CN115198288A - Integrated device and method for producing high-purity hydrogen peroxide by water-oxygen photoelectrocatalysis - Google Patents
Integrated device and method for producing high-purity hydrogen peroxide by water-oxygen photoelectrocatalysis Download PDFInfo
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- CN115198288A CN115198288A CN202110316197.XA CN202110316197A CN115198288A CN 115198288 A CN115198288 A CN 115198288A CN 202110316197 A CN202110316197 A CN 202110316197A CN 115198288 A CN115198288 A CN 115198288A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 150
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000746 purification Methods 0.000 claims abstract description 42
- 238000003860 storage Methods 0.000 claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 9
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 19
- 238000007670 refining Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000008213 purified water Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
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- 239000000463 material Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- Organic Chemistry (AREA)
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- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an integrated device for producing hydrogen peroxide by photoelectrocatalysis of water oxygen and a preparation method, comprising the following steps: a water oxygen purification system having a water inlet line and an air inlet line configured to deliver and purify water and air; the photoelectrocatalysis system is used for photoelectrocatalysis of water and air which are conveyed by the water oxygen purification system to generate hydrogen peroxide; the storage refinement system detects and purifies the produced hydrogen peroxide to obtain high-purity hydrogen peroxide; the photoelectrocatalysis system comprises a cathode chamber, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode chamber which are sequentially arranged in parallel, wherein a water inlet, an air inlet and an air outlet are formed in the cathode chamber. This integrated device can turn into the hydrogen peroxide solution of different purity and concentration with water and air high efficiency to store light energy and electric energy for the chemical energy of hydrogen peroxide, with the production and the purification integration of hydrogen peroxide, satisfied high-purity hydrogen peroxide solution along with producing along with using, avoid the decomposition and the safety problem of hydrogen peroxide.
Description
Technical Field
The invention belongs to the technical field of hydrogen peroxide synthesis, and particularly relates to an integrated device and method for producing high-purity hydrogen peroxide by photoelectrocatalysis of water oxygen.
Background
Hydrogen peroxide is a green chemical widely used in the fields of disinfection, water purification, industrial pulp bleaching, chemical synthesis, electronic industry, etc. In recent years, the annual demand for international hydrogen peroxide has increased year by year, and particularly in southeast asia, korea, japan, and the like, hydrogen peroxide is short in supply and demand, and thus exhibits great market potential. The main production mode of hydrogen peroxide is anthraquinone process, which has mature technology, but has high energy consumption and organic pollution, thus severely restricting the development of hydrogen peroxide. The direct synthesis of hydrogen peroxide by using hydrogen and oxygen is an environment-friendly and energy-saving alternative scheme for producing high-purity hydrogen peroxide, but the mixing of hydrogen and oxygen in the process brings safety problems, thereby hindering the practical application of the method. Therefore, research interest has gradually shifted to safer and more efficient hydrogen peroxide synthesis methods.
An electrochemical oxidation-reduction reaction based on two-electron transfer, namely, oxygen and water are simultaneously converted into hydrogen peroxide through electrocatalysis, and the method is a novel hydrogen peroxide synthesis mode. Compared with the former two production processes, the method has the advantages that: 1) Green natural resources are used, and fossil fuels are not consumed; 2) The environment is clean, and no organic waste is generated; 3) The reaction condition is mild, and no explosion danger exists; 4) Theoretically with the highest energy conversion efficiency. In recent years, although researchers have achieved some success in the development of hydrogen peroxide electrocatalysts, scale-up and on-site (on-site) production of hydrogen peroxide based on water-oxygen photoelectrocatalysis still has limitations.
Disclosure of Invention
The invention aims to provide an integrated device for producing high-purity hydrogen peroxide by photoelectrocatalysis of water oxygen, which can efficiently convert water and air into hydrogen peroxide solutions with different purities and concentrations, thereby storing light energy and electric energy into chemical energy of hydrogen peroxide and realizing the random use of the hydrogen peroxide solution.
