TW201934496A - A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters - Google Patents

A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters Download PDF

Info

Publication number
TW201934496A
TW201934496A TW107105889A TW107105889A TW201934496A TW 201934496 A TW201934496 A TW 201934496A TW 107105889 A TW107105889 A TW 107105889A TW 107105889 A TW107105889 A TW 107105889A TW 201934496 A TW201934496 A TW 201934496A
Authority
TW
Taiwan
Prior art keywords
deionization
desalination
type capacitor
exchange membrane
water
Prior art date
Application number
TW107105889A
Other languages
Chinese (zh)
Inventor
王鴻博
鄭翔駿
柯旻伶
Original Assignee
王鴻博
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 王鴻博 filed Critical 王鴻博
Priority to TW107105889A priority Critical patent/TW201934496A/en
Publication of TW201934496A publication Critical patent/TW201934496A/en

Links

Abstract

A novel high-efficiency flowing capacitive method and device is invented for desalination and disinfection of metal-contaminated underground, waste, brine, and sea/salt waters. The flowing electrodes containing carbon slurry can effectively perform electrosorption and regeneration during the capacitive deionization process in a continuous operation mode. Moreover, additional disinfection function can be obtained in the desalination process as the core-shell particles (e.g., Ag@C) are dispersed on the carbon electrodes. It is worth to noting that chemicals are not used except the circulated carbon slurry during desalination/disinfection of sea/waste waters for water recycling/ reuse.

Description

兼具海/廢水脫鹽與殺菌之高效流動電容方法與裝置 High-efficiency flow capacitor method and device with sea / wastewater desalination and sterilization

本發明係有關於一種新穎高效流動式電極兼具殺菌之電容去離子方法與裝置,詳言之,係關於流動式電極以碳材水漿溶液進行快速電吸附及脫附(再生),可連續操作,並大幅提升海水或廢水之去離子/脫鹽效率,另,添加奈米金屬核殼粒子於流動式碳電極,增加消毒殺菌功能,達到水回收再利用之目的。 The present invention relates to a novel and efficient method and device for deionizing capacitors with both sterilization and flow capacity. In particular, the invention relates to a rapid electrode adsorption and desorption (regeneration) of a flow type electrode with a carbon water slurry solution. Operation, and greatly improve the deionization / desalting efficiency of seawater or wastewater. In addition, nano metal core-shell particles are added to the flow-type carbon electrode to increase the disinfection and sterilization function to achieve the purpose of water recycling.

按,產業迅速發展,工業需水量日益增加,但新水源開發卻愈來愈困難,乾淨水源面臨嚴重匱乏不足的問題,例如:四面環海之台灣島,冬季多處於乾旱期,水源全年分配不均勻,突顯水資源多元化之重要性。 According to the industry's rapid development, the industrial water demand is increasing, but the development of new water sources is becoming more and more difficult, and clean water sources are facing serious shortages. For example, the island of Taiwan surrounded by the sea is mostly in the dry season in winter, and water resources are not distributed throughout the year. Uniformity underscores the importance of diversifying water resources.

海水或廢水(海/廢水)去離子/脫鹽可提供更有效水資源選擇,將含鹽分或金屬離子性污染物之受污染之地表水或地下水、滷水、廢水或海水等,透過移除水中之鹽分或離子污染物質,可達到水回收再利用之目的。 Deionization / desalination of seawater or wastewater (sea / wastewater) can provide more efficient water resource selection. Contaminated surface water or groundwater, brine, wastewater, or seawater containing salt or metal ion pollutants can be removed by removing Salt or ionic pollutants can achieve the purpose of water recycling and reuse.

電容去離子以多孔碳材(porous carbon materials)為非消耗性電極,通以微伏電壓,利用電吸(electrosorption)原理,在電極表面形成電 雙層以吸附、移除水中帶電荷之污染物質或離子,例如中華民國專利公告第I460135號電容脫鹽裝置。 Capacitive deionization uses porous carbon materials as non-consumable electrodes. Microvolts are applied to the electrodes to form electricity on the electrode surface using the principle of electrosorption. Double layer to adsorb and remove charged pollutants or ions in water, such as the Republic of China Patent Publication No. I460135 capacitor desalination device.

又,傳統固定式電極脫鹽效率偏低,設備所佔空間相對較大,無法進行高濃度鹵水之脫鹽。 In addition, the conventional fixed electrode desalination efficiency is relatively low, the equipment takes up a relatively large space, and it is impossible to desalinate high-concentration brine.

且,傳統海/廢水脫鹽方法缺少消毒殺菌功能,需另增加消毒殺菌單元,以符合飲用水標準。 In addition, the traditional sea / wastewater desalination method lacks a disinfection and sterilization function, and an additional disinfection and sterilization unit is required to meet drinking water standards.

因此,有必要提供一創新且實用之高效流動式電極兼具殺菌之電容去離子方法與裝置,將含鹽分或金屬離子性污染物之受污染之地表水或地下水、滷水、廢水或海水等,透過移除水中之鹽分或離子污染物質,達到水回收再利用之目的。 Therefore, it is necessary to provide an innovative and practical method and device for capacitive deionization of high-efficiency mobile electrodes and sterilization, which will contaminate surface water or groundwater, brine, wastewater or seawater containing salt or metal ionic pollutants. Removal of salt or ionic pollutants in water achieves the purpose of water recycling and reuse.

