addition of the reducing agent is calculated as R, and .
  • an alkaline solution is added to the removal container, and the ferric iron ions and the ferrous iron ions react with the alkaline solution to form a precipitate, comprising:
  • the real-time concentration of the ferric ions in the absorption liquid is measured as c;
  • the alkali solution reacts with the ferric ion and the ferrous ion simultaneously, and the reaction is: , the precipitate is ferrosoferric oxide.
  • stopping adding the alkali solution to the absorption liquid comprises:
  • the absorption liquid is a circulating absorption liquid
  • the removal container is provided with an inlet pipe and a liquid outlet pipe arranged opposite to each other, the inlet pipe is suitable for connecting to the analysis tower, and the outlet pipe is suitable for connecting to the absorption tower.
  • a plurality of magnetic rods arranged in a matrix are provided in the removal container, and the magnetic rods are detachably connected to the removal container, and the magnetic rods can absorb the precipitate.
  • an electrically controlled valve the electrically controlled valve being provided on the removal container, the electrically controlled valve having a first state and a second state.
  • the electrically controlled valve is used to add a reducing agent to the removal container so that part of the trivalent iron ions in the absorption liquid is reduced to divalent iron ions.
  • the electrically controlled valve is used to add an alkaline solution to the removal container, and the alkaline solution reacts with the trivalent iron ions and the divalent iron ions in the absorption liquid to generate a precipitate.
  • a magnetic rod is located in the removal container and is used to absorb the precipitate.
  • the device for removing iron ions from a carbon capture absorbent according to an embodiment of the present invention can improve the performance of the absorbent.
  • FIG1 is a schematic flow diagram of a method for removing iron ions from a carbon capture absorbent according to an embodiment of the present invention.
  • FIG2 is a schematic diagram of a device for removing iron ions from a carbon capture absorbent according to an embodiment of the present invention.
  • An embodiment of the present invention proposes a method for removing iron ions in a carbon capture absorbent, comprising transferring an absorption liquid to a removal container; determining a rate of adding a reducing agent based on the concentration of trivalent iron ions in the absorption liquid and a flow rate parameter of the absorption liquid, wherein some trivalent iron ions are reduced to divalent iron ions; when the concentration of trivalent iron ions in the absorption liquid is reduced to a preset concentration, adding an alkaline solution to the removal container, and the trivalent iron ions and divalent iron ions react with the alkaline solution to form a precipitate; when the pH value of the absorption liquid is adjusted to a preset range, stopping adding the alkaline solution to the absorption liquid; and discharging the precipitate.
  • the removal device of this embodiment is arranged between the absorption tower and the decomposition tower, that is, the lean liquid flows out of the decomposition tower and flows into the pipeline between the absorption tower.
  • the content of carbon dioxide in the lean liquid absorbent before entering the absorption tower is small, so as to prevent the reducing agent and alkali solution from affecting the carbon dioxide.
  • the temperature of the lean liquid is not high, and the reaction of iron ions with the reducing agent and alkali solution is not so violent, which is relatively safer, has a better effect on removing iron ions, and has less impact on the absorbent.
  • the reducing agent is sodium thiosulfate or sodium sulfite.
  • the flow rate parameters include the flow rate of the absorption liquid flowing to the removal container, the cross-sectional area of the pipe where the flow rate is measured, and the number of electrons lost by one molecule of the reducing agent during the reaction with the ferric ion.
  • the method for removing iron ions from the carbon capture absorbent in an embodiment of the present invention reduces the valence of the iron ions dissolved in the absorbent by adding a reducing agent to the absorbent, and then adds an alkali solution to the absorbent.
  • a reducing agent to the absorbent
  • an alkali solution to the absorbent.
  • the iron ions in the absorbent are co-precipitated with the alkali solution and converted into solid iron particles. This not only removes the iron ions in the absorbent, but also prevents the iron ions from participating in the degradation process of the absorbent, thereby slowing down the aging rate of the absorbent and improving the performance of the absorbent.
  • this embodiment discharges the solid iron particles produced by co-precipitation of iron ions and alkali solution to the outside of the removal container by filtering or magnetic attraction, thereby removing the iron ions in the absorption liquid and the iron particles generated by the reaction.
  • Combining chemical and physical methods not only improves the removal efficiency, but also makes the operation simple and cost-effective.
  • the long-term operation performance of the absorbent can be significantly improved, while reducing the corrosion risk of the equipment, thereby improving the capture efficiency, operation safety and stability of the carbon capture system.
  • the rate of adding the reducing agent is determined based on the concentration of the ferric iron ions in the absorption liquid and the flow rate parameter of the absorption liquid, including: measuring the flow rate of the absorption liquid flowing to the removal container as V; calculating the area of the pipe cross section at the flow rate measurement position as A; measuring the concentration of the ferric iron ions in the absorption liquid as ; Determine the number of electrons lost by a molecule of reducing agent during the reaction with trivalent iron ions as N; calculate the rate of addition of reducing agent as R, and .