In order to achieve the above object, according to one aspect of the present invention, there is provided an integrated apparatus for photoelectrocatalytic production of high-purity hydrogen peroxide from water oxygen, comprising: a water oxygen purification system having a water inlet line and an air inlet line configured to deliver and purify water and air, respectively; a photoelectrocatalysis system configured for photoelectrocatalysis generation of hydrogen peroxide from the water and air delivered by the water oxygen purification system; the storage refinement system is used for detecting and purifying the hydrogen peroxide produced by the photoelectrocatalysis system to obtain high-purity hydrogen peroxide; the photoelectrocatalysis system comprises a cathode chamber, a solid electrolyte and an anode chamber which are sequentially arranged in parallel, wherein an anion exchange membrane is arranged between the cathode chamber and the solid electrolyte, and a cation exchange membrane is arranged between the solid electrolyte and the anode chamber; and the cathode chamber is provided with a water inlet communicated with a water inlet pipeline of the water oxygen purification system, an air inlet communicated with an air inlet pipeline and an air outlet.
According to the invention, one side of the anode chamber is provided with an irradiation device configured to emit a visible light source to irradiate the anode chamber.
According to the invention, a water inlet, a water flow electromagnetic valve, a hydraulic press, a purification column, a water flow velocity valve and a water inlet passage electromagnetic valve are sequentially arranged on the water inlet pipeline; the water inlet passage solenoid valve has three outlets respectively communicated with the cathode chamber, the solid electrolyte and the anode chamber.
According to the invention, the air inlet pipeline is sequentially provided with an air inlet, an air pump, a filter screen and a gas flow rate valve, and the gas flow rate valve is communicated with the cathode chamber.
According to the invention, the cathode chamber has an outlet which is connected in series to a non-return valve and an air outlet. Preferably, the cathode chamber is provided with a pressure gauge.
Preferably, one end of the solid electrolyte is connected with the water inlet passage electromagnetic valve, and the other end of the solid electrolyte is connected with the detector.
Preferably, one end of the anode chamber is communicated with the water inlet passage electromagnetic valve, and the other end of the anode chamber is connected with the detector.
In accordance with the present invention, the storage refinement system further includes a detector in communication with the photoelectrocatalytic system and configured for quality detection of the produced hydrogen peroxide.
Preferably, the storage refinement system further comprises a hydrogen peroxide storage tank, a pressure pump and an air flow electromagnetic valve which are sequentially communicated with the detector, and the hydrogen peroxide in the hydrogen peroxide storage tank flows out from one end of the air flow electromagnetic valve through the pressure pump to obtain the high-purity hydrogen peroxide.
Preferably, the storage refinement system further comprises a refinement column disposed at an end of the gas flow solenoid valve and configured to refine the high purity hydrogen peroxide to obtain ultra-high purity hydrogen peroxide.
According to the invention, the purification column is a three-section purification column, and comprises an active carbon purification column, an adsorption resin purification column and an ultraviolet oxidation lamp which are sequentially arranged. Preferably, the filter screen comprises a dust removal bag and a two-section type filtering structure of a drying screen which are arranged in sequence.
According to the invention, the detector consists of a programmable controller, a CPU module carrying a DSP chip and a digital display screen, so as to detect the concentration and the storage capacity of the hydrogen peroxide solution, the internal working state of the machine, historical data query, consumable replacement prompt and failure alarm in real time. Preferably, the refining column is a two-stage refining column, and comprises an adsorption resin refining column with an anti-oxidation function and a nylon ultrafiltration membrane refining column.
