WO2023092618A1 - Method and device for preparing chlorine gas by means of photocatalytic oxidation of anthraquinone - Google Patents

Method and device for preparing chlorine gas by means of photocatalytic oxidation of anthraquinone Download PDF

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WO2023092618A1
WO2023092618A1 PCT/CN2021/134695 CN2021134695W WO2023092618A1 WO 2023092618 A1 WO2023092618 A1 WO 2023092618A1 CN 2021134695 W CN2021134695 W CN 2021134695W WO 2023092618 A1 WO2023092618 A1 WO 2023092618A1
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anthraquinone
chlorine gas
photocatalytic
reaction solution
photocatalytic oxidation
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PCT/CN2021/134695
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French (fr)
Chinese (zh)
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郑航桅
丁杰
赵焱
杨珊珊
武睿
高新磊
赵双阳
陈成新
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哈尔滨工业大学水资源国家工程研究中心有限公司
哈尔滨工业大学
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Publication of WO2023092618A1 publication Critical patent/WO2023092618A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside

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  • the invention belongs to the technical field of photocatalysts, and in particular relates to a method and a device for preparing chlorine gas by photocatalytic oxidation of anthraquinone.
  • the present invention provides a method and device for preparing chlorine by photocatalytic oxidation of anthraquinone in order to solve the problems of complex production process and high energy consumption of the existing chlorine gas.
  • the aeration system includes a fan, an air inlet pipe and an aeration head. One end of the air inlet pipe is connected to the fan, and the other end of the air inlet pipe is connected to the aeration head.
  • the aeration head is located at the bottom of the reaction generator.
  • the gas outlet, one end of the gas outlet pipe is connected with the gas outlet, and the other end of the gas outlet pipe extends into the chlorine gas collector, and the chlorine gas collecting liquid is housed in the chlorine gas collector.
  • the method and device for preparing chlorine by photocatalytic oxidation of anthraquinone in the present invention include the following beneficial effects:
  • the method for producing chlorine gas by photocatalysis of the present invention is green and energy-saving.
  • the photocatalytic reaction generator through visible light irradiation, in a high-concentration sodium chloride aqueous solution, anthraquinone with a sulfonic acid group can oxidize chloride ions, and under acidic conditions Chlorine gas is produced, which is then collected by a chlorine gas trap.
  • the operating parameters refer to the aeration flow rate and the gas composition of the aeration. and light intensity.
  • the device for generating chlorine gas by photocatalytic oxidation of anthraquinone of the present invention can operate efficiently and stably for a long time, and is applied to disinfect microorganisms in water bodies in situ and remove ammonia nitrogen and organic matter in water.
  • the method for preparing chlorine gas by photocatalytic oxidation of anthraquinone in this embodiment is implemented according to the following steps:
  • Embodiment 8 This embodiment is different from Embodiment 7 in that the gas used for aeration is air or oxygen.
  • Embodiment 11 The device for preparing chlorine by photocatalytic oxidation of anthraquinone in this embodiment includes an aeration system, a reaction generator 11 and a chlorine gas collector 12, and a photocatalytic reaction solution is installed in the reaction generator 11.
  • the photocatalytic The reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic acid groups, and a light source 9 is arranged in the reaction generator 11;
  • the aeration system includes a fan 1, an air inlet pipe 13 and an aeration head 6, one end of the air inlet pipe 13 is connected with the fan 1, and the other end of the air inlet pipe 13 is connected with the aeration head 6, and the aeration head 6 is located at the bottom of the reaction generator 11 , have gas outlet 8 on the top of reaction generator 11, and one end of gas outlet pipe 10 is connected with gas outlet 8, and the other end of gas outlet pipe 10 extends in the chlorine gas collector 12, and chlorine gas collection liquid is housed in the chlorine gas collector 12.
  • the main body of the reactor of the device for producing chlorine by photocatalytic oxidation of anthraquinone in this embodiment is a reaction generator made of plexiglass.
  • a tubular xenon lamp light source is placed in the center of the inner cylinder.
  • the upper end of the reaction generator is airtight, and a gas outlet is left on the top of the reaction generator.
  • the bottom of the reaction generator is equipped with an aeration head, the fan blows out the gas, the aeration volume is controlled by the flow meter, and the gas is dispersed into the reaction system from the bottom of the reaction generator through the aeration sand head.
  • the concentration of the sodium hydroxide (NaOH) solution is 0.1 mol/L.
  • a quartz sleeve is coaxially arranged in the reaction generator 11 to balance the flow velocity of the solution in the reactor.
  • Embodiment 15 This embodiment is different from Embodiment 11 to Embodiment 14 in that a water inlet pipe 5 is connected to the bottom of the reaction generator 1 .
  • a water outlet pipe 7 is communicated with the bottom of the reaction generator 1 .