本發明提供一種高效流動式電極兼具殺菌之電容去離子方法與裝置,其實施方法包括:(1)碳材水漿溶液流入施加微伏電壓之電極之間,使電極表面形成電雙層(electric double layer),電極間之帶電離子,受到靜電吸引力,分別透過陰、陽離子薄膜選別,向兩側陽、陰電極遷移與電吸附,因此,水中之帶電離子可以分離而達到去離子/脫鹽之功能;(2)此吸附飽和之碳材水漿溶液流入再生槽,不需調整電壓,進行連續操作。另外,可調高碳材水漿溶液流動速率,以因應高鹽度之海水脫鹽操作;(3)可添加奈米金屬核殼粒子(例如:銀或銅包覆於多孔碳層(Ag@C或Cu@C))增加消毒殺菌之功能,可以阻絕病毒、細菌及寄生蟲,達到淨化水質之目的。 The invention provides a capacitor deionization method and device with high-efficiency flow-type electrode and sterilization. The implementation method includes: (1) a carbon water slurry solution flows between the electrodes to which a microvolt voltage is applied, so that the surface of the electrode forms an electric double layer ( electric double layer), the charged ions between the electrodes are electrostatically attracted, and they are separated through the anion and cation membranes, and migrate to the positive and negative electrodes on both sides of the electrode, so that the charged ions in the water can be separated to achieve deionization / desalination. Function; (2) This adsorption saturated carbon material water slurry solution flows into the regeneration tank, and it does not need to adjust the voltage for continuous operation. In addition, the flow rate of the carbon water slurry solution can be adjusted to desalinate seawater in response to high salinity; (3) Nano metal core-shell particles (such as silver or copper can be coated on the porous carbon layer (Ag @ C) Or Cu @ C)) Increase the function of disinfection and sterilization, which can block viruses, bacteria and parasites, and achieve the purpose of purifying water.

緣是,本發明之高效流動式電極兼具殺菌之電容去離子方法與裝置,具低耗能、高效率、低二次污染、操作與維護簡易等優點。可將 含鹽分或離子性污染物之受污染之地表水或地下水、滷水、廢水或海水等,透過移除水中之鹽分或離子污染物質,又增加消毒殺菌之功能,可達到水回收再利用之目的。 The reason is that the high-efficiency flow-type electrode of the present invention has a method and a device for sterilizing the capacitor deionization, and has the advantages of low energy consumption, high efficiency, low secondary pollution, and simple operation and maintenance. Can Contaminated surface water or groundwater, brine, wastewater, or seawater containing salt or ionic pollutants can achieve the purpose of water recycling and reuse by removing the salt or ionic pollutants in the water and increasing the disinfection and sterilization function.

第1圖 說明本發明高效流動式電容去離子/脫鹽裝置之示意圖。 FIG. 1 is a schematic diagram illustrating a highly efficient flow type capacitor deionization / desalination apparatus according to the present invention.

第2圖 說明本發明高效流動式電容去離子可並聯電容去離子/脫鹽與再生槽等2個裝置進行連續式操作之示意圖。 FIG. 2 is a schematic diagram illustrating continuous operation of the high-efficiency flow-type capacitor deionization in accordance with the present invention, which can be operated in parallel with two devices, such as a capacitor deionization / desalination and regeneration tank.

第3圖 說明本發明之生質廢棄物研製高比表面積多孔洞碳材之合成方法。 Fig. 3 illustrates a method for synthesizing a porous carbon material with a high specific surface area by the biomass waste of the present invention.

第4圖 說明本發明之複合奈米金屬核殼粒子與碳材之合成方法。 Fig. 4 illustrates a method for synthesizing the composite nano metal core-shell particles and carbon material according to the present invention.

第5圖 說明本發明之氧化石墨烯陽離子交換膜之合成方法。 Fig. 5 illustrates a method for synthesizing the graphene oxide cation exchange membrane of the present invention.

第6圖 說明本發明之季銨化聚乙烯醇/幾丁質複合型陰離子交換膜之合成方法。 Fig. 6 illustrates a method for synthesizing the quaternized polyvinyl alcohol / chitin composite anion exchange membrane of the present invention.

第7圖 說明本發明高效流動型電容去離子鋰離子回收裝置示意圖。 Fig. 7 illustrates a schematic diagram of a highly efficient flow-type capacitor deionized lithium ion recovery device of the present invention.

為使本發明使用之技術手段、發明特徵,達成目的與功效易於了解,茲配合圖式及圖號詳細說明如下:本發明之實施例一:高效流動式電容去離子/脫鹽裝置。 In order to make it easy to understand the technical means, inventive features, achieved objectives and effects of the present invention, the drawings and figures are described in detail as follows: Embodiment 1 of the present invention: a high-efficiency flow type capacitor deionization / desalination device.

第1圖顯示本發明高效流動式電容去離子/脫鹽之裝置示意圖包含:電流收集器(1)、流動式電極通道(陰極(2)/陽極(3))、離子交換膜(陽離子交換膜(4)/陰離子交換膜(5))、及海/廢水流通道(6)。 Fig. 1 shows a schematic diagram of the device for efficient deionization / desalination of a capacitive capacitor of the present invention, including: a current collector (1), a flow electrode channel (cathode (2) / anode (3)), an ion exchange membrane (cation exchange membrane ( 4) / anion exchange membrane (5)), and sea / wastewater flow channel (6).

在本實施例中,流動式電極係混合分散均勻5~60%多孔碳材水漿溶液(slurry),具高比表面積及多孔洞之活性碳、奈米碳管或石墨烯可做為碳材。 In this embodiment, a 5 to 60% porous carbon material slurry solution is uniformly mixed and dispersed in a flow-type electrode system. Activated carbon with high specific surface area and porous holes, carbon nanotubes, or graphene can be used as the carbon material. .

具良好導電度之石墨板、鈦板或其他材質可做為電流收集器,將施加之電動式傳遞至上述流動式電極。 Graphite plates, titanium plates or other materials with good conductivity can be used as current collectors to transfer the applied electric type to the above-mentioned flowing electrodes.