According to another aspect of the present invention, there is also provided an integrated process for the photoelectrocatalytic production of high purity hydrogen peroxide from water oxygen, comprising the steps of: s1, opening a water inlet pipeline and a gas inlet pipeline of a water oxygen purification system to enable water to enter a purification column through a water flow electromagnetic valve and pressurization through a hydraulic press and to be pre-purified, and enabling the pre-purified water to enter a photoelectric catalytic system through a water inlet channel electromagnetic valve under the control of a water flow velocity valve; air on the air inlet pipeline is pressurized by an air pump, is filtered by a filter screen to obtain purified air, and enters a cathode chamber of the photoelectrocatalysis system after being regulated by a flow rate valve; s2, adjusting the inflow and outflow ratio of the gas in the cathode chamber to enable the working pressure of the gas to be 0-1 Mpa, and enabling the purified air to perform oxygen reduction reaction in the cathode chamber to generate pure hydrogen peroxide, wherein the hydrogen peroxide is HO 2- In the form of a cathodeThe anion exchange membrane between the chamber and the solid electrolyte is diffused into the solid electrolyte, and the redundant air flows out of the equipment from the other end of the cathode chamber through the check valve and the air outlet; s3, performing water oxidation reaction on the pre-purified water in the anode chamber to generate pure hydrogen peroxide and H + Hydrogen peroxide is washed out of the anode chamber and H + Diffusing into the solid electrolyte along a cation exchange membrane between the anode chamber and the solid electrolyte; s4, HO diffused from cathode chamber 2- With H diffused from the anode chamber + Binding to generate H 2 O 2 Then washed by water to form a photoelectrocatalysis system; s5, detecting the product quality of the hydrogen peroxide generated by the photoelectrocatalysis system through a detector, and then flowing into a storage tank for later use; hydrogen peroxide in the storage tank flows into the air flow electromagnetic valve through the pressure pump, and flows out of the equipment at one end of the air flow electromagnetic valve to obtain high-purity hydrogen peroxide; the hydrogen peroxide enters a refining column through the other end of the air flow electromagnetic valve for refining to obtain the ultra-pure hydrogen peroxide.
According to the invention, the cathode chamber of the photoelectrocatalysis system is mainly made of porous carbon oxide paper, and the working area is 100cm 2 Working current density 0.2A/cm 2 The working pressure of the cathode chamber is 0-1 Mpa. Preferably, the anode chamber electrode material is a porous carbon paper oxide-bismuth vanadate composite material, and the effective working area is 100cm 2 Working current density 0.2A/cm 2 . Preferably, the air on the air inlet pipeline enters the photoelectrocatalysis system at the flow rate of 100mL/min after being regulated by the air flow rate valve.
Preferably, the material of the solid electrolyte is styrene-divinylbenzene copolymer, and the thickness of the solid electrolyte is 0.5cm. Preferably, step S3 further includes a process of irradiating the anode chamber, wherein the light source for irradiation is a visible light source, and the power is 0 to 200W. Preferably, the flow rate of the water supply of the water oxygen purification system is 10-1000 mL/h, the pressure of the air pump is 20kPa, and the flow rate of the air supply is 100mL/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The integrated device can efficiently convert water and air into hydrogen peroxide solutions with different purities and concentrations, so that light energy and electric energy are stored as chemical energy of hydrogen peroxide, the production and purification of the hydrogen peroxide are integrated, a solution for producing the high-purity hydrogen peroxide solution on a medium and small scale is provided, the demand of the ultrahigh-purity hydrogen peroxide solution on production is met, and the decomposition and safety problems of the hydrogen peroxide in the processes of storage and transportation are avoided.
(2) The invention uses green natural resources, is environment-friendly, has mild reaction conditions and no explosion hazard; high-quality hydrogen peroxide is synthesized by co-catalysis of a cathode and an anode, and theoretically, the highest energy conversion efficiency is achieved.
(3) The cathode chamber has high-pressure reaction function, high oxygen utilization rate, high current density and H production 2 O 2 The efficiency is high; the anode chamber assists in illumination, light energy is directly converted into high value-added chemicals, and electricity resources are saved.
Drawings
FIG. 1 is a schematic structural diagram of an integrated apparatus for producing high-purity hydrogen peroxide by photoelectrocatalysis of water oxygen.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be emphasized that the specific embodiments described herein are merely illustrative of the invention, are some, not all, and therefore do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in FIG. 1, the present invention provides an integrated device for producing hydrogen peroxide by photoelectrocatalysis of water oxygen, comprising a water oxygen purification system, a photoelectrocatalysis system and a storage refinement system, wherein the water oxygen purification system is provided with a water inlet pipeline and an air inlet pipeline which are respectively configured to convey water and oxygen and purify the water and the oxygen. The photoelectrocatalysis system is configured to photoelectrocatalytically generate hydrogen peroxide for the water and oxygen delivered by the water oxygen purification system. The storage refinement system detects and purifies the hydrogen peroxide generated by the photoelectrocatalysis system, so that high-purity hydrogen peroxide is obtained. This integrated device can turn into the hydrogen peroxide solution of different purity and concentration with water and air high efficiency to store light energy and electric energy for the chemical energy of hydrogen peroxide, realize the hydrogen peroxide solution along with producing along with using, for fields such as medical treatment, electron, food facilitate, avoid decomposition and the safety problem that hydrogen peroxide appears in storage, transportation simultaneously.
