TWI671434B - Method for producing chlorine dioxide by using brine and producing chlorine dioxide equipment - Google Patents
Method for producing chlorine dioxide by using brine and producing chlorine dioxide equipment Download PDFInfo
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Abstract
一種利用鹵水生產二氧化氯的方法，包含以下步驟：提供一鹵水組分及一包含氫氧化鈉的第一鹼組分，其中，該鹵水組分包括至少一種由下列群組所組成的成分：一利用海水經一海水淡化處理所產生的鹵水及一利用該鹵水經一去除硫酸根及鈣離子的處理所產生的經處理鹵水；將該鹵水組分與至少部分的第一鹼組分混合並進行過濾處理，得到包含氯化鈉的濾液；將一包含該濾液的電解用組分進行一電解處理，生產二氧化氯及經電解處理的濾液。A method for producing chlorine dioxide using brine, comprising the steps of providing a brine component and a first alkali component containing sodium hydroxide, wherein the brine component includes at least one component composed of the following group: A brine produced by desalination using seawater and a treated brine produced by using the brine to remove sulfate and calcium ions; the brine component is mixed with at least part of the first alkali component and The filtering treatment is performed to obtain a filtrate containing sodium chloride; an electrolytic component containing the filtrate is subjected to an electrolytic treatment to produce chlorine dioxide and the electrolytically treated filtrate.
Description
本發明是有關於一種生產二氧化氯的方法，特別是指一種利用鹵水生產二氧化氯的方法。The invention relates to a method for producing chlorine dioxide, in particular to a method for producing chlorine dioxide by using brine.
由於生活及工業用水量不斷增加，以及全球氣候變遷的威脅日益顯著，導致缺水風險日增。目前除藉由雨水來供給生活用水或工業用水等水源外，藉由淡化海水來供給該水源已成為國際水資源利用的趨勢。雖淡化海水過程中可產生供給生活用水及工業用水等水源，但也會伴隨產出高鹽度鹵水。該鹵水的處理方式是直接排放至大海中。由於該鹵水具有大量的鹽類，會破壞海洋生態的平衡，繼而影響海洋中物種的生存、生長與繁殖。有鑒於此，為減少排放鹵水對海洋的生態環境造成影響，如何將該鹵水進行再利用，以提高該鹵水的應用價值是值得被研究及探討。Increasing domestic and industrial water consumption, and the increasing threat of global climate change, have led to increased water shortage risks. At present, in addition to supplying domestic water or industrial water by rainwater, it has become an international water resource utilization trend to supply this water source by desalinating seawater. Although water sources such as domestic water and industrial water can be produced during the desalination process, high-salinity brines are also produced. The brine is treated directly into the sea. Because the brine has a large amount of salt, it will destroy the balance of the marine ecology, and then affect the survival, growth and reproduction of species in the ocean. In view of this, in order to reduce the impact of the discharged brine on the ecological environment of the ocean, how to reuse the brine to increase the application value of the brine is worth studying and exploring.
因此，本發明的第一目的，即在提供一種利用鹵水生產二氧化氯的方法。Therefore, a first object of the present invention is to provide a method for producing chlorine dioxide using brine.
於是，本發明利用鹵水生產二氧化氯的方法，包含以下步驟：提供一鹵水組分及一包含氫氧化鈉的第一鹼組分，其中，該鹵水組分包括至少一種由下列群組所組成的成分：一利用一海水經海水淡化處理所產生的鹵水及一利用該鹵水經一去除硫酸根及鈣離子的處理所產生的經處理鹵水；將該鹵水組分與至少部分的第一鹼組分混合並進行一過濾處理，得到一包含氯化鈉的濾液；將一包含該濾液的電解用組分進行一電解處理，生產二氧化氯及經電解處理的濾液。Therefore, the method for producing chlorine dioxide using brine in the present invention includes the following steps: providing a brine component and a first alkali component containing sodium hydroxide, wherein the brine component includes at least one of the following groups Ingredients: a brine produced by seawater desalination and a treated brine produced by using the brine to remove sulfate and calcium ions; the brine component and at least part of the first base group Sub-mixing and performing a filtering treatment to obtain a filtrate containing sodium chloride; subjecting an electrolytic component containing the filtrate to an electrolytic treatment to produce chlorine dioxide and the electrolytic-treated filtrate.