首先,先將乾淨之流動式電極(碳材水漿溶液)(7)與海/廢水進流水(8)分別泵浦流入電極通道(陰極(2)/陽極(3))及水流通道(6)。兩離子交換膜(陰離子交換膜(5)/陽離子交換膜(4))可以選別溶液中離子的遷移,並隔絕流動式電極(7)及進流水(8)。 First, the clean flowing electrode (carbon water slurry solution) (7) and the sea / wastewater inflow water (8) are pumped into the electrode channel (cathode (2) / anode (3)) and the water flow channel (6) respectively. ). The two ion exchange membranes (anion exchange membrane (5) / cation exchange membrane (4)) can select the migration of ions in the solution and isolate the flow electrode (7) and the inflow water (8).

施加微伏電動勢於電流收集器,產生0.6~2.0伏電壓差於兩側電極進行電容去離子/脫鹽反應。 Applying a microvolt electromotive force to the current collector, a voltage difference of 0.6 to 2.0 volts is generated for the capacitive deionization / desalting reaction at the electrodes on both sides.

進流水中帶電離子受到靜電吸引力而往兩側電極遷移,陰離子通過陰離子交換膜(5)進入陽極(3),陽離子通過陽離子交換膜(4)進入陰極(2),陰、陽離子分別吸附於流動式電極之陽極及陰極。 The charged ions in the flowing water are electrostatically attracted to the electrodes on both sides, anions enter the anode (3) through the anion exchange membrane (5), and cations enter the cathode (2) through the cation exchange membrane (4). Anode and cathode of the flow electrode.

去除帶電離子之乾淨出流水(9),完成去離子/脫鹽程序,電吸附飽和之流動式電極(10)則流至再生槽進行反洗再生。 Remove the clean effluent water (9) of the charged ions, complete the deionization / desalting process, and the electro-saturated flow electrode (10) flows to the regeneration tank for backwash regeneration.

此外,請參閱第2圖,可並聯兩組裝置進行連續式操作,進流水(8)流經電容去離子/脫鹽裝置(12)進行電吸附得到乾淨出流水(9);吸附飽和之流動式電極則流至再生槽(13),施加與裝置(12)相反之逆向或零電壓進行反洗再生,附著於流動式電極之離子受到靜電排斥力作用排出滷水(11),完成流動式電極之反洗,再生之流動式電極可再次回流到電容去離子/脫鹽裝置(12)進行電吸附。此一系統結合電容去離子/脫鹽及反洗再生兩裝 置,可以連續式操作進行海/廢水脫鹽/去離子,又,可模組化多組裝置串聯或並聯,以提升海/廢水去離子/脫鹽之質與量,有利於依實務需求而工程放大。 In addition, please refer to Figure 2. Two sets of devices can be connected in parallel for continuous operation. The inflow water (8) flows through the capacitor deionization / desalination device (12) for electro-adsorption to obtain clean effluent water (9). The electrode flows to the regeneration tank (13). The reverse or zero voltage opposite to the device (12) is applied for backwash regeneration. The ions attached to the mobile electrode are discharged from the brine (11) by the electrostatic repulsive force to complete the flow electrode. Backwash, the regenerated flow electrode can be returned to the capacitor deionization / desalination device (12) for electrosorption. This system combines capacitor deionization / desalination and backwash regeneration. It can be used for continuous operation of sea / wastewater desalination / deionization, and it can be modularized with multiple sets of devices in series or in parallel to improve the quality and quantity of sea / wastewater deionization / desalination, which is conducive to engineering enlargement according to practical needs .

本發明之實施例二:生質廢棄物合成高比表面積多孔洞碳材。 Embodiment 2 of the present invention: Biomass waste is synthesized into a porous carbon material with a high specific surface area.

生物質(Biomass)包括:椰殼、稻殼、竹子、甘蔗渣等,此類生質廢棄物量大且成分相對單純,具高碳與低無機物含量,是相當適合作為活性碳原料的選擇,除可解決廢棄物處理的問題,也可以大幅減少石化燃料的依賴,是相對乾淨且可循環再利用的物質。 Biomass includes: coconut husk, rice husk, bamboo, bagasse, etc. This type of biomass waste is large in quantity and relatively simple in composition, with high carbon and low inorganic content. It is a suitable choice for activated carbon raw materials. It can solve the problem of waste disposal, and can also greatly reduce the dependence on petrochemical fuels. It is a relatively clean and recyclable substance.

使用生質廢棄物研製之活性碳應用於流動式電容去離子/脫鹽裝置,除兼具環境友善,也可以降低成本。 Activated carbon developed using biomass waste is used in mobile capacitor deionization / desalination plants. Besides being environmentally friendly, it can also reduce costs.

請參閱第3圖之步驟S31,將生質廢棄物浸泡於化學活化劑(例如:H3PO4、ZnCl2、或KOH等)2~6小時後,在60~150℃烘乾(步驟S32),除脫水作用,也可改變碳化過程,並抑制焦碳(char)與揮發性物質的產生,接著,將活化、乾燥完成之前驅物在400~800℃之下通入缺氧氣體進行熱解反應1~3小時(步驟S33),釋出氣體形成多孔性結構碳材。 Please refer to step S31 in FIG. 3, immerse the biomass waste in a chemical activator (for example: H 3 PO4, ZnCl 2 , or KOH, etc.) for 2 to 6 hours, and then dry at 60 to 150 ° C. (step S32) In addition to the dehydration effect, the carbonization process can also be changed, and the generation of char and volatile substances can be suppressed. Then, the precursors before activation and drying are completed by passing hypoxia gas at 400 ~ 800 ° C for pyrolysis. The reaction is performed for 1 to 3 hours (step S33), and the gas is released to form a porous structure carbon material.

待活性碳冷卻,以稀鹽酸及水清洗除去殘留之化學藥品(步驟S34)。請參考步驟S35,完成之生質活性碳分散於淡水生成水漿,即可應用於流動型電容去離子/脫鹽。 After the activated carbon is cooled, the remaining chemicals are removed by washing with dilute hydrochloric acid and water (step S34). Please refer to step S35. The completed biomass activated carbon is dispersed in fresh water to form a water slurry, which can be applied to flow-type capacitor deionization / desalination.