As shown in fig. 1, the water oxygen purification system comprises a water inlet pipeline and an air inlet pipeline, wherein the water inlet pipeline is sequentially provided with a water inlet, a water flow electromagnetic valve 1, a water press 2, a purification column 3, a water flow velocity valve 4 and a water inlet passage electromagnetic valve 5, and the water inlet passage electromagnetic valve 5 is provided with three outlets which are respectively communicated with a cathode chamber 9, a solid electrolyte 13 and an anode chamber 14. The entering water reaches the hydraulic press 2 through the water flow electromagnetic valve 1, enters the purifying column 3 for pre-purification through pressurization of the hydraulic press, and enters the photoelectrocatalysis system through the water inlet passage electromagnetic valve 5 at different flow rates (10-1000 mL/h) under the control of the water flow rate valve 4. Preferably, the purification column 3 on the water inlet pipeline is a three-section purification column, and comprises an activated carbon purification column, an adsorption resin purification column and an ultraviolet oxidation lamp which are sequentially arranged.
As shown in fig. 1, an air inlet, an air pump 6, a filter screen 7 and a gas flow rate valve 8 are sequentially arranged on the air inlet pipeline, wherein the gas flow rate valve 8 is communicated with the cathode chamber 9. Air enters through an air inlet, is pressurized through an air pump 6, is filtered through a filter screen 7 to obtain purified air, is adjusted through a gas flow rate valve 8, and finally enters into the photoelectrocatalysis system at the flow rate of 100mL/min. Preferably, the filter screen 7 on the air inlet pipeline of the water oxygen purification system adopts two-stage filtration, namely a dust removal bag and a drying screen in sequence.
The photoelectrocatalysis system comprises a cathode chamber 9, a solid electrolyte 13 and an anode chamber 14 which are sequentially arranged in parallel. An anion exchange membrane 16 is arranged between the cathode chamber 9 and the solid electrolyte 13, and a cation exchange membrane 17 is arranged between the solid electrolyte 13 and the anode chamber 14. The cathode chamber 9 is provided with a water inlet communicated with a water inlet pipeline, an air inlet communicated with an air inlet pipeline and an outlet, and the outlet is sequentially connected with a check valve 11 and an air outlet 12. Preferably, the cathode chamber 9 is provided with a pressure gauge 10.
Wherein, the solid electrolyte 13 and the anode chamber 14 are both provided with water inlets which are respectively communicated with the water inlet passage electromagnetic valve 5, and the other ends of the solid electrolyte and the anode chamber are both communicated with the detector 18. Preferably, an irradiation device is further disposed on one side of the anode chamber 14, and is configured to emit a visible light source 15 to irradiate the anode chamber 14. Specifically, the power of the visible light source 15 is 0 to 200W.
As shown in fig. 1, the storage refinement system also includes a detector 18 in communication with the solid electrolyte 13 and detecting the quality of the hydrogen peroxide produced. Preferably, the detector 18 is composed of a programmable controller, a CPU module carrying a DSP chip and a digital display screen, so as to detect the concentration and the storage capacity of the hydrogen peroxide solution, the internal working state of the machine, historical data query, consumable replacement prompt and fault alarm in real time.
According to the invention, the storage refinement system also comprises a hydrogen peroxide storage tank 19, a pressure pump 20 and a water flow electromagnetic valve 21 which are sequentially communicated with the detector 18, and hydrogen peroxide generated by the catalytic system flows into the hydrogen peroxide storage tank 19 for standby after the product quality is detected by the detector 18. Wherein, the hydrogen peroxide in the hydrogen peroxide storage tank 19 flows out from one end of a water flow electromagnetic valve 21 by a pressure pump 20 to obtain the high-purity hydrogen peroxide. And a refining column 22 is further arranged at the other end of the water flow electromagnetic valve 21 and is configured to be used for refining the high-purity hydrogen peroxide, and the hydrogen peroxide enters the refining column 22 through the other end of the water flow electromagnetic valve 21 to obtain the ultra-high-purity hydrogen peroxide. Preferably, the refinement column 22 of the storage refinement system is a two-stage refinement column including an adsorption resin refinement column having an anti-oxidation function and a nylon ultrafiltration membrane refinement column.