  • this embodiment calculates the rate of addition of the reducing agent by the flow rate of the absorption liquid entering the removal container, the area of the pipe cross-section at the flow rate measurement position, the concentration of trivalent iron ions in the absorption liquid, and the number of electrons lost by one molecule of the reducing agent, and associates the rate of addition of the reducing agent with the iron ions in the absorbent, thereby facilitating the reaction between the reducing agent and the trivalent iron ions and improving the reaction efficiency of the reducing agent and the trivalent iron ions.
  • the removal container in this embodiment is arranged between the absorption tower and the analysis tower, that is, the removal container is embedded in the circulation process of the rich liquid and the lean liquid. Since the absorption liquid is continuously circulating, the addition rate of the reducing agent is limited to facilitate the reaction of the reducing agent with the trivalent iron ions, thereby improving the distribution uniformity of the divalent iron ions in the absorption liquid.
  • the concentration of ferric ions is in mol/m 3
  • the flow rate of the absorption liquid is in m/min
  • the area of the pipe cross section at the flow rate measurement location is m 2
  • the rate of adding the reducing agent is in mol/min.
  • the reducing agent when the reducing agent is sodium thiosulfate, the number of electrons lost by one molecule of the reducing agent during the reaction with trivalent iron ions is 1.
  • the reducing agent when the reducing agent is sodium sulfite, the number of electrons lost by one molecule of the reducing agent during the reaction with trivalent iron ions is 2.
  • Sodium sulfite is used in this embodiment.
  • the alkali solution reacts with the ferric ions and the ferrous ions simultaneously, and the reaction is:
  • the precipitate is ferroferric oxide.
  • reaction of ferric ions under the action of a reducing agent is .
  • stopping adding the alkali solution to the absorption liquid comprises:
  • alkali solution is added into the removal container.
  • the alkaline environment facilitates the reaction of hydroxide in the alkali solution with trivalent iron ions and divalent iron ions.
  • the pH value of the absorption liquid continues to rise under the action of the alkali solution.
  • the electric control valve is closed and the addition of alkali solution into the removal container is stopped.
  • the amount of alkali solution added is limited by the pH value of the absorption liquid to facilitate the reaction of iron ions in the absorption liquid with the alkali solution.
  • the amount of alkali solution added is 5-10 times the amount of reducing agent added.
  • the absorption liquid is a circulating absorption liquid
  • the removal container is provided with a liquid inlet pipe and a liquid outlet pipe arranged relatively to each other.
  • the liquid inlet pipe is suitable for connecting to the analysis tower, and the liquid outlet pipe is suitable for connecting to the absorption tower.
  • the liquid inlet pipe is located on the left side of the removal container, and the liquid outlet pipe is located on the right side of the removal container.
  • One end of the liquid inlet pipe is connected to the decomposition tower, and the other end of the liquid inlet pipe is connected to the removal container to transfer the decomposed lean liquid into the removal container.
  • One end of the liquid outlet pipe is connected to the removal container, and the other end of the liquid outlet pipe is connected to the absorption tower to transfer the lean liquid in the removal container into the absorption tower.
  • the removal container is integrated into the carbon dioxide capture system by setting the liquid inlet pipe and the liquid outlet pipe.
  • This embodiment can be effectively integrated by directly embedding it into the carbon capture system without modifying the carbon capture system, thereby achieving the effect of significantly removing iron ions.
  • This embodiment does not limit the embedding position and can be set after the analysis tower and before the absorption tower. As long as the reduction precipitation method and the ferromagnetic adsorption method are used to remove the iron ions in the absorbent, they are within the protection scope of the embodiment.
  • a plurality of magnetic rods arranged in a matrix are provided in the removal container, and the magnetic rods are detachably connected to the removal container, and the magnetic rods can absorb the precipitate.
  • the outer contour of the magnetic rod on the projection surface perpendicular to the left-right direction and the front-back direction is a rectangle. Since the precipitate in this embodiment is ferroferric oxide, and ferroferric oxide is magnetic, the ferroferric oxide can be adsorbed on the outside of the magnetic rod by the magnetic rod. By introducing the setting of the magnetic rod in this embodiment, the reaction precipitate in the absorbent can be adsorbed and separated, thereby improving the removal efficiency.
  • the provision of multiple magnetic bars can also form a barrier to the absorption liquid, reduce the flow rate of the absorption liquid in the removal container, increase the contact time between the reducing agent and the alkaline solution and the absorption liquid, and improve the removal efficiency of iron ions.