  • Embodiment 16 This embodiment differs from Embodiment 11 to Embodiment 15 in that the light intensity of the light source 9 is controlled to be 50-100 mW/cm 2 .
  • Embodiment 17 This embodiment differs from Embodiment 11 to Embodiment 17 in that the aeration flow rate of the aeration head 6 is controlled to be 300-800 mL/min.
  • Embodiment 1 The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone in this embodiment is implemented according to the following steps:
  • the photocatalytic reaction solution contains 100 ⁇ mol/L AQ2S and 2mol/L NaCl.
  • This embodiment uses the device for preparing chlorine gas by photocatalytic oxidation of anthraquinone described in Embodiment 11.
  • the reaction generator 11 is a plexiglass cylinder with a diameter of 100 mm, a height of 400 mm, and an effective water depth of 350 mm. Wind the hose of the constant temperature water tank to keep the temperature of the reaction solution at 25 ⁇ 1°C; place a tubular xenon lamp light source in the center of the reaction generator 11 with a radiation intensity of 64mW/cm 2 .
  • Example 2 The difference between this example and Example 1 is that the pH of the solution is adjusted to 3 by 0.1 mol/L HCl in step 2.
  • Embodiment 3 The difference between this embodiment and Embodiment 1 is that the photocatalytic reaction solution in step 2 contains 100 ⁇ mol/L of anthraquinone-2-sodium sulfonate (AQ2S) and 0.5mol/L NaCl.
  • AQ2S anthraquinone-2-sodium sulfonate
  • Embodiment 5 The difference between this embodiment and Embodiment 1 is that the temperature of the reaction solution is maintained at 35 ⁇ 1°C.
  • Embodiment 6 The difference between this embodiment and embodiment 1 is that the step 2 photocatalytic reaction solution contains 300 ⁇ mol/L of AQ2S and 2mol/L NaCl.
  • the chlorine gas production process of the present invention has the advantages of low energy consumption, simplicity and high efficiency, and can realize in-situ production of chlorine gas, remove pollutants in water bodies or be used for water body disinfection.

Abstract

A method and device for preparing chlorine gas by means of photocatalytic oxidation of an anthraquinone, belonging to the technical field of photocatalysts, and aiming to solve the problems of existing chlorine gas production processes being complex and having high energy consumption. The method for preparing chlorine gas by means of photocatalytic oxidation of an anthraquinone comprises adding an anthraquinone having a sulfonic acid group into an NaCl solution, adjusting the system to be acidic to obtain a photocatalytic reaction solution, irradiating the photocatalytic reaction solution by using a visible light source, and performing a photocatalytic reaction to obtain chlorine gas. The invention also relates to a device for preparing chlorine gas by means of photocatalytic oxidation of an anthraquinone. The device comprises an aeration system, a reactor (11) and a chlorine gas collector (12), wherein the reactor (11) is filled with a photocatalytic reaction solution, and a light source (9) is arranged in the reactor (11). The method for producing chlorine gas by means of photocatalysis is environmentally friendly and energy-saving. In a photocatalysis reactor, under the irradiation of visible light, an anthraquinone having a sulfonic acid group in a high-concentration sodium chloride aqueous solution can oxidize chloride ions, and chlorine gas is produced under an acidic condition.

Description

一种蒽醌光催化氧化制备氯气的方法及装置A method and device for preparing chlorine gas by photocatalytic oxidation of anthraquinone 技术领域technical field
本发明属于光催化剂技术领域，具体涉及一种蒽醌光催化氧化制备氯气的方法及装置。The invention belongs to the technical field of photocatalysts, and in particular relates to a method and a device for preparing chlorine gas by photocatalytic oxidation of anthraquinone.
背景技术Background technique
随着工业的迅速发展、人口的急剧增加，我国作为人口大国，水资源短缺和污染问题日益严重，为了应对人类日益增长的需求，越来越多的结构稳定环境持久性强的新型化学物质被合成开发，并随着工业生产以及人类的使用而进入自然水体，对自然生态***造成严重的影响。但是，现有以生物处理技术为主的水处理工艺在实际应用过程中表现出处理能力和处理效率不足等状况，因此，亟待开发出一种绿色，高效且稳定的新型污水处理技术来应对上述问题。With the rapid development of industry and the rapid increase of population, as a country with a large population, the shortage of water resources and pollution problems are becoming increasingly serious. In order to meet the growing needs of human beings, more and more new chemical substances with stable structures and strong environmental durability are Synthetic development, and with industrial production and human use into the natural water body, causing serious impact on the natural ecosystem. However, the existing water treatment technology based on biological treatment technology shows insufficient treatment capacity and treatment efficiency in the actual application process. Therefore, it is urgent to develop a green, efficient and stable new sewage treatment technology to deal with the above question.
