Oxidation reaction method and device for reducing decomposition of hydrogen peroxide

Abstract

The invention discloses an oxidation reaction method and device for reducing decomposition of hydrogen peroxide. The method comprises the following steps: adding hydrogen peroxide into a reaction solution needing to be subjected to oxidation reaction by adopting a flowing type hydrogen peroxide mixer; the reaction liquid is a solution needing to be subjected to oxidation reaction with hydrogen peroxide; the flowing type hydrogen peroxide mixer comprises a main flow pipeline, an air pressure dynamic balance branch pipe and a hydrogen peroxide input branch pipe communicated with the main flow pipeline; reaction liquid is fed into the main flow pipeline of the flowing type hydrogen peroxide mixer, hydrogen peroxide is added into the hydrogen peroxide input branch pipe, and hydrogen peroxide or hydrogen peroxide and decomposed gas thereof are sucked into the main flow pipeline by utilizing negative pressure generated at the joint of liquid flow of the reaction liquid in the main flow pipeline and the hydrogen peroxide input branch pipe; the reaction liquid and the hydrogen peroxide and / or oxygen obtained by decomposing the hydrogen peroxide are mixed and compressed under the action of stress in the main flow pipeline, are subjected to oxidation reaction and then flow out of the main flow pipeline.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen peroxide oxidation reaction, and specifically relates to an oxidation reaction method and a device for reducing the decomposition of hydrogen peroxide. Background Art

[0002] Hydrogen peroxide is an oxidant commonly used in production and life; because the peroxide bond -OO- in hydrogen peroxide is a relatively fragile chemical bond, it is very unstable. Hydrogen peroxide mainly decomposes into water and oxygen in the following four situations: the first is catalysis by heavy metal oxides, such as manganese dioxide; the second is self-decomposition under alkaline conditions, such as the mixture of alkaline copper chloride ammonium etching solution for circuit boards and hydrogen peroxide; the third is catalysis by catalase; the fourth is catalysis by metal salt solution, such as the mixture of copper sulfate or ferric chloride solution and hydrogen peroxide.

[0003] Since hydrogen peroxide is easy to decompose under the above four conditions, when it comes into contact with an alkaline solution or a solution containing a metal salt during an oxidation reaction, it will rapidly decompose to produce water and oxygen. However, the oxygen produced by the decomposition is difficult to enter the reaction solution to continue the oxidation reaction. This not only wastes the raw materials of hydrogen peroxide, but also causes a high oxygen content in the air space of the production site, which is dangerous.

[0004] Hydrogen peroxide is widely used as an oxidant, but there are few existing technologies that improve the decomposition of hydrogen peroxide under the above four conditions. If the problem of hydrogen peroxide being easy to decompose and difficult to continue the oxidation reaction can be solved, the utilization rate of hydrogen peroxide chemical reactions can be improved, and the decomposition of hydrogen peroxide on the reaction liquid interface can be overcome during use, the process breakthrough will be very great. Summary of the invention

[0005] The first object of the present invention is to provide an oxidation reaction method for reducing the decomposition of hydrogen peroxide, which utilizes external force to mix and compress hydrogen peroxide and reaction liquid in a pipeline, so that hydrogen peroxide is dissolved in the reaction liquid for oxidation reaction, thereby achieving the purpose of reducing the decomposition of hydrogen peroxide.

[0006] The second object of the present invention is to provide an oxidation reaction device that reduces the decomposition of hydrogen peroxide to achieve the first object of the invention.

[0007] The first object of the present invention can be achieved by the following method.

[0008] An oxidation reaction method for reducing the decomposition of hydrogen peroxide comprises the following steps:

[0009] A flowing hydrogen peroxide mixer is used to add hydrogen peroxide to the reaction liquid to be oxidized;

[0010] The mobile hydrogen peroxide mixer comprises a mainstream pipeline, a pressure dynamic balance branch and a hydrogen peroxide injection branch connected to the mainstream pipeline; a reaction liquid is sent into the mainstream pipeline of the mobile hydrogen peroxide mixer, and hydrogen peroxide is added to the hydrogen peroxide injection branch, and the negative pressure generated by the reaction liquid flow in the mainstream pipeline at the interface between the mainstream pipeline and the hydrogen peroxide injection branch is used to absorb hydrogen peroxide or hydrogen peroxide and its decomposition gas into the mainstream pipeline, so that the reaction liquid and hydrogen peroxide and / or the oxygen obtained by the decomposition of hydrogen peroxide are mixed and compressed under the force in the mainstream pipeline and undergo oxidation reaction, and then flow out of the mainstream pipeline.

[0011] The reaction liquid of the present invention is a solution that needs to be oxidized with hydrogen peroxide. Preferably, the reaction liquid is a mixture of one or more of an alkaline solution, a solution containing a metal salt, an alkaline solid-liquid mixture, a solid-liquid mixture containing a metal salt, and a solid-liquid mixture containing a heavy metal oxide. The method of the present invention solves the problem that hydrogen peroxide is easily decomposed when mixed with the above reaction liquids, thereby affecting the oxidation reaction. When the reaction liquid is a solid-liquid mixture and the solid therein is a substance that needs to participate in the oxidation reaction, the volume and weight of the solid can enter the mobile hydrogen peroxide mixer with the reaction liquid for reaction.