  • the outer contour of the magnetic bar on a projection plane perpendicular to the left-right direction and the front-back direction is a circle.
  • the magnetic rod 4 is used to adsorb the iron-containing precipitate in the carbon capture absorbent, thereby reducing the content of iron impurities in the carbon capture absorbent, achieving the purpose of reducing the degradation of the absorbent and increasing the stability of long-term operation.
  • the magnetic rod 4 and the cover 5 or the bottom of the removal container 1 can be detachably connected by a flange, a clamp, a bolt plate or other means that can quickly release the clip. After running for a period of time, the magnetic rod 4 can be removed, which is convenient for regular cleaning of the magnetic rod 4 and reuse.
  • first and second are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to.
  • a feature defined as “first” or “second” may explicitly or implicitly include at least one such feature.
  • “plurality” means at least two, such as two, three, etc., unless otherwise specifically defined.
  • the terms “installed,” “connected,” “connect,” “fixed,” etc. should be understood in a broad sense. For example, they can refer to fixed connection, detachable connection, or integration; mechanical connection, electrical connection, or communication; direct connection or indirect connection through an intermediate medium; internal communication between two elements or interaction between two elements, unless otherwise specified.
  • installed e.g., a fixed connection, detachable connection, or integration
  • mechanical connection e.g., electrical connection, or communication
  • direct connection or indirect connection through an intermediate medium e.g., internal communication between two elements or interaction between two elements, unless otherwise specified.
  • a first feature being “above” or “below” a second feature may mean that the first and second features are in direct contact, or that the first and second features are in indirect contact through an intermediate medium.
  • a first feature being “above,” “above,” and “above” a second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is at a higher level than the second feature.
