CN113942977B - Method and device for preparing chlorine by anthraquinone photocatalytic oxidation - Google Patents

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

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Publication number
CN113942977B
CN113942977B CN202111417034.7A CN202111417034A CN113942977B CN 113942977 B CN113942977 B CN 113942977B CN 202111417034 A CN202111417034 A CN 202111417034A CN 113942977 B CN113942977 B CN 113942977B
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chlorine
anthraquinone
photocatalytic
reaction
solution
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CN113942977A (en
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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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Harbin Institute of Technology
National Engineering Research Center for Water Resources of Harbin Institute of Technology Co Ltd
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Harbin Institute of Technology
National Engineering Research Center for Water Resources of Harbin Institute of Technology Co Ltd
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Priority to PCT/CN2021/134695 priority patent/WO2023092618A1/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/03Preparation from chlorides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside

Abstract

The invention discloses a method and a device for preparing chlorine by anthraquinone photocatalytic oxidation, belongs to the technical field of photocatalysts, and aims to solve the problems of complex production process and high energy consumption of the existing chlorine. The method for preparing chlorine by anthraquinone photocatalytic oxidation is to add anthraquinone with sulfonic groups into NaCl solution, adjust the system to be acidic, obtain a photocatalytic reaction solution, irradiate the photocatalytic reaction solution by using a visible light source, and obtain the chlorine by photocatalytic reaction. The invention also relates to a device for preparing chlorine by utilizing the anthraquinone photocatalytic oxidation, which comprises an aeration system, a reaction generator and a chlorine collector, wherein the reaction generator is filled with photocatalytic reaction solution, and a light source is arranged in the reaction generator. The method for producing chlorine by photocatalysis is green and energy-saving, and in the photocatalysis reaction generator, the anthraquinone with sulfonic group in high-concentration sodium chloride aqueous solution can oxidize chloride ions under the irradiation of visible light, and the chlorine is produced under the acidic condition.