消毒过程是水处理过程中的最后一道屏障，对污染物质的去除起着重要作用。氯气最早用于水消毒的化学消毒剂，已成为世界各国水消毒的主要技术方法之一。其具有很多优点，如操作过程并不复杂、价格比较经济实惠，除此之外，还能在管网中存在具有消毒作用的余氯，能保证管网中水的安全性。除应用于水体的消毒外，还可以氧化降解水中的难降解有机污染物。然而，现阶段的最常用的氯气生产工艺为电解氯化钠的氯碱工艺。这一传统工艺不仅能耗高，且需要与电网相连或者配备高电压的蓄电池。除此之外，不论是氯气还是次氯酸盐的运输过程都相对繁琐，且由于化学稳定性较差，长距离运输会造成氯气的较大损耗。因此，急需一种低能耗且简便高效的氯气生产工艺，使其在使用地点可以实现原位生产。The disinfection process is the last barrier in the water treatment process and plays an important role in the removal of pollutants. Chlorine was the first chemical disinfectant used for water disinfection, and it has become one of the main technical methods for water disinfection in countries all over the world. It has many advantages, such as the operation process is not complicated, and the price is relatively affordable. In addition, residual chlorine with disinfection effect can also exist in the pipe network, which can ensure the safety of water in the pipe network. In addition to being applied to the disinfection of water bodies, it can also oxidize and degrade refractory organic pollutants in water. However, the most commonly used chlorine production process at this stage is the chlor-alkali process of electrolytic sodium chloride. This traditional process not only consumes a lot of energy, but also needs to be connected to the grid or equipped with high-voltage batteries. In addition, the transportation process of both chlorine gas and hypochlorite is relatively cumbersome, and due to poor chemical stability, long-distance transportation will cause a large loss of chlorine gas. Therefore, there is an urgent need for a low-energy, simple and efficient chlorine production process, so that it can be produced in situ at the place of use.
发明内容Contents of the invention
本发明是为了解决现有氯气生产工艺复杂，能耗高的问题，而提供一种蒽醌光催化氧化制备氯气的方法及装置。The present invention provides a method and device for preparing chlorine by photocatalytic oxidation of anthraquinone in order to solve the problems of complex production process and high energy consumption of the existing chlorine gas.
本发明蒽醌光催化氧化制备氯气的方法按照以下步骤实现：The method for preparing chlorine by anthraquinone photocatalytic oxidation of the present invention is realized according to the following steps:
一、配置NaCl溶液；1. Configure NaCl solution;
二、向NaCl溶液中加入带有磺酸基的蒽醌，调节体系呈酸性，得到光催化反应溶液；2. Add anthraquinone with a sulfonic acid group to the NaCl solution, adjust the system to be acidic, and obtain a photocatalytic reaction solution;
三、利用可见光源照射光催化反应溶液，光催化反应得到氯气。3. Utilize a visible light source to irradiate the photocatalytic reaction solution, and obtain chlorine gas through the photocatalytic reaction.
本发明蒽醌光催化氧化制备氯气的装置包括曝气***、反应发生器和氯气收集器，在反应发生器内装有光催化反应溶液，所述的光催化反应溶液为NaCl和带有磺酸基的蒽醌的混合溶液，在反应发生器内设置有光源；The device for preparing chlorine gas by photocatalytic oxidation of anthraquinone in the present invention includes an aeration system, a reaction generator and a chlorine gas collector, and a photocatalytic reaction solution is installed in the reaction generator, and the photocatalytic reaction solution is NaCl and has a sulfonic acid group The mixed solution of anthraquinone is provided with a light source in the reaction generator;
曝气***包括风机、进气管和曝气头，进气管的一端与风机相连，进气管的另一端与 曝气头相连，曝气头位于反应发生器的底部，在反应发生器的上部开有出气口，出气管的一端与出气口相连通，出气管的另一端延伸至氯气收集器中，氯气收集器内装有氯气收集液。The aeration system includes a fan, an air inlet pipe and an aeration head. One end of the air inlet pipe is connected to the fan, and the other end of the air inlet pipe is connected to the aeration head. The aeration head is located at the bottom of the reaction generator. The gas outlet, one end of the gas outlet pipe is connected with the gas outlet, and the other end of the gas outlet pipe extends into the chlorine gas collector, and the chlorine gas collecting liquid is housed in the chlorine gas collector.
本发明蒽醌光催化氧化制备氯气的方法中利用可见光激发AQ2S产生三线激发态，同时在反应体系中加入一定浓度的氯化钠来提供氯离子；产生的AQ2S三线激发态与氯离子反应进而产生氯气；最后依靠氢氧化钠溶液收集产生的氯气。In the method for preparing chlorine gas by photocatalytic oxidation of anthraquinone in the present invention, visible light is used to excite AQ2S to generate a triplet excited state, and at the same time, a certain concentration of sodium chloride is added to the reaction system to provide chloride ions; the generated AQ2S triplet excited state reacts with chloride ions to produce Chlorine gas; finally rely on sodium hydroxide solution to collect the generated chlorine gas.