  • a first feature being “below,” “below,” and “below” a second feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is at a lower level than the second feature.
  • the terms “one embodiment”, “some embodiments”, “examples”, “specific examples”, or “some examples” mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention.
  • the schematic expressions of the above terms do not necessarily refer to the same embodiment or example.
  • the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
  • those skilled in the art can combine and combine different embodiments or examples described in this specification and the features of different embodiments or examples without contradiction.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

本发明涉及碳捕集技术领域,具体涉及一种碳捕集吸收剂中铁离子的去除方法及装置,所述去除方法包括将吸收液传输至去除容器,根据吸收液中的三价铁离子的浓度以及吸收液的流速参数确定还原剂的加入速度,部分三价铁离子被还原成二价铁离子,吸收液中的三价铁离子的浓度降低至预设浓度时,向去除容器中加入碱液,三价铁离子和二价铁离子与碱液反应生成沉淀物,在吸收液的pH值调节至预设范围时,停止向吸收液中加入碱液,排出沉淀物,本发明实施例的碳捕集吸收剂中铁离子的去除方法,可以去除吸收剂中的铁离子,提高吸收剂的性能。

Description

碳捕集吸收剂中铁离子的去除方法及装置 技术领域
本发明涉及碳捕集技术领域,具体涉及一种碳捕集吸收剂中铁离子的去除方法及装置。
背景技术
在碳捕集系统的长期运行中,由于捕集吸收剂与烟气中的二氧化碳反应、系统的高温条件、以及反应产物的逐渐降解等复杂因素的相互作用,设备的腐蚀问题逐渐显现,设备腐蚀过程中铁质部分被逐渐侵蚀,导致吸收剂中会存在大量杂质铁离子,影响吸收剂的性能。相关技术中多采用吸附过滤的方式进行去除,但是吸附过滤的方式对溶液中的三价铁离子的去除效果较差,进而影响吸收剂的性能。
发明内容
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此,本发明的实施例提出了一种碳捕集吸收剂中铁离子的去除方法,可以去除吸收剂中的铁离子,提高吸收剂的性能。
本发明实施例还提出来一种碳捕集吸收剂中铁离子的去除装置。
本发明实施例的碳捕集吸收剂中铁离子的去除方法,包括:
将吸收液传输至去除容器;
根据所述吸收液中的三价铁离子的浓度以及所述吸收液的流速参数确定还原剂的加入速度,部分所述三价铁离子被还原成二价铁离子;
所述吸收液中的三价铁离子的浓度降低至预设浓度时,向所述去除容器中加入碱液,所述三价铁离子和所述二价铁离子与所述碱液反应生成沉淀物;
在所述吸收液的pH值调节至预设范围时,停止向所述吸收液中加入碱液;
排出所述沉淀物。
本发明实施例的碳捕集吸收剂中铁离子的去除方法,可以去除吸收剂中的铁离子,提高吸收剂的性能。
在一些实施例中,所述根据所述吸收液中的三价铁离子的浓度以及所述吸收液的流速参数确定还原剂的加入速度,包括:
测量所述吸收液流向所述去除容器的流速为V;
计算所述流速的测量位置的管道横截面的面积为A;
测量所述吸收液中的三价铁离子的浓度为 ;
确定一分子还原剂在和三价铁离子反应过程中失去电子的数目为N;
计算所述还原剂的加入速度为R,且 。
在一些实施例中,所述吸收液中的三价铁离子的浓度降低至预设浓度时,向所述去除容器中加入碱液,所述三价铁离子和所述二价铁离子与所述碱液反应生成沉淀物,包括:
测量所述吸收液中的三价铁离子的实时浓度为c;
在c=2/3× 时,利用电控阀向所述去除容器中加入碱液;
所述碱液与所述三价铁离子和所述二价铁离子同时反应,且所述反应为: ,所述沉淀物为四氧化三铁。
在一些实施例中,所述吸收液的pH值调节至预设范围时,停止向所述吸收液中加入碱液,包括:
测量所述去除容器中的吸收液的实时pH值为P;
当10≤P≤12时,关闭所述电控阀。
在一些实施例中,所述吸收液为循环吸收液,所述去除容器上设有相对布置的进液管和出液管,所述进液管适于与解析塔相连,所述出液管适于与所述吸收塔相连。
在一些实施例中,所述去除容器内设有多个呈矩阵排布的磁性棒,所述磁性棒与所述去除容器可拆卸地相连,所述磁性棒可吸附所述沉淀物。
本发明实施例的碳捕集吸收剂中铁离子的去除装置,包括:
去除容器;
进液管和出液管,所述进液管和所述出液管在所述去除容器的径向方向上相对布置,所述进液管适于与解析塔相连以向所述去除容器内传输吸收液,所述出液管适于与所述吸收塔相连以排出所述去除容器内的吸收液;