According to another aspect of the present invention, there is also provided an integrated process for the photoelectrocatalytic production of hydrogen peroxide from water oxygen, comprising the steps of: s1, opening a water inlet pipeline and an air inlet pipeline of a water oxygen purification system to enable water to enter a purification column 3 through a water flow electromagnetic valve 1 and pressurization through a water press 2 and to be pre-purified, and enabling the pre-purified water to enter a photoelectrocatalysis system through a water inlet passage electromagnetic valve 5 under the control of a water flow velocity valve 4; air on the air inlet pipeline is pressurized by an air pump 6, is filtered by a filter screen 7 to obtain purified air, and enters a cathode chamber 9 of the photoelectrocatalysis system after being regulated by a gas flow rate valve 8.
S2, adjusting the inflow-outflow ratio of the gas in the cathode chamber 9 to enable the working pressure of the gas to be 0-1 Mpa, and enabling the purified air to perform oxygen reduction reaction in the cathode chamber 9 to generate pure hydrogen peroxide, wherein the hydrogen peroxide is HO 2- The residual air is diffused into the solid electrolyte 13 through an anion exchange membrane 16 positioned between the cathode chamber 9 and the solid electrolyte 13, and the redundant air flows out from the other end of the cathode chamber 9 through a check valve 10 and an air outlet 11.
S3, the pre-purified water is subjected to water oxidation reaction in the anode chamber 14 to generate pure hydrogen peroxide and H + Hydrogen peroxide is washed out of anode chamber 14 and H + Diffuses into the solid-state electrolyte 13 along the cation exchange membrane 17 between the anode chamber 14 and the solid-state electrolyte 13.
S4, HO diffused from the cathode chamber 9 2- With H diffused from anode chamber 14 + Binding to form H 2 O 2 And then washed out of the photoelectrocatalytic system with water.
S5, detecting the product quality by a detector 18 and then flowing hydrogen peroxide generated by the catalysis of the photoelectric catalytic system into a storage tank 19 for later use; hydrogen peroxide in the storage tank 19 flows into a water flow electromagnetic valve 21 through a pressure pump 20 and flows out of the equipment at one end of the water flow electromagnetic valve 21 to obtain high-purity hydrogen peroxide; the hydrogen peroxide enters a refining column 22 through the other end of the water flow electromagnetic valve 21 for refining to obtain the ultra-high-purity hydrogen peroxide.
Preferably, the step S3 further includes a process of irradiating the anode chamber 14, wherein the irradiating light source is a visible light source 15, and the power is 0-200W.
According to the invention, the cathode chamber 9 of the photoelectrocatalysis system is mainly made of porous carbon oxide paper, and the effective working area is 100cm 2 Working current density of 0.2A/cm 2 The working pressure of the cathode chamber 9 is 0-1 Mpa. The oxygen reduction of the purified air in the cathode compartment 9 produces pure hydrogen peroxide, HO 2- Diffuses into the solid-state electrolyte 13 through the anion-exchange membrane 16, and H from the anode + Ion binding to form H 2 O 2 And then washed with water to make the photoelectrocatalysis system. The redundant air flows out of the equipment from the other end of the cathode chamber 9 through the check valve 11 and the air outlet 12。
The cathode compartment 9 reaction equation is as follows: o is 2 +H 2 O+2e - →HO 2- +OH -
Reaction pressure of cathode compartment 9 with HO 2- The yields are related as shown in table 1 below:
TABLE 1
| Reaction pressure (MPa) | 0 | 0.2 | 0.5 | 1 |
| HO 2- Yield (mmol/cm) 2 /h) | 2.0 | 2.3 | 2.7 | 3.0 |
The anode chamber 14 is mainly made of porous carbon paper oxide-bismuth vanadate composite electrode, and the effective working area is 100cm 2 Working current density of 0.2A/cm 2 . The pre-purified water undergoes a water oxidation reaction in the anode chamber 14 to produce H + With pure hydrogen peroxide (hydrogen peroxide yield 1mmol/cm at a water flow rate of 1000mL/h 2 /h)，H + Diffuse along the cation exchange membrane into the solid electrolyte 13, with HO from the cathode 2- Binding to generate H 2 O 2 And washed by water to form the photoelectrocatalysis system. The reaction equation for anode chamber 14 is as follows: 2H 2 O→H 2 O 2 +2(H + +e - )