本發明的功效在於：將該鹵水再利用以作為電解用組分，提高該鹵水的應用價值，並減少該鹵水對海洋生態的影響。The effect of the invention is that the brine is reused as a component for electrolysis, the application value of the brine is increased, and the impact of the brine on marine ecology is reduced.
本發明的第二目的，即在提供一種生產二氧化氯設備。A second object of the present invention is to provide a device for producing chlorine dioxide.
本發明生產二氧化氯設備，包含一海水淡化裝置、一電解裝置、一混合槽、一過濾器及一輸送單元。該海水淡化裝置用於將一海水進行一海水淡化處理以產生一淡化水及一鹵水。該電解裝置用於將一電解用組分進行一電解處理以產生二氧化氯及一包含氫氧化鈉的鹼組分。該混合槽連接該海水淡化裝置及該電解裝置，且用來將該鹵水與該鹼組分混合，形成一混合物。該過濾器位於該混合槽的下游處，且用來過濾該混合物而獲得一包含氯化鈉的濾液。該輸送單元連接該過濾器及該電解裝置，且用來將作為該電解用組分的濾液輸送至該電解裝置。The chlorine dioxide production equipment of the present invention comprises a seawater desalination device, an electrolytic device, a mixing tank, a filter and a conveying unit. The seawater desalination device is used for subjecting a seawater to a seawater desalination process to generate a desalinated water and a brine. The electrolytic device is used for subjecting an electrolytic component to an electrolytic treatment to produce chlorine dioxide and an alkali component containing sodium hydroxide. The mixing tank is connected to the seawater desalination device and the electrolytic device, and is used to mix the brine with the alkali component to form a mixture. The filter is located downstream of the mixing tank and is used to filter the mixture to obtain a filtrate containing sodium chloride. The transfer unit is connected to the filter and the electrolysis device, and is used to transfer the filtrate, which is a component for electrolysis, to the electrolysis device.
參閱圖1，本發明利用鹵水生產二氧化氯的方法的第一實施例包含以下步驟：步驟(一)，提供一鹵水組分及一包含氫氧化鈉的第一鹼組分；步驟(二)，將該鹵水組分與至少部分的第一鹼組分混合並進行一過濾處理，得到一包含氯化鈉的濾液；步驟(三)，將一包含該濾液的電解用組分進行一電解處理，生產二氧化氯及經電解處理的濾液。本第一實施例利用一生產二氧化氯設備來進行，且該生產二氧化氯設備包含一海水淡化裝置1、一電解裝置2、一混合槽3、一過濾器4，及一輸送單元5。Referring to FIG. 1, a first embodiment of a method for producing chlorine dioxide using brine in the present invention includes the following steps: step (a), providing a brine component and a first alkali component including sodium hydroxide; step (b) , Mixing the brine component with at least part of the first alkali component and subjecting it to a filtration treatment to obtain a filtrate containing sodium chloride; step (c), subjecting an electrolytic component containing the filtrate to an electrolytic treatment , Producing chlorine dioxide and the filtrate after electrolytic treatment. The first embodiment is performed by using a chlorine dioxide production device, and the chlorine dioxide production device includes a seawater desalination device 1, an electrolytic device 2, a mixing tank 3, a filter 4, and a transport unit 5.
在該步驟(一)中，該鹵水組分包括至少一種由下列群組所組成的成分：一利用一海水經海水淡化處理所產生的鹵水及一利用該鹵水經一去除硫酸根及鈣離子的處理所產生的經處理鹵水。In this step (1), the brine component includes at least one component composed of the following: a brine produced by seawater desalination treatment and a brine which is used to remove sulfate and calcium ions. Treat the resulting treated brine.