电控阀,所述电控阀设在所述去除容器上,所述电控阀具有第一状态和第二状态,在所述第一状态,所述电控阀用于向所述去除容器中加入还原剂以使所述吸收液中的部分三价铁离子被还原成二价铁离子,在所述第二状态,所述电控阀用于向所述去除容器内加入碱液,所述碱液与所述吸收液中的三价铁离子和所述二价铁离子反应生成沉淀物;
磁性棒,所述磁性棒位于所述去除容器内,所述磁性棒用于吸附所述沉淀物。
本发明实施例的碳捕集吸收剂中铁离子的去除装置,可以提高吸收剂的性能。
在一些实施例中,所述去除装置还包括盖体,所述去除容器的顶部开口设置,所述盖体盖合在所述去除容器上。
在一些实施例中,所述盖体上设有加入口,所述电控阀的一端与所述盖体相连并通过所述加入口与所述去除容器连通。
在一些实施例中,所述磁性棒的数量为多个,多个所述磁性棒呈矩阵分布,所述磁性棒与所述盖体或所述去除容器的底部可拆卸地相连。
附图说明
图1是本发明实施例的碳捕集吸收剂中铁离子的去除方法的流程示意图。
图2是本发明实施例的碳捕集吸收剂中铁离子的去除装置的示意图。
图3是本发明实施例的碳捕集吸收剂中铁离子的去除装置的另一视角的示意图。
附图标记:
去除容器1,进液管2,出液管3,磁性棒4,盖体5,加入口51。
本发明的实施方式
下面详细描述本发明的实施例,所述实施例的示例在附图中示出。下面通过参考附图描述的实施例是示例性的,旨在用于解释本发明,而不能理解为对本发明的限制。
本发明实施例提出了一种碳捕集吸收剂中铁离子的去除方法,包括将吸收液传输至去除容器;根据吸收液中的三价铁离子的浓度以及吸收液的流速参数确定还原剂的加入速度,部分三价铁离子被还原成二价铁离子;吸收液中的三价铁离子的浓度降低至预设浓度时,向去除容器中加入碱液,三价铁离子和二价铁离子与碱液反应生成沉淀物;吸收液的pH值调节至预设范围时,停止向吸收液中加入碱液;排出沉淀物。
需要说明的是,二氧化碳是酸性气体,二氧化碳在与有机胺类化合物发生化学反应时,会形成一个弱酸性的溶液体系,二氧化碳捕集系统是通过有机胺捕集并吸收二氧化碳。在碳捕集过程中,吸收剂中会存在大量杂质铁离子,杂质铁离子一方面会阻碍吸收剂与二氧化碳之间的有效反应,杂质铁离子另一方面会加速了有机胺吸收剂的降解过程,不但减少了吸收剂的有效性,而且还可能产生更多的腐蚀性物质,加剧设备的腐蚀现象,产生更多的铁离子杂质,本实施例是用于去除二氧化碳捕集系统的吸收剂中的铁离子的去除方法,以减少吸收剂中的铁离子的含量,从而确保碳捕集系统的高效、安全和稳定运行。
具体地,如图1所示,本实施例中将含有三价铁离子的吸收剂传输至去除容器中,向去除容器内添加还原剂,可以理解的是,溶解在溶液中的铁离子一般为三价铁离子,三价铁离子在还原剂的作用下被还原成二价铁离子,通过对吸收液中的三价铁离子的浓度进行实时检测,在吸收液中的三价铁离子的浓度与二价铁离子的浓度达到需求浓度时,向去除容器内添加碱液营造碱性环境,吸收液中的三价铁离子和二价铁离子与碱液发生反应并生成沉淀物,去除吸收液中的铁离子。
可选地,本实施例的去除装置设在吸收塔和解析塔之间,即贫液从解析塔中流出并流向吸收塔之间的管路上,进入吸收塔之前的贫液吸收剂里面二氧化碳的含量少,免得还原剂和碱液对二氧化碳产生影响,而且贫液经过与富液换热后,贫液的温度不高,铁离子与还原剂和碱液的反应没那么剧烈,相对更安全,去除铁离子的效果更好,对吸收剂的影响更小。
例如,还原剂为硫代硫酸钠或亚硫酸钠。
例如,流速参数包括吸收液流向去除容器的流速、流速的测量位置的管道横截面的面积、一分子还原剂在和三价铁离子反应过程中失去电子的数目。
本发明实施例的碳捕集吸收剂中铁离子的去除方法通过向吸收液中添加还原剂来还原溶解在吸收液中的铁离子的化合价,再向吸收液中添加碱液,通过调整还原剂和碱液的化学比例,使吸收液中的铁离子与碱液共沉淀转化为固态的铁颗粒,不仅去除了吸收液中的铁离子,还防止了铁离子参与吸收液的降解过程,从而减缓吸收剂的老化速度,提高吸收液的性能。
进一步地,本实施例通过过滤或磁吸的方式将铁离子与碱液共沉淀产生的固态铁颗粒排出至去除容器外,实现吸收液中的铁离子以及反应生成的铁颗粒的去除,结合化学和物理两种方式,不仅提高了去除效率,而且操作简便,成本效益高,而且通过减少吸收剂中的铁离子含量,可以显著提高吸收剂的长周期运行性能,同时降低设备的腐蚀风险,从而提高了碳捕集系统的捕集效率以及运行安全性和稳定性。
在一些实施例中,根据吸收液中的三价铁离子的浓度以及吸收液的流速参数确定还原剂的加入速度,包括:测量吸收液流向去除容器的流速为V;计算流速的测量位置的管道横截面的面积为A;测量吸收液中的三价铁离子的浓度为 ;确定一分子还原剂在和三价铁离子反应过程中失去电子的数目为N;计算还原剂的加入速度为R,且 。
具体地,本实施例通过对进入去除容器的吸收液的流速以及流速测量位置的管道横截面的面积、吸收液中的三价铁离子的浓度以及一分子还原剂失去电子的数目对还原剂的加入速度进行计算,将还原剂的加入速度与吸收剂中的铁离子进行关联,利于还原剂与三价铁离子的反应,提高还原剂与三价铁离子的反应效率。
进一步地,本实施例中的去除容器是设置在吸收塔和解析塔之间的,即将去除容器嵌入富液和贫液的循环过程中,由于吸收液是在不断循环的,通过对还原剂的加入速度进行限定,便于还原剂与三价铁离子的反应,进而提高吸收液中的二价铁离子的分布均匀性。