Description

Method and device for preparing chlorine by anthraquinone photocatalytic oxidation
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a method and a device for preparing chlorine through anthraquinone photocatalytic oxidation.
Background
The existing water treatment process mainly based on biological treatment technology shows insufficient treatment capacity, insufficient treatment efficiency and the like in the practical application process, so that development of a novel green, efficient and stable sewage treatment technology is needed to solve the problems.
The disinfection process is the last barrier in the water treatment process and plays an important role in removing pollutants. Chlorine gas is the earliest chemical disinfectant used for water disinfection and has become one of the main technical methods for water disinfection in countries around the world. The method has the advantages that the operation process is not complex, the price is economical and practical, in addition, residual chlorine with a disinfection effect can be existed in the pipe network, and the safety of water in the pipe network can be ensured. Besides being applied to disinfection of water, the water treatment agent can also oxidize and degrade refractory organic pollutants in water. However, the most common chlorine production process at this stage is the chlor-alkali process of electrolysis of sodium chloride. The traditional process has high energy consumption and needs to be connected with a power grid or be provided with a high-voltage storage battery. In addition, the transport process of both chlorine and hypochlorite is relatively cumbersome and long distance transport causes large loss of chlorine due to poor chemical stability. Therefore, there is an urgent need for a low energy consumption and simple and efficient chlorine production process that allows in situ production at the site of use.
Disclosure of Invention
The invention provides a method and a device for preparing chlorine by anthraquinone photocatalytic oxidation, which aims to solve the problems of complex production process and high energy consumption of the existing chlorine.
The method for preparing chlorine by anthraquinone photocatalytic oxidation is realized according to the following steps:
1. preparing NaCl solution;
2. adding anthraquinone with sulfonic group into NaCl solution, regulating system to be acidic to obtain photocatalytic reaction solution;
3. and irradiating the photocatalytic reaction solution by using a visible light source, and performing photocatalytic reaction to obtain chlorine.
The device for preparing chlorine by anthraquinone photocatalytic oxidation comprises an aeration system, a reaction generator and a chlorine collector, wherein a photocatalytic reaction solution is filled in the reaction generator, the photocatalytic reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic groups, and a light source is arranged in the reaction generator;
the aeration system comprises a fan, an air inlet pipe and an aeration head, one end of the air inlet pipe is connected with the fan, the other end of the air inlet pipe is connected with the aeration head, the aeration head is positioned at the bottom of the reaction generator, an air outlet is formed in the upper part of the reaction generator, one end of the air outlet pipe is communicated with the air outlet, the other end of the air outlet pipe extends into a chlorine gas collector, and a chlorine gas collecting liquid is filled in the chlorine gas collector.
In the method for preparing chlorine by anthraquinone photocatalytic oxidation, AQ2S is excited by visible light to generate a triplet excited state, and sodium chloride with a certain concentration is added into a reaction system to provide chloride ions; the generated AQ2S triplet excited state reacts with chloride ions to generate chlorine; finally, the generated chlorine is collected by means of sodium hydroxide solution.
Compared with the prior art, the method and the device for preparing the chlorine by the photocatalytic oxidation of the anthraquinone have the following beneficial effects:
the method for producing the chlorine by photocatalysis is green and energy-saving, in a photocatalysis reaction generator, through visible light irradiation, in a high-concentration sodium chloride aqueous solution, anthraquinone with sulfonic groups can oxidize chloride ions, and the chlorine is produced under an acidic condition, and then the chlorine is collected by a chlorine collector. The in-situ chlorine production process under the visible light condition is realized by adjusting the water quality condition of the reaction solution, optimizing the operation parameters of the reactor and the like, and the loss in the chlorine transportation process is reduced, wherein the operation parameters refer to aeration flow, aeration gas components and illumination intensity. The device for generating chlorine by anthraquinone photocatalytic oxidation can be operated for a long time with high efficiency and stability, and is applied to in-situ disinfection of microorganisms in water and removal of ammonia nitrogen and organic matters in water.
The method for generating chlorine is simple, safe, efficient, low in energy consumption, convenient in production process control and wide in application prospect.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing chlorine by photocatalytic oxidation of anthraquinone according to the present invention;
FIG. 2 is a graph showing the photocatalytic oxidation of anthraquinone to chlorine in the examples.
Detailed Description
The first embodiment is as follows: the method for preparing chlorine by anthraquinone photocatalytic oxidation according to the embodiment is implemented according to the following steps:
1. preparing NaCl solution;
2. adding anthraquinone with sulfonic group into NaCl solution, regulating system to be acidic to obtain photocatalytic reaction solution;
3. and irradiating the photocatalytic reaction solution by using a visible light source, and performing photocatalytic reaction to obtain chlorine.
The anthraquinone with sulfonic acid group of the embodiment can be used as a photosensitizer, after irradiation of visible light, chloride ions are oxidized to generate dichloro free radicals under the acidic condition, so that chlorine gas is further generated, and meanwhile, semi-quinone free radicals are generated, and the semi-quinone free radicals can reduce molecular oxygen to generate hydrogen peroxide (H) 2 O 2 ) The semiquinone free radical can return to the ground state and continue to participate in the photocatalytic chlorine production reaction.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is that the concentration of NaCl in the photocatalytic reaction solution in the second step is 0.5 mol/L to 4 mol/L.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that the acid solution is used to adjust the system to be acidic in the second step.
The acid solution described in this embodiment is a hydrochloric acid solution.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that the pH of the adjustment system in step two=1 to 3.
Fifth embodiment: this embodiment differs from the first to fourth embodiments in that the concentration of the sulfonic acid group-containing anthraquinone in the photocatalytic reaction solution in the second step is 30 to 500. Mu. Mol/L.
Specific embodiment six: the present embodiment differs from one to fifth embodiments in that the visible light source is a xenon lamp, an LED light source, or a mercury lamp.
Seventh embodiment: this embodiment differs from one to six embodiments in that aeration is performed to collect chlorine gas in the photocatalytic reaction solution in the third step.
Eighth embodiment: the present embodiment differs from the seventh embodiment in that the gas used for aeration is air or oxygen.
Detailed description nine: the present embodiment differs from one to eight of the embodiments in that the temperature of the photocatalytic reaction solution in the third step is 15 to 35 ℃.