In particular, the anode chamber 14 can convert light energy into photoelectrons by irradiation with an external visible light source 15, and the photoelectrons are biased to the cathode chamber 9 to participate in the generation of H 2 O 2 . When the reaction pressure is 1MPa and the water flow rate is 1000mL/H, the power of the visible light source 15 and the cathode chamber H 2 O 2 The yields are related as shown in table 2 below:
TABLE 2
| Luminous power (W) | 0 | 50 | 100 | 200 |
| H 2 O 2 Yield (mmol/cm) 2 /h) | 3.0 | 3.3 | 3.6 | 3.7 |
By changing the flow rate of the supplied water, aqueous hydrogen peroxide solutions of different mass fractions can be obtained. Collected H under 200W illumination 2 O 2 The relationship between mass fraction and water flow rate is shown in table 3 below:
TABLE 3
| Water flow rate (mL/h) | 10 | 50 | 100 | 500 | 1000 |
| H 2 O 2 Mass fraction (wt.%) | 30 | 18 | 10 | 2 | 1 |
Preferably, the air on the air inlet pipeline enters the photoelectrocatalysis system at the flow rate of 100mL/min after being regulated by the air flow rate valve 8. Wherein, the solid electrolyte 13 can be made of styrene-divinylbenzene copolymer with a thickness of 0.5cm. The solid electrolyte can avoid the influence of the reaction medium on the purity and the property of the hydrogen peroxide to the maximum extent, such as: impurities are easy to introduce into a liquid reaction medium, so that the impurity removal difficulty is improved, and the cost is increased; the pH of the liquid medium affects the stability of the hydrogen peroxide, etc.
Preferably, the water flow rate of the water oxygen purification system is 10-1000 mL/h, the pressure of the air pump 6 is 20kPa, and the air supply flow rate is 100mL/min
The working principle of the invention is as follows: tap water enters a purification column 3 through an electromagnetic valve 1 and a hydraulic press 2 under the pressurization and is pre-purified, and the pre-purified water is controlled by a flow rate valveEnters the catalytic system through the electromagnetic valve 5 at different flow rates (10-1000 mL/h). The air inlet passage is sequentially provided with an air pump 6, a filter screen 7 and a flow rate valve 8, the air is pressurized by the air pump 6, purified air is obtained through the filter screen 7 and is adjusted by the flow rate valve 8, and finally the purified air enters the photoelectrocatalysis system at the flow rate of 100mL/min. The working pressure of the cathode chamber 9 is adjusted to be 0-1 MPa by adjusting the ratio of gas inflow to gas outflow in the cathode chamber 9 of the photoelectrocatalysis system. The oxygen reduction of the purified air in the cathode compartment 9 produces pure hydrogen peroxide, HO 2- Diffuses into the solid-state electrolyte 13 through the anion-exchange membrane 16, with H from the anode + Ion binding to form H 2 O 2 And then washed out of the catalytic system with water. The redundant air flows out from the other end of the cathode chamber 9 through a check valve 10 and an air outlet 11. The pre-purified water undergoes a water oxidation reaction in the anode chamber 14 to produce purified hydrogen peroxide and H + Hydrogen peroxide is washed out of anode chamber 14 and H + Diffuses into the solid electrolyte 13 along the cation exchange membrane 17, with HO 2- Combined to form H 2 O 2 . By changing the reaction pressure of the cathode chamber 9, the flow rate of the supplied water and the illumination power of the anode chamber 14, aqueous hydrogen peroxide solutions with different mass fractions (1 to 30 wt.%) can be obtained. The generated hydrogen peroxide is detected by the detector 18 for product quality and then flows into the storage tank 19 for standby. Hydrogen peroxide in the storage tank 19 flows into a water flow electromagnetic valve 21 through a pressure pump 20 and flows out of the equipment at one end of the water flow electromagnetic valve 21 to obtain high-purity hydrogen peroxide; the high-purity hydrogen peroxide enters the refining column 22 through the other end of the water flow electromagnetic valve 21 and flows out of the equipment to obtain the ultra-high-purity hydrogen peroxide.