与现有技术相比，本发明蒽醌光催化氧化制备氯气的方法及装置包括以下有益效果：Compared with the prior art, the method and device for preparing chlorine by photocatalytic oxidation of anthraquinone in the present invention include the following beneficial effects:
本发明光催化生产氯气的方法绿色节能，在光催化反应发生器中，通过可见光照射，在高浓度的氯化钠水溶液中，带有磺酸基的蒽醌可以氧化氯离子，在酸性条件下产生氯气，接着氯气被氯气收集器收集。通过调整反应溶液的水质条件以及优化反应器的运行参数等技术手段实现了可见光条件下的原位产氯过程，减少氯气运输过程中的损失，其中运行参数指曝气流量、曝气的气体成分和光照强度。本发明蒽醌光催化氧化产生氯气的装置能够高效稳定地长期运行，应用于原位消杀水体中的微生物、去除水中的氨氮和有机物。The method for producing chlorine gas by photocatalysis of the present invention is green and energy-saving. In the photocatalytic reaction generator, through visible light irradiation, in a high-concentration sodium chloride aqueous solution, anthraquinone with a sulfonic acid group can oxidize chloride ions, and under acidic conditions Chlorine gas is produced, which is then collected by a chlorine gas trap. By adjusting the water quality conditions of the reaction solution and optimizing the operating parameters of the reactor, the in-situ chlorine production process under visible light conditions is realized, and the loss during chlorine gas transportation is reduced. The operating parameters refer to the aeration flow rate and the gas composition of the aeration. and light intensity. The device for generating chlorine gas by photocatalytic oxidation of anthraquinone of the present invention can operate efficiently and stably for a long time, and is applied to disinfect microorganisms in water bodies in situ and remove ammonia nitrogen and organic matter in water.
本发明产生氯气方法简单，安全、高效、能耗低、生产过程控制方便，具有广阔的应用前景。The invention has the advantages of simple method for generating chlorine gas, safety, high efficiency, low energy consumption, convenient production process control and broad application prospect.
附图说明Description of drawings
图1为本发明蒽醌光催化氧化制备氯气的装置的结构示意图；Fig. 1 is the structural representation of the device for preparing chlorine by anthraquinone photocatalytic oxidation of the present invention;
图2为实施例中蒽醌光催化氧化制备氯气的测试图。Fig. 2 is a test diagram for preparing chlorine gas by photocatalytic oxidation of anthraquinone in the embodiment.
具体实施方式Detailed ways
具体实施方式一：本实施方式蒽醌光催化氧化制备氯气的方法按照以下步骤实施：Specific embodiment one: the method for preparing chlorine gas by photocatalytic oxidation of anthraquinone in this embodiment is implemented according to the following steps:
一、配置NaCl溶液；1. Configure NaCl solution;
二、向NaCl溶液中加入带有磺酸基的蒽醌，调节体系呈酸性，得到光催化反应溶液；2. Add anthraquinone with a sulfonic acid group to the NaCl solution, adjust the system to be acidic, and obtain a photocatalytic reaction solution;
三、利用可见光源照射光催化反应溶液，光催化反应得到氯气。3. Utilize a visible light source to irradiate the photocatalytic reaction solution, and obtain chlorine gas through the photocatalytic reaction.
本实施方式带有磺酸基的蒽醌可作为一种光敏剂，经过可见光照射后，在酸性条件下氧化氯离子生成二氯自由基，进而产生氯气，同时产生半醌自由基，这种半醌自由基能够还原分子氧，产生过氧化氢(H 2O 2)，半醌自由基可以返回基态，继续参与光催化产氯的反应。 Anthraquinone with sulfonic acid groups in this embodiment can be used as a photosensitizer. After visible light irradiation, it oxidizes chlorine ions to generate dichloride free radicals under acidic conditions, and then generates chlorine gas, and at the same time generates semiquinone free radicals. The quinone free radical can reduce molecular oxygen to produce hydrogen peroxide (H 2 O 2 ), and the semiquinone free radical can return to the ground state and continue to participate in the reaction of photocatalytic chlorine production.
具体实施方式二：本实施方式与具体实施方式一不同的是步骤二中光催化反应溶液中NaCl的浓度为0.5mol/L～4mol/L。Embodiment 2: This embodiment differs from Embodiment 1 in that the concentration of NaCl in the photocatalytic reaction solution in step 2 is 0.5 mol/L˜4 mol/L.
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤二中通过酸溶液调节体系呈酸性。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that in step 2, the acid solution is used to adjust the system to be acidic.