例如,三价铁离子的浓度单位为mol/m 3,吸收液的流速单位为m/min,流速的测量位置的管道横截面的面积为m 2,加入还原剂的速度为mol/min。
例如,还原剂为硫代硫酸钠时,一分子还原剂在和三价铁离子反应过程中失去电子的数目为1,还原剂为亚硫酸钠时,一分子还原剂在和三价铁离子反应过程中失去电子的数目为2,本实施例中使用亚硫酸钠。
在一些实施例中,吸收液中的三价铁离子的浓度降低至预设浓度时,向去除容器中加入碱液,三价铁离子和二价铁离子与碱液反应生成沉淀物,包括:测量吸收液中的三价铁离子的实时浓度为c;在c=2/3× 时,利用电控阀向去除容器中加入碱液;碱液与三价铁离子和二价铁离子同时反应,且反应为:
,沉淀物为四氧化三铁。
具体地,在还原剂的作用下,吸收液中的三价铁离子被还原成二价铁离子,在1/3的三价铁离子变成二价铁离子时,向去除容器内添加碱液,通过对吸收液中的三价铁离子和二价铁离子的浓度进行限定,只有三价铁离子和二价铁离子共同参与反应时,才会生成四氧化三铁的沉淀物,便于碱液同时与三价铁离子和二价铁离子进行反应,将铁离子以铁磁矿四氧化三铁的形式形成共沉淀析出。
可选地,三价铁离子在还原剂的作用下的反应为 。
例如,三价铁离子的浓度可以通过离子色谱进行检测,预设浓度为原来吸收液中三价铁离子的2/3。
在一些实施例中,吸收液的pH值调节至预设范围时,停止向吸收液中加入碱液,包括:
测量去除容器中的吸收液的实时pH值为P;
当10≤P≤12时,关闭电控阀。
具体地,向去除容器内添加碱液,碱性环境便于碱液中的氢氧根与三价铁离子和二价铁离子反应,随着碱液的不断加入,吸收液在碱液的作用下pH值不断上升,直至碱液的pH值为预设范围10-12时,关闭电控阀,停止向去除容器内添加碱液,通过吸收液的pH值对碱液的加入量进行限定,便于吸收液中的铁离子与碱液的反应。
例如,碱液的加入量为还原剂的加入量的5-10倍。
在一些实施例中,吸收液为循环吸收液,去除容器上设有相对布置的进液管和出液管,进液管适于与解析塔相连,出液管适于与吸收塔相连。
具体地,如图2和图3所示,进液管位于去除容器的左侧,出液管位于去除容器的右侧,进液管的一端与解析塔相连,进液管的另一端与去除容器相连以将解析后的贫液传输至去除容器内,出液管的一端与去除容器相连,出液管的另一端与吸收塔相连以将去除容器内的贫液传输至吸收塔内,通过进液管和出液管的设置以将去除容器集成二氧化碳捕集系统中。
本实施例通过直接嵌入碳捕集系统中,可以有效集成,无需改造碳捕集系统,达到显著去除铁离子的效果,本实施例并不对嵌入位置进行限定,可以设置在解析塔之后,吸收塔之前,只要使用还原沉淀的方式以及铁磁吸附的方式去除吸收剂中的铁离子的去除方式,都在实施例的保护范围内。
在一些实施例中,去除容器内设有多个呈矩阵排布的磁性棒,磁性棒与去除容器可拆卸地相连,磁性棒可吸附沉淀物。
具体地,如图2和图3所示,磁性棒在正交于左右方向和前后方向的投影面上的外轮廓为矩形,由于本实施例中沉淀物为四氧化三铁,而四氧化三铁具有磁性,可以通过磁性棒将四氧化三铁吸附在磁性棒的外侧,本实施例中通过引入磁性棒的设置,可以吸附并分离吸收剂中的反应沉淀物,提高去除效率。
进一步地,多个磁性棒的设置,还可以对吸收液形成阻挡,降低吸收液在去除容器中的流速,增加还原剂以及碱液与吸收液的接触时间,提高铁离子的去除效率。
例如,磁性棒在正交于左右方向和前后方向的投影面上的外轮廓为圆形。
例如,磁性棒为钕铁硼磁铁棒或电磁铁棒。
本发明实施例的碳捕集吸收剂中铁离子的去除装置,包括去除容器1、进液管2、出液管3、电控阀(图中未示出)和磁性棒4。进液管2和出液管3在去除容器1的径向方向上相对布置,进液管2适于与解析塔相连以向去除容器1内传输吸收液,出液管3适于与吸收塔相连以排出去除容器1内的吸收液;电控阀设在去除容器1上,电控阀具有第一状态和第二状态,在第一状态,电控阀用于向去除容器1中加入还原剂以使吸收液中的部分三价铁离子被还原成二价铁离子,在第二状态,电控阀用于向去除容器1内加入碱液,碱液与吸收液中的三价铁离子和二价铁离子反应生成沉淀物;磁性棒4位于去除容器1内,磁性棒4用于吸附沉淀物。
具体地,如图1所示,如图2和图3所示,去除容器1在正交于左右方向和前后方向的投影面上的外轮廓为圆形,吸收液从进液管2进入去除容器1后,吸收液的流速会变缓,便于吸收液在去除容器1内与还原剂和碱液发生反应。
进液管2位于去除容器1的左侧,出液管3位于去除容器1的右侧,进液管2的一端与解析塔相连,进液管2的另一端与去除容器1相连以将解析后的贫液传输至去除容器1内,出液管3的一端与去除容器1相连,出液管3的另一端与吸收塔相连以将去除容器1内的贫液传输至吸收塔内,通过进液管2和出液管3的设置以将去除容器1集成二氧化碳捕集系统中。
本发明实施例通过进液管2将吸收液传输至去除容器1内,再通过出液管3将去除容器1内的吸收液排出,将去除装置嵌入碳捕集系统中,通过调整电控阀为第一状态以向去除容器1内添加还原剂,三价铁离子在还原剂的作用下部分变成二价铁离子,并在吸收液中的三价铁离子的浓度为预设浓度时,调整电控阀为第二状态以向去除容器1内添加碱液,碱液与三价铁离子和二价铁离子共同反应生成沉淀物,最后通过磁性棒4将沉淀物吸附,耦合利用化学沉淀剂和磁性吸附作用,除去碳捕集吸收剂中的铁离子。