該海水淡化處理是利用該海水淡化裝置1來進行，以將一海水淡化並產生一淡化水及該鹵水。該海水選自於表層海水、中層海水、深層海水，或上述任意組合。在該第一實施例中，該海水為深度650米的海洋深層水。該海水淡化處理並無特別限制，採用以往用來淡化海水的海水淡化處理方式，舉例來說，該海水淡化處理為逆滲透處理或蒸餾處理等。該海水淡化裝置1例如但不限於逆滲透裝置或蒸餾裝置等。在該第一實施例中，該海水淡化處理為薄膜透析法，且該鹵水包含複數種鹽類及複數種離子，且該鹽類例如但不限於氯化鈉、氯化鎂、硫酸鎂、硫酸鈣、硫酸鉀、碳酸鈣或溴化鎂等，而該離子例如但不限於氯離子、鈉離子、鎂離子、硫酸根、鈣離子、鉀離子、碳酸氫根、溴離子、鍶離子等。The seawater desalination process is performed using the seawater desalination device 1 to desalinate a seawater and generate a desalinated water and the brine. The seawater is selected from surface seawater, middle seawater, deep seawater, or any combination thereof. In the first embodiment, the seawater is deep ocean water with a depth of 650 meters. This seawater desalination process is not particularly limited, and a conventional seawater desalination process used to desalinate seawater is used. For example, the seawater desalination process is a reverse osmosis process or a distillation process. The seawater desalination device 1 is, for example, but not limited to, a reverse osmosis device or a distillation device. In the first embodiment, the seawater desalination process is a thin film dialysis method, and the brine contains a plurality of salts and a plurality of ions, and the salts are, for example, but not limited to, sodium chloride, magnesium chloride, magnesium sulfate, calcium sulfate, Potassium sulfate, calcium carbonate, magnesium bromide, and the like, and the ion is, for example, but not limited to, chloride, sodium, magnesium, sulfate, calcium, potassium, bicarbonate, bromide, strontium, and the like.
該去除硫酸根及鈣離子的處理目的在於避免因硫酸根或鈣離子與該電解裝置2的電極或電極上的塗層作用，或因硫酸根或鈣離子的存在於該電解處理的過程中產生不必要的析出物，而造成該電解裝置2的耗損，使得該電解裝置2使用期限變短。在該去除硫酸根及鈣離子的處理中，該硫酸根及該鈣離子的去除可利用離子交換樹脂膜來進行。除上述外，該硫酸根也可利用氯化鋇來進行，使該硫酸根轉變成硫酸鋇而析出，而該鈣離子也可利用碳酸鈉來進行，使該鈣離子轉變成碳酸鈣而析出。在該第一實施例中，該鹵水組分為該經處理鹵水，且該經處理鹵水是利用氯化鋇及碳酸鈉進行去除硫酸根及鈣離子的處理。The purpose of the treatment for removing sulfate and calcium ions is to avoid the effects of sulfate or calcium ions and the coating on the electrodes or electrodes of the electrolytic device 2 or the existence of sulfate or calcium ions during the electrolytic treatment. Unnecessary precipitates cause wear of the electrolytic device 2 and shorten the life of the electrolytic device 2. In the process of removing sulfate and calcium ions, the removal of sulfate and calcium ions can be performed using an ion exchange resin membrane. In addition to the above, the sulfate can also be performed using barium chloride to convert the sulfate to barium sulfate and precipitate, and the calcium ion can also be performed using sodium carbonate to convert the calcium ion to calcium carbonate and precipitate. In the first embodiment, the brine component is the treated brine, and the treated brine is treated with barium chloride and sodium carbonate to remove sulfate and calcium ions.