The specification of the hydrogen peroxide produced by adopting the integrated device is as follows: high-purity aqueous hydrogen peroxide (total organic carbon content is less than or equal to 20ppm, total metal impurity content is less than or equal to 200ppb, particle size is more than or equal to 0.5 mu m (piece/mL) is less than or equal to 25, and total hydrogen peroxide content is 1-30 wt.%), and ultra-high-purity aqueous hydrogen peroxide (total organic carbon content is less than or equal to 10ppm, total metal impurity content is less than or equal to 2ppb, particle size is more than or equal to 0.2 mu m (piece/mL) is less than or equal to 5, and total hydrogen peroxide content is 1-30 wt.%).
The above description is only a preferred application of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Claims (10)
1. An integrated device for producing hydrogen peroxide by photoelectrocatalysis of water oxygen, which is characterized by comprising:
a water oxygen purification system having a water inlet line and an air inlet line configured to deliver and purify water and air, respectively;
a photoelectrocatalysis system configured for photoelectrocatalytically generating hydrogen peroxide for the water and air delivered by the water oxygen purification system; and
the storage refinement system is used for detecting and purifying the hydrogen peroxide produced by the photoelectrocatalysis system to obtain the hydrogen peroxide;
the photoelectrocatalysis system comprises a cathode chamber (9), a solid electrolyte (13) and an anode chamber (14) which are sequentially arranged in parallel, an anion exchange membrane (16) is arranged between the cathode chamber (9) and the solid electrolyte (13), and a cation exchange membrane (17) is arranged between the solid electrolyte (13) and the anode chamber (14); the cathode chamber (9) is provided with a water inlet communicated with a water inlet pipeline of the water oxygen purification system, an air inlet communicated with an air inlet pipeline and an air outlet.
2. The integrated apparatus according to claim 1, wherein one side of the anode compartment (14) is provided with an irradiation device configured for emitting a visible light source (15) for irradiating the anode compartment (14).
3. The integrated device of claim 1, wherein the water inlet pipeline is provided with a water inlet, a water flow electromagnetic valve (1), a water press (2), a purification column (3), a water flow velocity valve (4) and a water inlet passage electromagnetic valve (5) in sequence; the water inlet passage electromagnetic valve (5) is provided with three outlets which are respectively communicated with the cathode chamber (9), the solid electrolyte (13) and the anode chamber (14).
4. The integrated device according to claim 1, characterized in that an air inlet, an air pump (6), a filter screen (7) and a gas flow rate valve (8) are arranged on the air inlet pipeline in sequence, and the gas flow rate valve (8) is communicated with the cathode chamber (9).
5. The integrated device according to claim 1, characterized in that the cathode chamber (9) has an outlet which is connected in series to a non-return valve (11) and to an air outlet (12). Preferably, the cathode chamber (9) is provided with a pressure gauge (10).
Preferably, the solid electrolyte (13) and the anode chamber (14) are both provided with water inlets which are respectively connected with the water inlet pipeline electromagnetic valve (5), and the other ends of the solid electrolyte and the anode chamber are both connected with the detector (18).
6. The integrated apparatus of claim 1, wherein the storage refinement system further comprises a detector (18) coupled to the photoelectrocatalytic system configured to detect a quality of the hydrogen peroxide produced.
Preferably, the storage refinement system further comprises a hydrogen peroxide storage tank (19), a pressure pump (20) and a water flow electromagnetic valve (21) which are sequentially communicated with the detector (18), wherein hydrogen peroxide in the hydrogen peroxide storage tank (19) flows out from the pressure pump (20) through one end of the water flow electromagnetic valve (21) to obtain hydrogen peroxide.
Preferably, the storage refinement system further comprises a refinement column (22) arranged at the tail end of the water flow electromagnetic valve (21) and configured to be used for further refining the hydrogen peroxide to obtain the hydrogen peroxide with higher purity.
7. The integrated device according to claim 3, wherein the purification column (3) is a three-stage purification column comprising an activated carbon purification column, an adsorbent resin purification column and an ultraviolet oxidation lamp arranged in sequence.