本实施方式所述的酸溶液为盐酸溶液。The acid solution described in this embodiment is a hydrochloric acid solution.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤二中调节体系的pH＝1～3。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the pH of the system is adjusted to 1-3 in step 2.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤二中光催化反应溶液中带有磺酸基的蒽醌的浓度为30～500μmol/L。Embodiment 5: This embodiment differs from Embodiments 1 to 4 in that the concentration of anthraquinone with sulfonic acid groups in the photocatalytic reaction solution in step 2 is 30-500 μmol/L.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是可见光源为氙灯、LED光源或者汞灯。Embodiment 6: This embodiment differs from Embodiments 1 to 5 in that the visible light source is a xenon lamp, an LED light source or a mercury lamp.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是步骤三中向光催化反应溶液中曝气以收集氯气。Embodiment 7: The difference between this embodiment and one of Embodiments 1 to 6 is that in step 3, aeration is made into the photocatalytic reaction solution to collect chlorine gas.
具体实施方式八：本实施方式与具体实施方式七不同的是曝气所用气体为空气或氧气。Embodiment 8: This embodiment is different from Embodiment 7 in that the gas used for aeration is air or oxygen.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是步骤三中光催化反应溶液的温度为15℃～35℃。Embodiment 9: The difference between this embodiment and Embodiment 1 to Embodiment 8 is that the temperature of the photocatalytic reaction solution in step 3 is 15°C-35°C.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是步骤二所述的带有磺酸基的蒽醌为蒽醌-2-磺酸钠(AQ2S)或者蒽醌-1-磺酸(AQ1S)。Embodiment 10: The difference between this embodiment and Embodiment 1 to Embodiment 9 is that the anthraquinone with a sulfonic acid group described in step 2 is anthraquinone-2-sodium sulfonate (AQ2S) or anthraquinone-1- Sulfonic acid (AQ1S).
具体实施方式十一：本实施方式蒽醌光催化氧化制备氯气的装置包括曝气***、反应发生器11和氯气收集器12，在反应发生器11内装有光催化反应溶液，所述的光催化反应溶液为NaCl和带有磺酸基的蒽醌的混合溶液，在反应发生器11内设置有光源9；Embodiment 11: The device for preparing chlorine by photocatalytic oxidation of anthraquinone in this embodiment includes an aeration system, a reaction generator 11 and a chlorine gas collector 12, and a photocatalytic reaction solution is installed in the reaction generator 11. The photocatalytic The reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic acid groups, and a light source 9 is arranged in the reaction generator 11;
曝气***包括风机1、进气管13和曝气头6，进气管13的一端与风机1相连，进气管13的另一端与曝气头6相连，曝气头6位于反应发生器11的底部，在反应发生器11的上部开有出气口8，出气管10的一端与出气口8相连通，出气管10的另一端延伸至氯气收集器12中，氯气收集器12内装有氯气收集液。The aeration system includes a fan 1, an air inlet pipe 13 and an aeration head 6, one end of the air inlet pipe 13 is connected with the fan 1, and the other end of the air inlet pipe 13 is connected with the aeration head 6, and the aeration head 6 is located at the bottom of the reaction generator 11 , have gas outlet 8 on the top of reaction generator 11, and one end of gas outlet pipe 10 is connected with gas outlet 8, and the other end of gas outlet pipe 10 extends in the chlorine gas collector 12, and chlorine gas collection liquid is housed in the chlorine gas collector 12.
本实施方式出气管10的材质为聚四氟乙烯(PTFE)。氯气收集器外表面遮光。The material of the air outlet pipe 10 in this embodiment is polytetrafluoroethylene (PTFE). The outer surface of the chlorine gas collector is shaded.
本实施方式蒽醌光催化氧化制备氯气的装置的反应器主体是有机玻璃材质的反应发生器，反应发生器外部缠绕恒温水箱软管，圆筒内部还可设有同轴的石英套筒，以平衡溶液在反应发生器中的流动速度，内筒中心放置管型氙灯光源。反应发生器的上端进行气密性处理，并在反应发生器顶部留有一个出气口。反应发生器底部设有曝气头，风机吹出气体，曝气量受流量计控制，气体通过曝气砂头从反应发生器底部分散进入反应体系。为防止强酸性的反应溶液倒流，曝气***在流量计和曝气砂头之间设置止回阀。反应溶液经进水管进入反应器，光催化产氯反应器与氯气收集器通过聚四氟乙烯(PTFE)出气管相连，通过曝气装置将反应过程中产生的氯气从反应溶液中吹出，减少氯气在反应溶液中的停留时间，降低其与溶液中产生的过氧化氢发生反应的概率，进入氯气收集器。氯气收集器材质为玻 璃管，具有非气密性，外表面遮光，氯气收集液为氢氧化钠(NaOH)溶液。The main body of the reactor of the device for producing chlorine by photocatalytic oxidation of anthraquinone in this embodiment is a reaction generator made of plexiglass. To balance the flow rate of the solution in the reaction generator, a tubular xenon lamp light source is placed in the center of the inner cylinder. The upper end of the reaction generator is airtight, and a gas outlet is left on the top of the reaction generator. The bottom of the reaction generator is equipped with an aeration head, the fan blows out the gas, the aeration volume is controlled by the flow meter, and the gas is dispersed into the reaction system from the bottom of the reaction generator through the aeration sand head. In order to prevent the strongly acidic reaction solution from flowing back, the aeration system sets a check valve between the flow meter and the aeration sand head. The reaction solution enters the reactor through the water inlet pipe, and the photocatalytic chlorine production reactor is connected with the chlorine gas collector through the polytetrafluoroethylene (PTFE) outlet pipe, and the chlorine gas generated during the reaction is blown out from the reaction solution through the aeration device to reduce the chlorine gas concentration. The residence time in the reaction solution reduces the probability of it reacting with the hydrogen peroxide generated in the solution and enters the chlorine gas collector. The material of the chlorine gas collector is a glass tube, which is non-airtight, and the outer surface is light-shielded. The chlorine gas collection liquid is sodium hydroxide (NaOH) solution.