在該步驟(二)中，該鹵水組分與該第一鹼組分的混合利用該混合槽3來進行，且該混合槽3連接該海水淡化裝置1，而該過濾處理利用位於該混合槽3下游處的該過濾器4來進行。該混合槽3並無特別限制，只要能將該鹵水組分與該第一鹼組分混合即可，舉例來說，該混合槽3為一具有攪拌器的攪拌槽。該第一鹼組分的目的在於去除該鹵水組分中的鎂離子及鐵離子，以使該鎂離子及鐵離子分別轉變成氫氧化鎂及氫氧化鐵而析出，繼而避免因鎂及鐵的存在使得於該電解處理的過程中產生不必要的析出物，而造成該電解裝置2的耗損以及造成電壓下降，導致電能的耗損提升。該過濾處理目的在於將該鹵水組分中存在的懸浮物移除或將該鹵水組分與該第一鹼組分混合後所產生的析出物移除。該過濾器4並無特別限制，只要能將該懸浮物及該析出物移除即可。在該第一實施例中，將該第一鹼組分加入該鹵水組分中，並將pH控制在7至11間，以利該電解處理的進行，繼而提高二氧化氯的生產效益。In the step (2), the mixing of the brine component and the first alkali component is performed by using the mixing tank 3, and the mixing tank 3 is connected to the desalination device 1, and the filtering process is performed by using the mixing tank. 3 downstream of this filter 4. The mixing tank 3 is not particularly limited as long as the brine component can be mixed with the first alkali component. For example, the mixing tank 3 is a stirring tank with a stirrer. The purpose of the first alkali component is to remove the magnesium ions and iron ions in the brine component, so that the magnesium ions and iron ions are converted into magnesium hydroxide and iron hydroxide, respectively, and then precipitated. Existence causes unnecessary precipitates to be generated during the electrolytic treatment, which causes the loss of the electrolytic device 2 and the voltage drop, which leads to an increase in the loss of electrical energy. The purpose of the filtering treatment is to remove the suspended matter existing in the brine component or remove the precipitate generated after mixing the brine component with the first alkali component. The filter 4 is not particularly limited as long as the suspended matter and the precipitate can be removed. In the first embodiment, the first alkali component is added to the brine component, and the pH is controlled between 7 and 11, so as to facilitate the electrolytic treatment, and then improve the production efficiency of chlorine dioxide.
於該步驟(三)中，該電解處理利用該電解裝置2來進行，而該包含該濾液的電解用組分利用連接該過濾器4及該電解裝置2的輸送單元5輸送至該電解裝置2中。該電解裝置2界定出一陽極室210及一陰極室220，且包括一容置在該陽極室210的一陽極單元21、一容置在該陰極室220的陰極單元22，及一將該陽極室210及該陰極室220隔開的隔離膜單元23。該陽極室210具有一供該電解用組分進入的入液口10、一供該經電解處理的濾液排出的出液口20，及一供二氧化氯氣體排出的出氣口30。該陰極室220具有一排液口40。相對於該濾液，該經電解處理的濾液包含少量的氯化鈉、氯氣、次氯酸鹽及氯酸鹽。該次氯酸鹽例如次氯酸鈉。該氯酸鹽例如氯酸鈉。In the step (3), the electrolytic treatment is performed using the electrolytic device 2, and the electrolytic component containing the filtrate is transferred to the electrolytic device 2 by a transport unit 5 connected to the filter 4 and the electrolytic device 2. in. The electrolytic device 2 defines an anode chamber 210 and a cathode chamber 220, and includes an anode unit 21 accommodated in the anode chamber 210, a cathode unit 22 accommodated in the cathode chamber 220, and an anode The separation membrane unit 23 is separated from the chamber 210 and the cathode chamber 220. The anode chamber 210 has a liquid inlet 10 through which the components for electrolysis enter, a liquid outlet 20 through which the electrolytically processed filtrate is discharged, and a gas outlet 30 through which chlorine dioxide gas is discharged. The cathode chamber 220 has a liquid discharge port 40. Relative to the filtrate, the electrolytically treated filtrate contains a small amount of sodium chloride, chlorine gas, hypochlorite and chlorate. The hypochlorite is, for example, sodium hypochlorite. The chlorate is, for example, sodium chlorate.
參閱圖2，本發明利用鹵水生產二氧化氯的方法的第二實施例與該第一實施例不同在於：該電解用組分經該電解處理還生產一包含氫氧化鈉的第二鹼組分。將該第二鹼組分作為該第一鹼組分的來源。本發明第二實施例的好處在於當進行該電解處理後，直接使用該第二鹼組分作為該第一鹼組分，而不需由外界再提供該第一鹼組分，以降低生產成本，同時，以減少該第二鹼組分的排放處理費用，並減少因排放該第二鹼組分對環境造成的影響，而符合環保需求。Referring to FIG. 2, the second embodiment of the method for producing chlorine dioxide using brine is different from the first embodiment in that the electrolysis component also produces a second alkali component including sodium hydroxide after the electrolytic treatment. . The second base component is used as a source of the first base component. The advantage of the second embodiment of the present invention is that after the electrolytic treatment is performed, the second alkali component is directly used as the first alkali component, and the first alkali component does not need to be provided by the outside to reduce production costs. At the same time, in order to reduce the disposal cost of the second alkali component and reduce the environmental impact caused by the discharge of the second alkali component, it meets environmental protection requirements.