进一步地,本实施例通过化学还原沉淀法和磁吸法的耦合,有效去除二氧化碳捕集吸收剂中的铁离子,利用化学还原反应将溶解状态的铁离子转化为可被磁性分离的固态形式,然后通过磁吸法将其从吸收剂中分离出来,从而达到净化吸收剂、延长其使用寿命和提高碳捕集效率的目的。
进一步地,本实施例的去除装置作为流动式的去除装置嵌入碳捕集系统中的吸收液的循环管道上,在不影响碳捕集系统的正常运行的情况下,实现吸收液中的铁离子的去除。
在一些实施例中,去除装置还包括盖体5,去除容器1的顶部开口设置,盖体5盖合在去除容器1上。
具体地,盖体5的设置实现去除装置的封闭设置,避免空气中的灰尘进入吸收液中,而且盖体5的设置便于对去除容器1进行清理。
在一些实施例中,盖体5上设有加入口51,电控阀的一端与盖体5相连并通过加入口51与去除容器1连通。
具体地,如图2和图3所示,通过加入口51向去除容器1内加入还原剂和碱液,通过电控阀的设置,便于对加入去除容器1内的还原剂和碱液的容量和加入进行控制,提高反应精度。
本发明实施例的去除装置通过将碳捕集吸收剂导入去除容器1中,在去除容器1上方的盖板上开口,通过电控阀控制加入的还原剂和碱液的加入量和速度,在还原剂的作用下,部分三价铁离子变成二价铁离子,在碱液的作用下,三价铁离子和二价铁离子与碱液反应生成沉淀物,铁离子以铁磁矿四氧化三铁的形式形成共沉淀析出,从而被高强度磁性棒4所吸附,利用磁性棒4吸附碳捕集吸收剂中的含铁沉淀物,实现降低碳捕集吸收剂中含铁杂质含量的作用,达到降低吸收剂降解的目的,增加长周期运行的稳定性。
在一些实施例中,磁性棒4的数量为多个,多个磁性棒4呈矩阵分布,磁性棒4与盖体5或去除容器1的底部可拆卸地相连。
具体地,多个磁性棒4的设置,还可以对吸收液形成阻挡,降低吸收液在去除容器1中的流速,增加还原剂以及碱液与吸收液的接触时间,提高铁离子的去除效率。
例如,磁性棒4与盖体5或去除容器1的底部之间可以通过法兰、卡箍、螺栓板或者其他可以快速释放夹扣的方式实现可拆卸连接,在运行一段时间后,可以将磁性棒4取出,便于定期清理磁性棒4,实现重复使用。
在本发明的描述中,需要理解的是,术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。
此外,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。
在本发明中,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或成一体;可以是机械连接,也可以是电连接或彼此可通讯;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通或两个元件的相互作用关系,除非另有明确的限定。对于本领域的普通技术人员而言,可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中,除非另有明确的规定和限定,第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触,或第一和第二特征通过中间媒介间接接触。而且,第一特征在第二特征“之上”、“上方”和“上面”可以是第一特征在第二特征正上方或斜上方,或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方,或仅仅表示第一特征水平高度小于第二特征。
在本发明中,术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (10)

  1. 一种碳捕集吸收剂中铁离子的去除方法,其特征在于,包括:
    将吸收液传输至去除容器;
    根据所述吸收液中的三价铁离子的浓度以及所述吸收液的流速参数确定还原剂的加入速度,其中,部分所述三价铁离子被还原成二价铁离子;
    所述吸收液中的三价铁离子的浓度降低至预设浓度时,向所述去除容器中加入碱液,所述三价铁离子和所述二价铁离子与所述碱液反应生成沉淀物;
    在所述吸收液的pH值调节至预设范围时,停止向所述吸收液中加入碱液;
    排出所述沉淀物。
  2. 根据权利要求1所述的碳捕集吸收剂中铁离子的去除方法,其特征在于,所述根据所述吸收液中的三价铁离子的浓度以及所述吸收液的流速参数确定还原剂的加入速度,包括:
    测量所述吸收液流向所述去除容器的流速为V;
    计算所述流速的测量位置的管道横截面的面积为A;
    测量所述吸收液中的三价铁离子的浓度为 ;
    确定一分子还原剂在和三价铁离子反应过程中失去电子的数目为N;
    计算所述还原剂的加入速度为R,且 。
  3. 根据权利要求2所述的碳捕集吸收剂中铁离子的去除方法,其特征在于,所述吸收液中的三价铁离子的浓度降低至预设浓度时,向所述去除容器中加入碱液,所述三价铁离子和所述二价铁离子与所述碱液反应生成沉淀物,包括:
    测量所述吸收液中的三价铁离子的实时浓度为c;
    在c=2/3× 时,利用电控阀向所述去除容器中加入碱液;
    所述碱液与所述三价铁离子和所述二价铁离子同时反应,且所述反应为: ,所述沉淀物为四氧化三铁。
  4. 根据权利要求3所述的碳捕集吸收剂中铁离子的去除方法,其特征在于,所述吸收液的pH值调节至预设范围时,停止向所述吸收液中加入碱液,包括:
    测量所述去除容器中的吸收液的实时pH值为P;
    当10≤P≤12时,关闭所述电控阀。
  5. 根据权利要求1所述的碳捕集吸收剂中铁离子的去除方法,其特征在于,所述吸收液为循环吸收液,所述去除容器上设有相对布置的进液管和出液管,所述进液管适于与解析塔相连,所述出液管适于与所述吸收塔相连。
  6. 根据权利要求3所述的碳捕集吸收剂中铁离子的去除方法,其特征在于,所述去除容器内设有多个呈矩阵排布的磁性棒,所述磁性棒与所述去除容器可拆卸地相连,所述磁性棒可吸附所述沉淀物。
  7. 一种碳捕集吸收剂中铁离子的去除装置,其特征在于,包括:
    去除容器;
    进液管和出液管,所述进液管和所述出液管在所述去除容器的径向方向上相对布置,所述进液管适于与解析塔相连以向所述去除容器内传输吸收液,所述出液管适于与所述吸收塔相连以排出所述去除容器内的吸收液;
    电控阀,所述电控阀设在所述去除容器上,所述电控阀具有第一状态和第二状态,在所述第一状态,所述电控阀用于向所述去除容器中加入还原剂以使所述吸收液中的部分三价铁离子被还原成二价铁离子,在所述第二状态,所述电控阀用于向所述去除容器内加入碱液,所述碱液与所述吸收液中的三价铁离子和所述二价铁离子反应生成沉淀物;
    磁性棒,所述磁性棒位于所述去除容器内,所述磁性棒用于吸附所述沉淀物。
  8. 根据权利要求7所述的碳捕集吸收剂中铁离子的去除装置,其特征在于,还包括盖体,所述去除容器的顶部开口设置,所述盖体盖合在所述去除容器上。
  9. 根据权利要求8所述的碳捕集吸收剂中铁离子的去除装置,其特征在于,所述盖体上设有加入口,所述电控阀的一端与所述盖体相连并通过所述加入口与所述去除容器连通。
  10. 根据权利要求8所述的碳捕集吸收剂中铁离子的去除装置,其特征在于,所述磁性棒的数量为多个,多个所述磁性棒呈矩阵分布,所述磁性棒与所述盖体或所述去除容器的底部可拆卸地相连。
PCT/CN2025/085489 2024-03-28 2025-03-27 碳捕集吸收剂中铁离子的去除方法及装置 Pending WO2025201488A1 (zh)

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RU2257626C2 (ru) * 2003-04-24 2005-07-27 ФГУП "Производственное объединение "Маяк" Способ переработки альфа-активных азотно-кислых растворов, содержащих трехвалентное железо
US20190160421A1 (en) * 2017-02-01 2019-05-30 Mitsubishi Heavy Industries Engineering, Ltd. Exhaust gas treatment system
US20200317552A1 (en) * 2019-04-03 2020-10-08 Northeast Normal University High-purity separation method of iron ions from an aqueous solution containing heavy metal ions
CN118059676A (zh) * 2024-03-28 2024-05-24 中国华能集团清洁能源技术研究院有限公司 碳捕集吸收剂中铁离子的去除方法及装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2091135A (en) * 1980-11-28 1982-07-28 British Nuclear Fuels Ltd Method of and apparatus for treating liquors by magnetic filtration
RU2257626C2 (ru) * 2003-04-24 2005-07-27 ФГУП "Производственное объединение "Маяк" Способ переработки альфа-активных азотно-кислых растворов, содержащих трехвалентное железо
US20190160421A1 (en) * 2017-02-01 2019-05-30 Mitsubishi Heavy Industries Engineering, Ltd. Exhaust gas treatment system
US20200317552A1 (en) * 2019-04-03 2020-10-08 Northeast Normal University High-purity separation method of iron ions from an aqueous solution containing heavy metal ions
CN118059676A (zh) * 2024-03-28 2024-05-24 中国华能集团清洁能源技术研究院有限公司 碳捕集吸收剂中铁离子的去除方法及装置

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