具体实施方式十二：本实施方式与具体实施方式十一不同的是在进气管13上设置有流量计2和止回阀3。Embodiment 12: This embodiment differs from Embodiment 11 in that a flow meter 2 and a check valve 3 are provided on the intake pipe 13 .
具体实施方式十三：本实施方式与具体实施方式十一或十二不同的是所述的氯气收集液为氢氧化钠(NaOH)溶液。Embodiment 13: This embodiment is different from Embodiment 11 or Embodiment 12 in that the chlorine gas collection liquid is sodium hydroxide (NaOH) solution.
本实施方式氢氧化钠(NaOH)溶液的浓度为0.1mol/L。In this embodiment, the concentration of the sodium hydroxide (NaOH) solution is 0.1 mol/L.
具体实施方式十四：本实施方式与具体实施方式十一至十三之一不同的是在反应发生器11内设置有套筒4。Specific Embodiment Fourteen: The difference between this embodiment and one of the eleventh to thirteenth specific embodiments is that a sleeve 4 is provided in the reaction generator 11 .
本实施方式在反应发生器11内同轴设置石英套筒，来平衡溶液在反应器中的流动速度。In this embodiment, a quartz sleeve is coaxially arranged in the reaction generator 11 to balance the flow velocity of the solution in the reactor.
具体实施方式十五：本实施方式与具体实施方式十一至十四之一不同的是在反应发生器1的底部连接有进水管5。Embodiment 15: This embodiment is different from Embodiment 11 to Embodiment 14 in that a water inlet pipe 5 is connected to the bottom of the reaction generator 1 .
本实施方式在反应发生器1的底部连通有出水管7。In this embodiment, a water outlet pipe 7 is communicated with the bottom of the reaction generator 1 .
具体实施方式十六：本实施方式与具体实施方式十一至十五之一不同的是控制光源9的光强为50-100mW/cm 2。 Embodiment 16: This embodiment differs from Embodiment 11 to Embodiment 15 in that the light intensity of the light source 9 is controlled to be 50-100 mW/cm 2 .
具体实施方式十七：本实施方式与具体实施方式十一至十七之一不同的是控制曝气头6的曝气流量为300-800mL/min。Embodiment 17: This embodiment differs from Embodiment 11 to Embodiment 17 in that the aeration flow rate of the aeration head 6 is controlled to be 300-800 mL/min.
实施例1：本实施例蒽醌光催化氧化制备氯气的方法按照以下步骤实施：Embodiment 1: The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone in this embodiment is implemented according to the following steps:
一、将NaCl溶解在去离子水中，配置NaCl溶液；1. Dissolve NaCl in deionized water and prepare NaCl solution;
二、向NaCl溶液中加入蒽醌-2-磺酸钠(AQ2S)光敏剂，通过0.1mol/L的HCl将溶液pH调至2，得到光催化反应溶液；2. Add anthraquinone-2-sodium sulfonate (AQ2S) photosensitizer to the NaCl solution, and adjust the pH of the solution to 2 by 0.1mol/L HCl to obtain a photocatalytic reaction solution;
三、利用可见光源照射光催化反应溶液，光催化反应得到氯气；3. Utilize visible light source to irradiate the photocatalytic reaction solution, and obtain chlorine gas through photocatalytic reaction;
其中光催化反应溶液中含有100μmol/L的AQ2S和2mol/L NaCl。The photocatalytic reaction solution contains 100 μmol/L AQ2S and 2mol/L NaCl.