本發明之實施例三:合成新型複合奈米金屬核殼/生質活性碳電極。 Embodiment 3 of the present invention: A novel composite nano metal core-shell / bio-active carbon electrode is synthesized.

藉由添加可調粒徑奈米金屬之核殼材料於上述生質活性 碳,可製備具消毒殺菌功能之流動式電極(碳材水漿溶液)。 By adding a core-shell material with adjustable particle size nano metal to the above bioactive Carbon can be used to prepare mobile electrodes (carbon water slurry solution) with disinfection and sterilization function.

由於銅或銀金屬可破壞微生物體內之蛋白質及遺傳物質,使其失去活性而死亡,達到水之消毒殺菌目的。 Because copper or silver metal can destroy the protein and genetic material in microorganisms, make them inactivate and die, and achieve the purpose of disinfection and sterilization of water.

合成方法請參閱第4圖之說明,將醣類化合物(例如:澱粉)螯合萃取金屬離子形成錯合物(步驟S42),在40~150℃乾燥24~72小時(步驟S43)。 For the synthesis method, please refer to the description in FIG. 4. The sugar compound (for example, starch) is chelated to extract metal ions to form a complex (step S42), and dried at 40 to 150 ° C. for 24 to 72 hours (step S43).

將乾燥之錯合物與生質活性碳前驅物均勻混合(步驟S44),於400~600℃以缺氧氣體進行碳化1~3小時,生成奈米金屬核殼粒子與生質活性碳複合材料(步驟S45)。 The dry complex is uniformly mixed with the biomass activated carbon precursor (step S44), and carbonized with an oxygen-deficient gas at 400 to 600 ° C for 1 to 3 hours to generate nano metal core-shell particles and the biomass activated carbon composite material. (Step S45).

具消毒殺菌之核殼粒子與生質活性碳複合材料(步驟S46)應用於流動式電容去離子/脫鹽,達到兼具殺菌(>90%)之高效海/廢水去離子/脫鹽之目的。 Core-shell particles with sterilization and bioactive activated carbon composite material (step S46) are applied to the flow capacitor deionization / desalination to achieve the purpose of high-efficiency sea / wastewater deionization / desalination with sterilization (> 90%).

本發明之實施例四:合成新型氧化石墨烯陽離子交換膜。 Embodiment 4 of the present invention: Synthesis of a novel graphene oxide cation exchange membrane.

氧化石墨烯之帶負電之酸性活性基團例如:含氧官能基及磺酸根,可以選擇性增加陽離子通透性,並同時阻擋陰離子之傳輸。 The negatively charged acidic active groups of graphene oxide, such as oxygen-containing functional groups and sulfonate groups, can selectively increase the permeability of cations, and at the same time block the transmission of anions.

利用氧化石墨烯具可調多元官能基且容易修飾之特性,可以磺酸根修飾氧化石墨烯,此種磺酸化氧化石墨烯作為流動式電容去離子/脫鹽裝置之陽離子交換膜,可以增加去離子/脫鹽效率,並降低成本。 Using graphene oxide with adjustable multifunctional functional groups and easy modification, graphene oxide can be modified by sulfonate. This kind of sulfonated graphene oxide is used as a cation exchange membrane of mobile capacitor deionization / desalination device, which can increase deionization / Desalination efficiency and reduce costs.

請參閱第5圖,首先,將石墨片(S51)進行化學剝離(S52),並以稀鹽酸及水清洗產物至中性,乾燥後得到氧化石墨烯(S53)。 Referring to FIG. 5, first, the graphite sheet (S51) is chemically stripped (S52), and the product is washed with dilute hydrochloric acid and water to neutrality, and then graphene oxide (S53) is obtained after drying.

將氧化石墨烯分散於水溶液,並震盪至均勻,在50~70℃,加入氨基苯磺酸及亞硝酸鹽類,進行磺酸化反應12~24小時(步驟S54)後,清 洗至中性並乾燥。 Disperse the graphene oxide in the aqueous solution and shake to homogeneity. Add aminobenzenesulfonic acid and nitrite at 50 ~ 70 ℃, and perform sulfonation reaction for 12 ~ 24 hours (step S54). Wash until neutral and dry.

參閱步驟S55,將磺酸化氧化石墨烯分散於聚乙烯醇稀溶液,並且攪拌4~6小時,在塗佈於玻璃上,經50~90℃烘乾12~24小時,成為氧化石墨烯陽離子交換膜(步驟S56),可應用於流動式電容去離子/脫鹽裝置。 Refer to step S55, disperse the sulfonated graphene oxide in a dilute polyvinyl alcohol solution, stir for 4-6 hours, coat on glass, and dry at 50-90 ° C for 12-24 hours to become cation exchange of graphene oxide. The membrane (step S56) can be applied to a flow-type capacitor deionization / desalination apparatus.

本發明之實施例五:合成新型複合型陰離子交換膜。 Embodiment 5 of the present invention: A novel composite anion exchange membrane is synthesized.

修飾聚乙烯醇及幾丁質鹼性官能基,可以選擇性增加陰離子通透性,並同時阻擋陽離子之傳輸。 Modified polyvinyl alcohol and chitin basic functional groups can selectively increase the permeability of anions, and at the same time block the transmission of cations.

以新型季銨化聚乙烯醇/幾丁質複合型陰離子交換膜應用於流動式電容去離子/脫鹽裝置,可以增加海/廢水去離子/脫鹽效率,並降低成本。 A new type of quaternized polyvinyl alcohol / chitin composite anion exchange membrane is applied to the flow type capacitor deionization / desalination device, which can increase the deionization / desalination efficiency of sea / wastewater and reduce the cost.