參閱圖3，本發明利用鹵水生產二氧化氯的方法的第三實施例與該第二實施例不同在於：還包含一將至少部分經電解處理的濾液與該濾液混合形成該電解用組分的混合步驟。該第三實施例的一變化態樣為在該混合步驟前對該至少部分經電解處理的濾液進行除氯處理的除氯步驟。該除氯處理目的在於避免進行該電解處理時形成過多的氯氣，使得二氧化氯的純度降低。該除氯處理可利用一包含亞氯酸鹽或硫代硫酸鹽的裝置(圖未示)來進行。該亞氯酸鹽例如但不限於亞氯酸鈉。該硫代硫酸鹽例如但不限於硫代硫酸鈉。為避免該經電解處理的濾液中的氯酸鹽影響於進行該電解處理時二氧化氯的生產效益以及為避免當需將該經電解處理的濾液排放至環境中時該經電解處理的濾液中的氯酸鹽對環境及人類的不良影響，該第三實施例的另一變化態樣為在該除氯步驟前對該至少部分經電解處理的濾液進行除去氯酸鹽處理的除鹽步驟。該除鹽處理可利用一鹽酸來進行。Referring to FIG. 3, the third embodiment of the method for producing chlorine dioxide using brine is different from the second embodiment in that it further includes a method for mixing at least part of the filtrate subjected to electrolytic treatment with the filtrate to form the component for electrolysis. Mixing steps. A variation of the third embodiment is a dechlorination step of performing a dechlorination treatment on the at least partially electrolytically treated filtrate before the mixing step. The purpose of the dechlorination treatment is to avoid the formation of excessive chlorine gas during the electrolytic treatment, so that the purity of the chlorine dioxide is reduced. The dechlorination treatment can be performed using an apparatus (not shown) containing chlorite or thiosulfate. The chlorite is, for example, but is not limited to, sodium chlorite. The thiosulfate is, for example, but is not limited to, sodium thiosulfate. To prevent the chlorate in the electrolytically treated filtrate from affecting the production efficiency of chlorine dioxide during the electrolytic treatment and to avoid the electrolytically treated filtrate from being discharged to the environment when the electrolytically treated filtrate is required to be discharged to the environment The chlorate has an adverse effect on the environment and humans. Another variation of the third embodiment is that the chlorate-removing step is performed on the at least part of the filtrate subjected to electrolytic treatment before the chlorine-removing step. This desalting process can be performed using a hydrochloric acid.
參閱圖4，本發明利用鹵水生產二氧化氯的方法的第四實施例與該第三實施例不同在於：還包含將該至少部分經電解處理的濾液與該第二鹼組分混合後再與該濾液混合形成該電解用組分的混合步驟。該第四實施例的一變化態樣為對該至少部分經電解處理的濾液進行除氯處理的除氯步驟。該除氯處理利如上述，故不再贅述。該第四實施例的另一變化態樣為在該除氯步驟前對該至少部分經電解處理的濾液進行除去氯酸鹽處理的除鹽步驟。該除鹽處理可利用一鹽酸來進行。Referring to FIG. 4, a fourth embodiment of the method for producing chlorine dioxide using brine is different from the third embodiment in that the method further includes mixing the at least partially electrolytically-treated filtrate with the second alkali component, and then The filtrates are mixed to form a mixing step of the components for electrolysis. A variation of the fourth embodiment is a dechlorination step of performing a dechlorination treatment on the at least partially electrolytically-treated filtrate. The benefit of the chlorine removal treatment is as described above, so it will not be described again. In another variation of the fourth embodiment, before the chlorine removal step, the at least part of the filtrate subjected to the electrolytic treatment is subjected to a chlorate removal salt removal step. This desalting process can be performed using a hydrochloric acid.