本实施例使用具体实施方式十一所述的蒽醌光催化氧化制备氯气的装置，反应发生器11为有机玻璃圆筒，圆筒的直径为100mm，高400mm，有效水深为350mm，圆筒外部缠绕恒温水箱软管，保持反应溶液温度为25±1℃；反应发生器11中心放置管型氙灯光源，辐射强度为64mW/cm 2。 This embodiment uses the device for preparing chlorine gas by photocatalytic oxidation of anthraquinone described in Embodiment 11. The reaction generator 11 is a plexiglass cylinder with a diameter of 100 mm, a height of 400 mm, and an effective water depth of 350 mm. Wind the hose of the constant temperature water tank to keep the temperature of the reaction solution at 25±1°C; place a tubular xenon lamp light source in the center of the reaction generator 11 with a radiation intensity of 64mW/cm 2 .
在反应发生器11内装有3L光催化反应溶液，氯气收集器中装有100mL的0.1mol/L的NaOH，控制反应发生器11内的曝气流速为600mL/min。The reaction generator 11 is equipped with 3L photocatalytic reaction solution, the chlorine gas collector is equipped with 100 mL of 0.1 mol/L NaOH, and the aeration flow rate in the reaction generator 11 is controlled to be 600 mL/min.
实施例2：本实施例与实施例1不同的是步骤二通过0.1mol/L的HCl将溶液pH调至3。Example 2: The difference between this example and Example 1 is that the pH of the solution is adjusted to 3 by 0.1 mol/L HCl in step 2.
实施例3：本实施例与实施例1不同的是步骤二光催化反应溶液中含有100μmol/L的蒽醌-2-磺酸钠(AQ2S)和0.5mol/L NaCl。Embodiment 3: The difference between this embodiment and Embodiment 1 is that the photocatalytic reaction solution in step 2 contains 100 μmol/L of anthraquinone-2-sodium sulfonate (AQ2S) and 0.5mol/L NaCl.
实施例4：本实施例与实施例1不同的是步骤二加入的光敏剂为蒽醌-1-磺酸(AQ1S)。Embodiment 4: The difference between this embodiment and embodiment 1 is that the photosensitizer added in step 2 is anthraquinone-1-sulfonic acid (AQ1S).
实施例5：本实施例与实施例1不同的是反应溶液温度保持为35±1℃。Embodiment 5: The difference between this embodiment and Embodiment 1 is that the temperature of the reaction solution is maintained at 35±1°C.
实施例6：本实施例与实施例1不同的是步骤二光催化反应溶液中含有300μmol/L的AQ2S和2mol/L NaCl。Embodiment 6: The difference between this embodiment and embodiment 1 is that the step 2 photocatalytic reaction solution contains 300 μmol/L of AQ2S and 2mol/L NaCl.
实施例7：本实施例与实施例1不同的是反应发生器11内的曝气流速为800mL/min。Embodiment 7: The difference between this embodiment and Embodiment 1 is that the aeration flow rate in the reaction generator 11 is 800 mL/min.
其中，实施例1-7氯气收集器中氯气的浓度由N-N-diethyl-p-phenylenediamine(DPD)分光光度法测得。该方法适合测定低浓度的氯气。具体步骤如下：从氯气收集器中取1.5mL样品溶液，再加入0.3mL的DPD指示溶液以及1.5mL磷酸盐缓冲溶液中，将样品加入到厚度为1cm的石英比色皿后，氯气的吸光度在515nm波长处测得。Wherein, the concentration of chlorine in the chlorine gas collector of Embodiment 1-7 is measured by N-N-diethyl-p-phenylenediamine (DPD) spectrophotometry. This method is suitable for the determination of low concentrations of chlorine. The specific steps are as follows: take 1.5mL sample solution from the chlorine gas collector, add 0.3mL DPD indicator solution and 1.5mL phosphate buffer solution, and add the sample to a quartz cuvette with a thickness of 1cm. Measured at a wavelength of 515nm.
按照上述相同方法测试实施例1～7产氯方法的氯气产量，具体如表1所示：Test the chlorine output of embodiment 1～7 chlorine production method according to above-mentioned same method, specifically as shown in table 1:
表1Table 1
Figure PCTCN2021134695-appb-000001
Figure PCTCN2021134695-appb-000001
本发明的氯气生产工艺具有低能耗、简便、高效的优点，能实现原位生产氯气，去除水体中的污染物或用于水体消毒。The chlorine gas production process of the present invention has the advantages of low energy consumption, simplicity and high efficiency, and can realize in-situ production of chlorine gas, remove pollutants in water bodies or be used for water body disinfection.

Claims (10)

  1. 蒽醌光催化氧化制备氯气的方法，其特征在于该制备氯气的方法按照以下步骤实现：The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone is characterized in that the method for preparing chlorine gas is realized according to the following steps:
    一、配置NaCl溶液；1. Configure NaCl solution;
    二、向NaCl溶液中加入带有磺酸基的蒽醌，调节体系呈酸性，得到光催化反应溶液；2. Add anthraquinone with a sulfonic acid group to the NaCl solution, adjust the system to be acidic, and obtain a photocatalytic reaction solution;
    三、利用可见光源照射光催化反应溶液，光催化反应得到氯气。3. Utilize a visible light source to irradiate the photocatalytic reaction solution, and obtain chlorine gas through the photocatalytic reaction.