請參閱第6圖之步驟S61,首先,將聚乙烯醇加入縮水甘油三甲基氯化銨與氫氧化鉀,在50~80℃反應2~6小時,並以無水酒精清洗產物至中性並乾燥。 Please refer to step S61 in FIG. 6. First, polyvinyl alcohol is added to glycidyl trimethyl ammonium chloride and potassium hydroxide, and the reaction is performed at 50 to 80 ° C for 2 to 6 hours, and the product is washed with absolute alcohol to neutrality and dry.

將幾丁質加入縮水甘油三甲基氯化銨並於50~80℃反應2~6小時,清洗產物至中性後乾燥(步驟S62)。 Chitin is added to glycidyl trimethylammonium chloride and reacted at 50 ~ 80 ° C for 2 ~ 6 hours. The product is washed to be neutral and then dried (step S62).

請參閱步驟S63,將季銨化之聚乙烯醇及幾丁質溶於水中,加入戊二醛在50~80℃進行交聯反應1~3小時,再將混合溶液塗佈於玻璃上,在50~70℃烘乾,生成合成新型複合型陰離子交換膜(步驟S64),可應用於流動式電容去離子/脫鹽。 Please refer to step S63. Dissolve the quaternized polyvinyl alcohol and chitin in water, add glutaraldehyde at 50 ~ 80 ℃ for 1 ~ 3 hours, and then coat the mixed solution on the glass at 50 ~ Dry at 70 ° C to produce a new composite anion exchange membrane (step S64), which can be applied to flow capacitor deionization / desalination.

本發明之實施例六:鹽水之流動式電容去離子/脫鹽。 Embodiment 6 of the present invention: Flow-type capacitive deionization / desalting of brine.

實施步驟如同實例一所述。其中進流水以鹽水([NaCl]=5000 ppm)通入,經流動式電容去離子/脫鹽進行電吸附反應,經12組串聯模組,可去除大部分鹽分,並得到乾淨水([NaCl]<50ppm)。 The implementation steps are as described in Example 1. The inflow water is brine ([NaCl] = 5000 (ppm), pass through the electrolytic capacitor deionization / desalting to perform the electro-adsorption reaction. After 12 groups of modules in series, most of the salt can be removed and clean water ([NaCl] <50ppm) can be obtained.

本發明之實施例七:半導體製程RO廢水之流動式電容去離子。 Embodiment 7 of the present invention: Flow-type capacitor deionization of RO wastewater from semiconductor processes.

實施步驟如同實例一所述。其中進流水RO廢水經流動式電容去離子進行電吸附反應,經8組串聯模組,可進一步去除金屬鹽類,回收純水。 The implementation steps are as described in Example 1. The influent water RO wastewater undergoes electro-adsorption reaction through flowing capacitor deionization. After 8 sets of series modules, metal salts can be further removed and pure water can be recovered.

本發明之實施例八:海水之流動式電容去離子/脫鹽。 Embodiment 8 of the present invention: Flow-type capacitor deionization / desalting of seawater.

實施步驟如同實例一所述。其中進流水海水([NaCl]=35,000ppm)通入,經流動式電容去離子/脫鹽進行電吸附反應,經30組串聯模組,可去除大部分鹽分,並得到乾淨水([NaCl]<50ppm)。 The implementation steps are as described in Example 1. The inflow water seawater ([NaCl] = 35,000ppm) was passed in, and the electro-adsorption reaction was carried out through the flow capacitor deionization / desalting. After 30 series modules, most of the salt could be removed and clean water ([NaCl] < 50ppm).

本發明之實施例九:含重金屬污染地下水之流動式電容去離子。 Embodiment 9 of the present invention: Flow-type capacitor deionization of heavy metal contaminated groundwater.

實施步驟如同實例一所述。其中進流水以含重金屬汙染地下水通入,經流動式電容去離子進行電吸附反應,經8組串聯模組,可去除金屬鹽類,回收乾淨水。 The implementation steps are as described in Example 1. The inflow water flows into the groundwater contaminated with heavy metals and undergoes an electro-adsorption reaction through mobile capacitor deionization. After 8 sets of series modules, metal salts can be removed and clean water can be recovered.

本發明之實施例十:含重金屬污染廢水之流動式電容去離子。 Embodiment 10 of the present invention: Flow-type capacitor deionization of heavy metal-contaminated wastewater.

實施步驟如同實例一所述。其中進流水以含重金屬汙染廢水通入,經流動式電容去離子進行電吸附反應,經10組串聯模組,可去除金屬鹽類,回收乾淨水。 The implementation steps are as described in Example 1. The influent water is passed in as heavy metal-contaminated wastewater, which is subjected to electro-adsorption reaction through mobile capacitor deionization. After 10 sets of series modules, metal salts can be removed and clean water can be recovered.

本發明之實施例十一:流動型電容去離子鋰離子回收。 The eleventh embodiment of the present invention: Flow type capacitor deionized lithium ion recovery.

鋰化合物之應用相當廣泛例如:充電電池、核融合以及飛機機殼之合金等,導致近幾年鋰的需求量大幅增加。 The applications of lithium compounds are quite extensive, such as: rechargeable batteries, nuclear fusion, and alloys for aircraft casings, leading to a significant increase in the demand for lithium in recent years.

可開採之陸地鋰礦約16.7GT,但海水中鋰濃度雖低(0.17mg/L),總鋰量高達230GT。由於需求甚大,從海水中回收鋰之技術逐漸受到重視。 The land lithium mine that can be mined is about 16.7GT, but the lithium concentration in seawater is low (0.17mg / L), and the total lithium amount is as high as 230GT. Due to the high demand, the technology of recovering lithium from seawater has gradually received attention.

傳統方法以鋰錳氧化物當作吸附劑,但效率不佳導致耗時長,且須以酸液反洗萃取,恐有環境汙染問題。 The traditional method uses lithium manganese oxide as an adsorbent, but the poor efficiency results in long time consumption, and it must be back-extracted with an acid solution, which may cause environmental pollution problems.