Preferably, the filter screen (7) comprises a two-section type filtering structure of a dust removal bag and a drying screen which are arranged in sequence.
8. The integrated device of claim 1, wherein the detector (18) of the storage refinement system is composed of a programmable controller, a CPU module carrying a DSP chip and a digital display screen, so as to detect the concentration and the storage capacity of the hydrogen peroxide solution, the internal working state of the machine, historical data inquiry, consumable replacement prompt and fault alarm in real time.
Preferably, the refinement column (22) of the storage refinement system is a two-stage refinement column, and comprises an adsorption resin refinement column with an anti-oxidation function and a nylon ultrafiltration membrane refinement column.
9. An integrated method for producing hydrogen peroxide by photoelectrocatalysis of water oxygen is characterized by comprising the following steps:
s1, opening a water inlet pipeline and a gas inlet pipeline of a water oxygen purification system to enable water to enter a purification column (3) through a water flow electromagnetic valve (1) and pressurization through a water press (2) and to be pre-purified, and enabling the pre-purified water to enter a photoelectrocatalysis system through a water inlet passage electromagnetic valve (5) under the control of a water flow velocity valve (4); air on the air inlet pipeline is pressurized by an air pump (6), is filtered by a filter screen (7) to obtain purified air, and enters a cathode chamber (9) of the photoelectrocatalysis system after being adjusted by a gas flow rate valve (8);
s2, adjusting the gas inflow and outflow ratio in the cathode chamber (9) to ensure that the working pressure is 0-1 Mpa, and performing oxygen reduction reaction on the purified air in the cathode chamber (9) to generate pure hydrogen peroxide, wherein the hydrogen peroxide is HO 2- The air is diffused into the solid electrolyte (13) through an anion exchange membrane (16) positioned between the cathode chamber (9) and the solid electrolyte (13), and the redundant air flows out of the equipment from the other end of the cathode chamber (9) through a check valve (10) and an air outlet (11);
s3, the pre-purified water is subjected to water oxidation reaction in the anode chamber (14) to generate pure hydrogen peroxide and H + Hydrogen peroxide is washed out of the anode compartment (14) and H + Diffusing into the solid-state electrolyte (13) along a cation exchange membrane (17) between the anode chamber (14) and the solid-state electrolyte (13);
s4, HO diffused from the cathode chamber (9) 2- With H diffused from the anode chamber (14) + Binding to generate H 2 O 2 Then washed by water to form a photoelectrocatalysis system;
s5, detecting the product quality of hydrogen peroxide generated by the catalysis of the photoelectrocatalysis system through a detector (18), and then, allowing the hydrogen peroxide to flow into a storage tank (19) for later use; hydrogen peroxide in the storage tank (19) flows into the water flow electromagnetic valve (21) through the pressure pump (20), and flows out of the equipment at one end of the water flow electromagnetic valve (21) to obtain hydrogen peroxide; the hydrogen peroxide enters a refining column (22) for refining through the other end of the water flow electromagnetic valve (21) to obtain the hydrogen peroxide with higher purity.
10. Integrated process according to claim 9, characterized in that the main material of the cathodic compartment (9) of the photoelectrocatalytic system is a porous carbon oxide paper with a working area of 100cm 2 Working current density 0.2A/cm 2 The working pressure of the cathode chamber (9) is 0-1 Mpa.
Preferably, the electrode material of the anode chamber (14) is a porous carbon paper oxide-bismuth vanadate composite material, and the effective working area is 100cm 2 The working current density is 0.2A/cm 2 。
Preferably, the air on the air inlet pipeline enters the photoelectrocatalysis system at the flow rate of 100mL/min after being adjusted by the air flow rate valve (8).
Preferably, the material of the solid electrolyte (13) is styrene-divinylbenzene copolymer, and the thickness is 0.5cm.
Preferably, the step S3 further includes a process of irradiating the anode chamber (14), wherein the irradiating light source is a visible light source (15) and has a power of 0-200W.
Preferably, the water supply flow rate of the water oxygen purification system is 10-1000 mL/h, the pressure of the air pump (6) is 20kPa, and the air supply flow rate is 100mL/min.
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