Detailed description ten: this embodiment differs from one of the first to ninth embodiments in that the sulfonic acid group-containing anthraquinone described in the second step is anthraquinone-2-sodium sulfonate (AQ 2S) or anthraquinone-1-sulfonic acid (AQ 1S).
Eleventh embodiment: the device for preparing chlorine by anthraquinone photocatalytic oxidation in the embodiment comprises an aeration system, a reaction generator 11 and a chlorine collector 12, wherein a photocatalytic reaction solution is filled in the reaction generator 11, the photocatalytic reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic groups, and a light source 9 is arranged in the reaction generator 11;
the aeration system comprises 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, the other end of the air inlet pipe 13 is connected with the aeration head 6, the aeration head 6 is positioned at the bottom of the reaction generator 11, an air outlet 8 is formed in the upper part of the reaction generator 11, one end of an air outlet pipe 10 is communicated with the air outlet 8, the other end of the air outlet pipe 10 extends into a chlorine gas collector 12, and a chlorine gas collecting liquid is filled in the chlorine gas collector 12.
The material of the outlet pipe 10 of this embodiment is Polytetrafluoroethylene (PTFE). The outer surface of the chlorine collector is shaded.
The reactor main body of the device for preparing chlorine by anthraquinone photocatalytic oxidation in the embodiment is a reaction generator made of organic glass, a constant-temperature water tank hose is wound outside the reaction generator, a coaxial quartz sleeve can be further arranged inside a cylinder to balance the flowing speed of solution in the reaction generator, and a tubular xenon lamp light source is arranged in the center of the inner cylinder. The upper end of the reaction generator is subjected to airtight treatment, and an air outlet is reserved at the top of the reaction generator. The bottom of the reaction generator is provided with an aeration head, the fan blows out gas, the aeration amount is controlled by a flowmeter, and the gas is dispersed from the bottom of the reaction generator into the reaction system through the aeration sand head. In order to prevent the strong acid reaction solution from flowing backwards, the aeration system is provided with a check valve between the flowmeter and the aeration sand head. The reaction solution enters the reactor through a water inlet pipe, the photocatalysis chlorine production reactor is connected with a chlorine gas collector through a Polytetrafluoroethylene (PTFE) air outlet pipe, chlorine gas generated in the reaction process is blown out of the reaction solution through an aeration device, the residence time of the chlorine gas in the reaction solution is reduced, the probability of the reaction between the chlorine gas and hydrogen peroxide generated in the solution is reduced, and the chlorine gas enters the chlorine gas collector. The chlorine collector is made of glass tube, has non-airtight and light-shielding outer surface, and the chlorine collecting liquid is sodium hydroxide (NaOH) solution.
Twelve specific embodiments: the present embodiment differs from the eleventh embodiment in that the intake pipe 13 is provided with the flow meter 2 and the check valve 3.
Thirteen specific embodiments: this embodiment differs from the eleventh or twelfth embodiment in that the chlorine gas collection liquid is a sodium hydroxide (NaOH) solution.
The concentration of the sodium hydroxide (NaOH) solution in this embodiment was 0.1 mol/L.
Fourteen specific embodiments: this embodiment differs from one of the eleventh to thirteenth embodiments in that a sleeve 4 is provided in the reaction generator 11.
In this embodiment, a quartz sleeve is coaxially provided in the reaction generator 11 to balance the flow rate of the solution in the reactor.
Fifteen embodiments: this embodiment differs from one of the eleventh to fourteenth embodiments in that a water inlet pipe 5 is connected to the bottom of the reaction generator 1.
In this embodiment, a water outlet pipe 7 is connected to the bottom of the reaction generator 1.
Sixteen specific embodiments: the present embodiment and the specific embodimentOne of the eleventh to fifteenth embodiments is different in that the light intensity of the light source 9 is controlled to be 50-100 mW/cm 2
Seventeenth embodiment: this embodiment differs from one of the eleventh to seventeenth embodiments in that the aeration flow rate of the aeration head 6 is controlled to 300 to 800mL/min.
Example 1: the method for preparing chlorine by anthraquinone photocatalytic oxidation according to the embodiment is implemented according to the following steps:
1. dissolving NaCl in deionized water, and preparing NaCl solution;
2. adding anthraquinone-2-sodium sulfonate (AQ 2S) photosensitizer into NaCl solution, and regulating the pH of the solution to 2 through 0.1 mol/L HCl to obtain photocatalysis reaction solution;
3. irradiating the photocatalytic reaction solution by using a visible light source, and performing photocatalytic reaction to obtain chlorine;
wherein the photocatalytic reaction solution contains AQ2S of 100 mu mol/L and NaCl of 2 mol/L.
In this example, the apparatus for preparing chlorine by photocatalytic oxidation of anthraquinone according to embodiment eleven was used, the reaction generator 11 was a plexiglass cylinder, the diameter of the cylinder was 100 mm, the height was 400 mm, the effective water depth was 350 mm, a constant temperature water tank hose was wound around the outside of the cylinder, and the temperature of the reaction solution was kept at 25±1 ℃; the center of the reaction generator 11 is provided with a tubular xenon lamp light source with the radiation intensity of 64 mW/cm 2
3L photocatalytic reaction solution was contained in the reaction generator 11, and 100 mL of 0.1 mol/L NaOH was contained in the chlorine gas collector, and the aeration flow rate in the reaction generator 11 was controlled to be 600 mL/min.
Example 2: this example differs from example 1 in that the solution pH is adjusted to 3 by means of 0.1 mol/L HCl in step two.
Example 3: this example differs from example 1 in that the step two photocatalytic reaction solution contains 100. Mu. Mol/L sodium anthraquinone-2-sulfonate (AQ 2S) and 0.5 mol/L NaCl.
Example 4: this example differs from example 1 in that the photosensitizer added in step two is anthraquinone-1-sulfonic acid (AQ 1S).
Example 5: this example differs from example 1 in that the reaction solution temperature was maintained at 35.+ -. 1 ℃.
Example 6: this example differs from example 1 in that the step two photocatalytic reaction solution contains 300. Mu. Mol/L AQ2S and 2 mol/L NaCl.
Example 7: this example differs from example 1 in that the aeration flow rate in the reaction generator 11 was 800mL/min.
Wherein the concentration of chlorine in the chlorine collectors of examples 1-7 was determined spectrophotometrically by N-N-diethyl-p-phenylenediamine (DPD). The method is suitable for measuring low-concentration chlorine. The method comprises the following specific steps: 1.5 g mL sample solution was taken from the chlorine gas collector, and then 0.3mL of DPD indicator solution and 1.5 g mL phosphate buffer solution were added, and after the sample was added to a quartz cuvette having a thickness of 1 cm, the absorbance of chlorine gas was measured at 515 nm wavelength.
The chlorine yields of the chlorine generating methods of examples 1 to 7 were measured in the same manner as described above, and are specifically shown in Table 1:
TABLE 1
Group of Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Chlorine yield/(mg) 0.50 0.21 0.11 0.18 0.55 1.6 1.2
The chlorine production process has the advantages of low energy consumption, simplicity, convenience and high efficiency, and can realize in-situ production of chlorine, remove pollutants in water or be used for water disinfection.