綜上所述，本發明將該鹵水再利用以作為電解用組分，提高該鹵水的應用價值，並減少該鹵水對海洋生態的影響。再者，該電解用組分經該電解處理還生產一包含氫氧化鈉的第二鹼組分。將該第二鹼組分作為該第一鹼組分的來源，而不需由外界再提供該第一鹼組分，可降低生產成本、減少該第二鹼組分的排放處理費用，並減少因排放該第二鹼組分對環境造成的影響，而符合環保需求，故確實能達成本發明的目的。In summary, the present invention reuses the brine as a component for electrolysis, improves the application value of the brine, and reduces the impact of the brine on marine ecology. Furthermore, the electrolytic component also undergoes the electrolytic treatment to produce a second alkali component containing sodium hydroxide. Using the second alkali component as a source of the first alkali component without providing the first alkali component from the outside can reduce production costs, reduce the disposal cost of the second alkali component, and reduce Because the discharge of the second alkali component has an impact on the environment and meets environmental protection requirements, it can indeed achieve the purpose of cost invention.
惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, any simple equivalent changes and modifications made according to the scope of the patent application and the contents of the patent specification of the present invention are still Within the scope of the invention patent.
1‧‧‧海水淡化裝置1‧‧‧ desalination plant
2‧‧‧電解裝置2‧‧‧ Electrolysis device
21‧‧‧陽極單元21‧‧‧Anode unit
210‧‧‧陽極室210‧‧‧Anode Room
10‧‧‧入液口10‧‧‧Inlet
20‧‧‧出液口20‧‧‧ Outlet
30‧‧‧出氣口30‧‧‧ Outlet
22‧‧‧陰極單元22‧‧‧ cathode unit
220‧‧‧陰極室220‧‧‧ cathode chamber
40‧‧‧排液口40‧‧‧ drain port
23‧‧‧隔離膜單元23‧‧‧Isolation membrane unit
3‧‧‧混合槽3‧‧‧ mixing tank
4‧‧‧過濾器4‧‧‧ filter
5‧‧‧輸送單元 5‧‧‧Conveying unit
本發明的其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是一流程示意圖，用來說明本發明利用鹵水生產二氧化氯的方法的第一實施例； 圖2是一流程示意圖，用來說明本發明利用鹵水生產二氧化氯的方法的第二實施例； 圖3是一流程示意圖，用來說明本發明利用鹵水生產二氧化氯的方法的第三實施例；及 圖4是一流程示意圖，用來說明本發明利用鹵水生產二氧化氯的方法的第四實施例。Other features and effects of the present invention will be clearly presented in the embodiment with reference to the drawings, in which: FIG. 1 is a schematic flow chart for explaining a first embodiment of the method for producing chlorine dioxide using brine in the present invention; FIG. 2 is a schematic flowchart for explaining a second embodiment of the method for producing chlorine dioxide using brine in the present invention; FIG. 3 is a schematic flowchart for explaining the third embodiment of the method for producing chlorine dioxide using brine in the present invention Example; and FIG. 4 is a schematic flow chart for explaining a fourth embodiment of the method for producing chlorine dioxide using brine in the present invention.
Claims (5)
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| TW105129887A TWI671434B (en) | 2016-09-13 | 2016-09-13 | Method for producing chlorine dioxide by using brine and producing chlorine dioxide equipment |
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| TWI671434B true TWI671434B (en) | 2019-09-11 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319332A (en) * | 2007-06-07 | 2008-12-10 | 邓军 | Chlorine dioxide generating device and method |
| TWI359879B (en) * | 2007-12-19 | 2012-03-11 | Ind Tech Res Inst | Apparatus for chlorine dioxide generation and meth |
| CN102534649A (en) * | 2012-01-11 | 2012-07-04 | 吉林大学 | Method for preparing chlorine dioxide solution by using electrooxidation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319332A (en) * | 2007-06-07 | 2008-12-10 | 邓军 | Chlorine dioxide generating device and method |
| TWI359879B (en) * | 2007-12-19 | 2012-03-11 | Ind Tech Res Inst | Apparatus for chlorine dioxide generation and meth |
| CN102534649A (en) * | 2012-01-11 | 2012-07-04 | 吉林大学 | Method for preparing chlorine dioxide solution by using electrooxidation |
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