利用靜電場輔助配合流動式電容去離子裝置,可以有效提升鋰離子之吸附效率,且施加逆向或零電壓即可將鋰離子從碳材脫附,減少二次汙染之疑慮。 The use of an electrostatic field assisted with a flow-type capacitive deionization device can effectively improve the adsorption efficiency of lithium ions, and the reverse or zero voltage can be applied to desorb lithium ions from the carbon material, reducing the concerns of secondary pollution.

在本實施利中,如第7圖,陽極為流動式多孔性碳材(18),陰極為流動式鋰錳氧化物(17)作為鋰離子之吸附劑。 In this embodiment, as shown in FIG. 7, the anode is a mobile porous carbon material (18), and the cathode is a mobile lithium manganese oxide (17) as an adsorbent for lithium ions.

首先,先將碳材水漿溶液(流動式電極)及海水或含鋰之廢水(8)以泵浦分別流入電極通道(陰極(2)/陽極(3))及水流通道(8),流入陰極(2)電極通道之碳材水漿溶液(流動式電極)另添加10~60%之錳氧化物(例如:H2TiO3),氫錳氧化物也可選別吸附海水中微量鋰離子形成鋰錳氧化物。離子交換膜(陰離子交換膜(5)/陽離子交換膜(4))可以限制溶液中離子的遷移並隔絕懸浮電極溶液及含鋰進流水。 First, the carbon material water slurry solution (mobile electrode) and seawater or lithium-containing wastewater (8) are pumped into the electrode channel (cathode (2) / anode (3)) and the water flow channel (8), respectively. The carbon material water slurry solution (mobile electrode) of the cathode (2) electrode channel is additionally added with 10 to 60% of manganese oxide (for example: H 2 TiO 3 ), and the manganese hydrogen oxide can also be formed without adsorbing trace lithium ions in seawater. Lithium manganese oxide. The ion exchange membrane (anion exchange membrane (5) / cation exchange membrane (4)) can limit the migration of ions in the solution and isolate the suspended electrode solution and lithium-containing inflow water.

施加一電動勢於電流收集器,產生0.6~2.0伏電壓差於兩側電極進行離子電吸附。 An electromotive force is applied to the current collector, and a voltage difference of 0.6 to 2.0 volts is generated at the electrodes on both sides for ion electrosorption.

海水中帶電離子受到靜電吸引力而往兩側電極遷移,鋰錳氧化物可以選擇性吸附鋰離子,使鋰離子之回收率遠大於其餘正電離子。 The charged ions in seawater migrate to the electrodes on both sides due to electrostatic attraction, and lithium manganese oxide can selectively adsorb lithium ions, so that the recovery rate of lithium ions is much larger than the other positively charged ions.

進行電吸附得到乾淨出流水(9);吸附飽和之流動式電極則流至再生槽,施加相反之逆向或零電壓進行反洗再生,附著於流動式電極之離子受到靜電排斥力作用排出滷水,完成流動式電極之反洗,再生之流動式電極可再次回流到電容去離子/脫鹽裝置進行電吸附。 Clean adsorption water (9) is obtained by electro-adsorption; the flow-type electrode saturated with adsorption flows to the regeneration tank, and reverse reverse or zero voltage is applied for backwash regeneration. The ions attached to the flow-type electrode are discharged by brine by electrostatic repulsion. The backwashing of the flow-type electrode is completed, and the regenerated flow-type electrode can be returned to the capacitor deionization / desalination device for electrosorption.

將吸附飽和之鋰錳氧化物流入鋰回收槽,並施加逆向或零電壓可將鋰離子從碳材脫附,並通入CO2,生成Li2CO3沉澱,完成鋰離子之分離回收。 The adsorption-saturated lithium manganese oxide flows into the lithium recovery tank, and reverse or zero voltage is applied to desorb lithium ions from the carbon material and pass into CO 2 to generate Li 2 CO 3 precipitates to complete the separation and recovery of lithium ions.

綜上所述,本發明實施例確能達到所預期之功效,又其展示之具體功能,不僅未曾見諸同類產品中,亦未曾公開於申請前,誠已完全符合專利法之規定與要求,爰依法提出發明專利之申請,懇請惠予審查,並賜准專利,則實感德便。 To sum up, the embodiments of the present invention can indeed achieve the expected effects, and the specific functions shown by them are not only not seen in similar products, nor disclosed before the application, and they have fully complied with the provisions and requirements of the Patent Law. I filed an application for an invention patent in accordance with the law, and I urge you to examine it and grant the patent.

Claims (10)