Claims (6)

1. The method for preparing chlorine by anthraquinone photocatalytic oxidation is characterized by comprising the following steps of:
1. preparing NaCl solution;
2. adding anthraquinone with sulfonic acid group into NaCl solution, and regulating pH value of the system to 1-3 to obtain photocatalytic reaction solution;
3. irradiating the photocatalytic reaction solution by using a visible light source, and performing photocatalytic reaction to obtain chlorine;
wherein the concentration of NaCl in the photocatalytic reaction solution in the second step is 0.5 mol/L to 4 mol/L, and the concentration of anthraquinone with sulfonic groups in the photocatalytic reaction solution is 30 mu mol/L to 500 mu mol/L;
and in the third step, aeration is carried out on the photocatalytic reaction solution to collect chlorine.
2. The method for preparing chlorine by photocatalytic oxidation of anthraquinone according to claim 1, wherein the visible light source is a xenon lamp, an LED light source or a mercury lamp.
3. The method for preparing chlorine by photocatalytic oxidation of anthraquinone according to claim 1, wherein the anthraquinone with sulfonic acid group in the second step is anthraquinone-2-sodium sulfonate or anthraquinone-1-sulfonic acid.
4. The device for preparing chlorine by the photocatalytic oxidation of anthraquinone according to the method of claim 1, characterized in that the device comprises an aeration system, a reaction generator (11) and a chlorine collector (12), wherein the reaction generator (11) is internally provided with a photocatalytic reaction solution, the photocatalytic reaction solution is a mixed solution of NaCl and anthraquinone with sulfonic group, and the reaction generator (11) is internally provided with a light source (9);
the aeration system comprises 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), the other end of the air inlet pipe (13) is connected with the aeration head (6), the aeration head (6) is positioned at the bottom of a reaction generator (11), an air outlet (8) is formed in the upper portion of the reaction generator (11), one end of an air outlet pipe (10) is communicated with the air outlet (8), the other end of the air outlet pipe (10) extends into a chlorine collector (12), and a chlorine collection liquid is filled in the chlorine collector (12).
5. The apparatus for preparing chlorine by photocatalytic oxidation of anthraquinone according to claim 4, characterized in that the light intensity of the light source (9) is controlled to be 50-100 mW/cm 2
6. The apparatus for preparing chlorine by photocatalytic oxidation of anthraquinone according to claim 4 or 5, characterized in that the aeration flow rate of the aeration head (6) is controlled to be 300-800 mL/min.
CN202111417034.7A 2021-11-25 2021-11-25 Method and device for preparing chlorine by anthraquinone photocatalytic oxidation Active CN113942977B (en)

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PCT/CN2021/134695 WO2023092618A1 (en) 2021-11-25 2021-12-01 Method and device for preparing chlorine gas by means of photocatalytic oxidation of anthraquinone

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