  2. 根据权利要求1所述的蒽醌光催化氧化制备氯气的方法，其特征在于步骤二中光催化反应溶液中NaCl的浓度为0.5mol/L～4mol/L。The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone according to claim 1, characterized in that the concentration of NaCl in the photocatalytic reaction solution in step 2 is 0.5mol/L-4mol/L.
  3. 根据权利要求1或2所述的蒽醌光催化氧化制备氯气的方法，其特征在于步骤二中调节体系的pH＝1～3。The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone according to claim 1 or 2, characterized in that the pH of the system is adjusted to 1-3 in step 2.
  4. 根据权利要求1至3任一项所述的蒽醌光催化氧化制备氯气的方法，其特征在于步骤二中光催化反应溶液中带有磺酸基的蒽醌的浓度为30～500μmol/L。The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone according to any one of claims 1 to 3, characterized in that the concentration of anthraquinone with sulfonic acid groups in the photocatalytic reaction solution in step 2 is 30-500 μmol/L.
  5. 根据权利要求1至4任一项所述的蒽醌光催化氧化制备氯气的方法，其特征在于可见光源为氙灯、LED光源或者汞灯。The method for preparing chlorine gas by photocatalytic oxidation of anthraquinone according to any one of claims 1 to 4, characterized in that the visible light source is a xenon lamp, an LED light source or a mercury lamp.
  6. 根据权利要求1至5任一项所述的蒽醌光催化氧化制备氯气的方法，其特征在于步骤三中向光催化反应溶液中曝气以收集氯气。According to the method for producing chlorine by photocatalytic oxidation of anthraquinone according to any one of claims 1 to 5, it is characterized in that in step 3, the photocatalytic reaction solution is aerated to collect chlorine.
  7. 根据权利要求1至6任一项所述的蒽醌光催化氧化制备氯气的方法，其特征在于步骤二所述的带有磺酸基的蒽醌为蒽醌-2-磺酸钠或者蒽醌-1-磺酸。According to the method for preparing chlorine by anthraquinone photocatalytic oxidation according to any one of claims 1 to 6, it is characterized in that the anthraquinone with sulfonic acid group described in step 2 is anthraquinone-2-sodium sulfonate or anthraquinone -1-sulfonic acid.
  8. 蒽醌光催化氧化制备氯气的装置，其特征在于该装置包括曝气***、反应发生器(11)和氯气收集器(12)，在反应发生器(11)内装有光催化反应溶液，所述的光催化反应溶液为NaCl和带有磺酸基的蒽醌的混合溶液，在反应发生器(11)内设置有光源(9)；The device for preparing chlorine by anthraquinone photocatalytic oxidation is characterized in that the device comprises an aeration system, a reaction generator (11) and a chlorine gas collector (12), and a photocatalytic reaction solution is housed in the reaction generator (11), the described The photocatalytic reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic acid groups, and a light source (9) is arranged in the reaction generator (11);
    曝气***包括风机(1)、进气管(13)和曝气头(6)，进气管(13)的一端与风机(1)相连，进气管(13)的另一端与曝气头(6)相连，曝气头(6)位于反应发生器(11)的底部，在反应发生器(11)的上部开有出气口(8)，出气管(10)的一端与出气口(8)相连通，出气管(10)的另一端延伸至氯气收集器(12)中，氯气收集器(12)内装有氯气收集液。The aeration system includes fan (1), air intake pipe (13) and aeration head (6). One end of the air intake pipe (13) is connected to the fan (1), and the other end of the air intake pipe (13) is connected to the aeration head (6). ), the aeration head (6) is located at the bottom of the reaction generator (11), and an air outlet (8) is opened on the upper part of the reaction generator (11), and one end of the air outlet pipe (10) is connected with the air outlet (8) Through, the other end of gas outlet pipe (10) extends in the chlorine gas collector (12), and chlorine gas collection liquid is housed in the chlorine gas collector (12).
  9. 根据权利要求8所述的蒽醌光催化氧化制备氯气的装置，其特征在于控制光源(9)的光强为50-100mW/cm 2。 The device for preparing chlorine gas by photocatalytic oxidation of anthraquinone according to claim 8, characterized in that the light intensity of the light source (9) is controlled to be 50-100mW/cm 2 .
  10. 根据权利要求8或9所述的蒽醌光催化氧化制备氯气的装置，其特征在于控制曝气头(6)的曝气流量为300-800mL/min。The device for preparing chlorine by photocatalytic oxidation of anthraquinone according to claim 8 or 9, characterized in that the aeration flow rate of the aeration head (6) is controlled to be 300-800mL/min.
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