高效流動式電容去離子/脫鹽及殺菌方法與裝置,包括以下步驟:(a)將碳材水漿溶液及進流水以泵浦分別流入電極通道及水流通道,以陰/陽離子交換膜限制溶液中離子的遷移,並隔絕碳材水漿溶液與進流水。 (b)施加0.6~2.0伏電壓差於兩側電極進行電容去離子與脫鹽。進流水中帶電離子受到靜電吸引力而往兩側電極遷移,陰離子通過陰離子交換膜進入陽極,陽離子通過陽離子交換膜進入陰極,陰、陽離子分別吸附於陽極及陰極之碳材水漿溶液。 (c)回收乾淨水,完成去離子/脫鹽程序,吸附飽和之碳材則回流至再生槽進行反洗再生。 High-efficiency flow-type capacitor deionization / desalting and sterilization method and device, including the following steps: (a) The carbon material water slurry solution and inflow water are pumped into the electrode channel and the water flow channel respectively, and the solution is restricted by an anion / cation exchange membrane The migration of ions, and the carbon water slurry solution and the inflow water are isolated. (b) Applying a voltage difference of 0.6 to 2.0 volts to the electrodes on both sides for capacitive deionization and desalination. The charged ions in the flowing water are electrostatically attracted and migrate to the electrodes on both sides. The anions enter the anode through the anion exchange membrane, the cations enter the cathode through the cation exchange membrane, and the anions and cations are adsorbed on the carbon water solution of the anode and the cathode, respectively. (c) Recover clean water, complete the deionization / desalination process, and adsorb the saturated carbon material back to the regeneration tank for backwash regeneration. 如請求項一之高效流動式電容去離子/脫鹽之裝置與方法,其中,在步驟(a)中,碳材以生質廢棄物所合成高比表面積、多孔洞碳材作為電容去離子/脫鹽之流動電極材料,應用於流動式電容去離子/脫鹽,除兼具環境友善,亦可以降低成本。 The high-efficiency flow type capacitor deionization / desalination device and method according to claim 1, wherein, in step (a), the carbon material uses the high specific surface area, porous carbon material synthesized by the biomass waste as the capacitor deionization / desalination. The mobile electrode material is applied to the flow capacitor deionization / desalination. Besides being environmentally friendly, it can also reduce costs. 如請求項一之高效流動式電容去離子/脫鹽之裝置與方法,其中,在步驟(a)中,使用複合奈米金屬核殼粒子與碳材作為流動電極材料,利用醣類化合物與金屬離子螯合萃取後,與碳材混合,在400~600℃進行碳化1~3小時,生成複合奈米金屬核殼碳材,應用於流動式電容去離子,可達到高效脫鹽兼具殺菌之目的。 The device and method for high-efficiency flow-type capacitor deionization / desalination according to claim 1, wherein, in step (a), composite nano-metal core-shell particles and carbon material are used as the flow electrode material, and sugar compounds and metal ions are used. After chelating extraction, it is mixed with carbon materials and carbonized at 400 ~ 600 ° C for 1 ~ 3 hours to produce composite nano-metal core-shell carbon materials, which are applied to the flow type capacitor deionization, which can achieve the purpose of high efficiency desalination and sterilization. 如請求項一之高效流動式電容去離子/脫鹽之裝置與方法,其中,在步驟(a)中,陽離子交換膜以磺酸化氧化石墨烯陽離子交換膜作為該電容去離 子之陽離子交換膜。以簡單之化學方法將氧化石墨烯磺酸化,配製聚乙烯醇及磺酸化氧化石墨稀溶液,烘乾後,應用於流動式電容去離子裝置之陽離子交換膜,可增加陽離子之選擇性與通透性,並可阻擋陰離子之傳輸。 The device and method for high-efficiency flow-type capacitor deionization / desalination according to claim 1, wherein, in step (a), the cation exchange membrane uses a sulfonated graphene oxide cation exchange membrane as the capacitor removal Cation exchange membrane. Graphene oxide is sulfonated by a simple chemical method. Polyvinyl alcohol and dilute solution of sulfonated graphite oxide are prepared. After drying, it is applied to the cation exchange membrane of the flow capacitor deionization device, which can increase the selectivity and permeability of cations. And can block the transmission of anions. 如請求項一之高效流動式電容去離子/脫鹽之裝置與方法,其中,在步驟(a)中,陰離子交換膜以季銨化聚乙烯醇/幾丁質複合型陰離子交換膜作為電容去離子之陰離子交換膜。以縮水甘油三甲基氯化銨修飾聚乙烯醇及幾丁質,帶正電的官能基可以增加陰離子之選擇性與通透性,並可阻擋陽離子之傳輸。分別將聚乙烯醇及幾丁質進行季銨化反應,並分別在50~80℃反應2~6小時,清洗乾燥後,與戊二醛在50~80℃進行交聯反應1~3小時,烘乾後,生成季銨化聚乙烯醇/幾丁質複合型陰離子交換膜,應用於流動式電容去離子/脫鹽裝置之陰離子交換膜,可增加陰離子之選擇性與通透性,並可阻擋陽離子之傳輸。 The high-efficiency flow type capacitor deionization / desalting device and method according to claim 1, wherein in step (a), the anion exchange membrane uses a quaternized polyvinyl alcohol / chitin composite anion exchange membrane as the capacitor deionization Anion exchange membrane. Modified polyvinyl alcohol and chitin with glycidyl trimethyl ammonium chloride, the positively charged functional group can increase the selectivity and permeability of anions, and can block the transmission of cations. Perform quaternization of polyvinyl alcohol and chitin, and react at 50 ~ 80 ℃ for 2 ~ 6 hours. After washing and drying, crosslink with glutaraldehyde at 50 ~ 80 ℃ for 1 ~ 3 hours. After drying, a quaternized polyvinyl alcohol / chitin composite anion exchange membrane is generated and applied to the anion exchange membrane of the flow type capacitor deionization / desalination device, which can increase the selectivity and permeability of anions, and can block Cation transport. 如申請專利範圍第一項至第五項所述高效流動式電容去離子/脫鹽及殺菌方法與裝置,其中,高效流動式電容去離子/脫鹽之裝置可應用於從鹽水中脫鹽,回收乾淨水。 As described in the first to fifth items in the scope of the patent application, the high-efficiency flow type capacitor deionization / desalting and sterilization method and device, wherein the high-efficiency flow type capacitor deionization / desalting device can be applied to desalination from brine and recover clean water. . 如申請專利範圍第一項至第五項所述高效流動式電容去離子/脫鹽及殺菌方法與裝置,其中,高效流動式電容去離子/脫鹽之裝置可應用於半導體製程RO廢水去離子,回收乾淨水。 As described in the first to fifth items in the scope of the patent application, the high-efficiency flow type capacitor deionization / desalting and sterilization method and device, wherein the high-efficiency flow type capacitor deionization / desalting device can be applied to the deionization and recovery of RO wastewater in the semiconductor process. Clean water. 如申請專利範圍第一項至第五項所述高效流動式電容去離子/脫鹽及殺菌方法與裝置,其中,高效流動式電容去離子/脫鹽之裝置可應用於海水脫鹽,回收乾淨水。 As described in the first to fifth items of the scope of the patent application, the high-efficiency flow type capacitor deionization / desalting and sterilization method and device, wherein the high-efficiency flow type capacitor deionization / desalting device can be applied to seawater desalination and recover clean water. 如申請專利範圍第一項至第五項所述高效流動式電容去離子/脫鹽及殺菌方法與裝置,其中,高效流動式電容去離子/脫鹽之裝置可應用於含重金屬污染地下水去離子,回收乾淨水。 As described in the first to fifth items in the scope of the patent application, the high-efficiency flow type capacitor deionization / desalting and sterilization method and device, wherein the high-efficiency flow type capacitor deionization / desalting device can be used for deionization and recovery of groundwater containing heavy metal pollution. Clean water. 如申請專利範圍第一項至第五項所述高效流動式電容去離子/脫鹽及殺菌方法與裝置,其中,在步驟(a)中陰極流動式懸浮溶液選用鋰錳氧化物作為鋰離子之吸附劑。鋰錳氧化物可以選擇性吸附鋰離子,使鋰離子之回收率遠大於其餘正電離子。將吸附飽和之鋰錳氧化物流入另一串連裝置,並以二次水將去鋰離子從離猛氧化物上脫附至溶液中,完成鋰離子之濃縮回收。應用於流動式電容去離子裝置之陰極懸浮溶液,可以有效提升鋰離子之吸附效率,且施加逆向或零電壓即可將鋰離子從碳材脫附,不會有二次污染之疑慮。 As described in the first to fifth items of the patent application scope, the high-efficiency flow type capacitor deionization / desalting and sterilization method and device, wherein in step (a), the cathode flow type suspension solution selects lithium manganese oxide for lithium ion adsorption Agent. Lithium manganese oxide can selectively adsorb lithium ions, so that the recovery rate of lithium ions is much larger than that of other positively charged ions. The adsorption-saturated lithium manganese oxide is flowed into another series of devices, and the delithium ions are desorbed from the ion oxide into the solution with secondary water to complete the lithium ion concentration recovery. The cathode suspension solution applied to the flow-type capacitor deionization device can effectively improve the adsorption efficiency of lithium ions, and can apply reverse or zero voltage to desorb the lithium ions from the carbon material without the concern of secondary pollution.
TW107105889A 2018-02-14 2018-02-14 A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters TW201934496A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW107105889A TW201934496A (en) 2018-02-14 2018-02-14 A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW107105889A TW201934496A (en) 2018-02-14 2018-02-14 A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters

Publications (1)

Publication Number Publication Date
TW201934496A true TW201934496A (en) 2019-09-01

Family

ID=68618527

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107105889A TW201934496A (en) 2018-02-14 2018-02-14 A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters

Country Status (1)

Country Link
TW (1) TW201934496A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111410274A (en) * 2020-04-17 2020-07-14 清华大学深圳国际研究生院 Titanium-based material, preparation method thereof and application thereof in flow electrode
TWI728772B (en) * 2020-04-07 2021-05-21 范振軒 Can be used for both series and parallel solution flow channels

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI728772B (en) * 2020-04-07 2021-05-21 范振軒 Can be used for both series and parallel solution flow channels
CN111410274A (en) * 2020-04-17 2020-07-14 清华大学深圳国际研究生院 Titanium-based material, preparation method thereof and application thereof in flow electrode

Similar Documents

Publication Publication Date Title
Xing et al. Versatile applications of capacitive deionization (CDI)-based technologies
Tang et al. Various cell architectures of capacitive deionization: Recent advances and future trends
Zhang et al. Selective ion separation by capacitive deionization (CDI) based technologies: a state-of-the-art review
US11261109B2 (en) Single module, flow-electrode apparatus and method for continous water desalination and ion separation by capacitive deionization
Zou et al. Using activated carbon electrode in electrosorptive deionisation of brackish water
US6462935B1 (en) Replaceable flow-through capacitors for removing charged species from liquids
Oyarzun et al. Adsorption and capacitive regeneration of nitrate using inverted capacitive deionization with surfactant functionalized carbon electrodes
CN103936116B (en) A kind of manganese dioxide/carbon combined electrode for heavy metal ion in electro-adsorption water and electro-adsorption method
KR101004707B1 (en) Electrode and electronic cell using it for eliminating ions in water
CN102603039A (en) Coupling desalination method and device
Shin et al. Improving the feasibility and applicability of flow-electrode capacitive deionization (FCDI): Review of process optimization and energy efficiency
TW201934496A (en) A flowing capacitive method and its divice for desalination and disinfection of sea/waste waters
CN103359809B (en) Ion removing device
Wang et al. Removal of low concentrations of nickel ions in electroplating wastewater using capacitive deionization technology
Yu et al. A comprehensive review on flow-electrode capacitive deionization: Design, active material and environmental application
Tong et al. Advances in efficient desalination technology of capacitive deionization for water recycling
KR102004687B1 (en) A module for lithium ion recycling of seawater and method for recycling lithium ion thereof
Maddah et al. Activated carbon cloth for desalination of brackish water using capacitive deionization
KR101944954B1 (en) Deionization and sterilization system including silver electrode and methods of deionization and sterilization using the same
JP2017225927A (en) Desalinization capacitor
US10662082B2 (en) Devices and methods for removing dissolved ions from water using composite resin electrodes
CN204981434U (en) A processing system for industry desalination
US20210171369A1 (en) Methods of removing contaminants from a solution, and related systems
CN203904046U (en) Continuous wastewater treatment device using membrane capacitive deionization
CN203866079U (en) Nano titanium carburization electrode CDI (capacitive deionization) device