[0012] The mobile hydrogen peroxide mixer of the present invention applies the principle of Bernoulli fluid mechanics, utilizes the rapid flow of the reaction liquid in the mainstream pipeline, and generates a negative pressure force at the interface between the reaction liquid and the hydrogen peroxide input branch pipe to help the hydrogen peroxide delivered from outside to mix into the reaction liquid. By mixing and compressing the reaction liquid and the hydrogen peroxide, the decomposition of the hydrogen peroxide in the process of dissolving into the reaction liquid is reduced, and the process problem of easy decomposition of the added hydrogen peroxide is solved. At the same time, a large amount of reaction liquid in the pipeline is used to dilute the hydrogen peroxide, so that the oxidant and the reductant can fully contact each other and create conditions for the reaction liquid to wrap the hydrogen peroxide and / or tiny oxygen bubbles for a safe oxidation reaction, thereby fully utilizing the added hydrogen peroxide.

[0013] As an embodiment of the present invention, the discharge port of the mainstream pipeline of the mobile hydrogen peroxide mixer discharges the mixture undergoing oxidation reaction to the reaction tank. At this time, there are two discharge methods: one is to insert the discharge port of the mainstream pipeline into the liquid surface of the reaction tank for discharge; the other is to discharge the discharge port of the mainstream pipeline on the liquid surface of the reaction tank. When the reaction liquid is a solid-liquid mixture and its solid reactant is large in volume and will precipitate or be fixed in a certain place in the reaction tank, the discharge liquid of the mainstream pipeline is preferentially sprayed toward the solid reactant to promote the oxidation reaction of the solid reactant; the solid reactant is a metal, a low-valent metal oxide, or a low-valent metal salt.

[0014] The air pressure dynamic balance branch pipe of the present invention is connected to the hydrogen peroxide input branch pipe, and / or is connected to the interface between the mainstream pipeline and the hydrogen peroxide input branch pipe. Because hydrogen peroxide will violently decompose and produce oxygen when it encounters the reaction liquid at the interface between the mainstream pipeline and the hydrogen peroxide input branch pipe, a large pressure is generated in the mobile hydrogen peroxide mixer, so that the externally added hydrogen peroxide cannot be added to the mixer for oxidation reaction. The air pressure dynamic balance branch pipe can solve the problem that hydrogen peroxide cannot be added when the internal pressure is high due to the violent decomposition of hydrogen peroxide, and can also avoid the siphon phenomenon of the hydrogen peroxide input branch pipe after the addition of hydrogen peroxide is completed, which continuously sucks hydrogen peroxide into the reaction tank and creates danger.

[0015] As a preferred embodiment of the present invention, the diameter of the main pipeline is narrowed at the interface with the hydrogen peroxide injection branch pipe or at the rear section of the main pipeline to reduce the cross-sectional area of ​​the liquid flow, so as to accelerate the flow rate of the reaction liquid at the interface under the condition of stable liquid flow at the inlet of the main pipeline to generate a greater negative pressure suction force, resulting in an increased mixing compression force of the reaction liquid, hydrogen peroxide and its decomposition bubbles, further reducing the decomposition of hydrogen peroxide during the injection and mixing process.

[0016] The function of the flowing hydrogen peroxide mixer of the present invention is to use the flowing reaction liquid to guide hydrogen peroxide and / or decomposed oxygen into the reaction liquid for oxidation reaction, and can be applied to the following typical production examples to make full use of hydrogen peroxide and improve oxidation efficiency.

[0017] First, the stripping liquid in the copper electroplating industry is used to strip the excess copper layer on the fixture, and then put it back on line after corrosion removal. The oxidation reaction of the stripping liquid stripping copper is:

[0018] H2SO4+H2O2+Cu→CuSO4+2H2O

[0019] Second, the oxidation reaction of acidic ferrous chloride and hydrogen peroxide to produce ferric chloride:

[0020] 2FeCl2+2HCl+H2O2→2FeCl3+2H2O

[0021] The present invention can be improved as follows: the outlet of the main pipeline of the mobile hydrogen peroxide mixer is connected to the reaction tank or faces the inlet of the reaction tank, and the air pressure dynamic balance branch pipe is connected to at least one exhaust port of the reaction tank, so that the reaction tank becomes an air pressure dynamic balance absorption tank. When the internal pressure of the mobile hydrogen peroxide mixer is high, it is discharged to the reaction tank. When the mobile hydrogen peroxide mixer works normally, the remaining oxygen in the reaction tank can be re-introduced into the mobile hydrogen peroxide mixer for gas-liquid mixing and reused.

[0022] The present invention can also be improved as follows: a vacuum ejector is added and used in combination with the flowing hydrogen peroxide mixer, wherein the air intake port of the vacuum ejector is connected to at least one exhaust port of the reaction tank to absorb the remaining oxygen in the reaction tank for reuse, so as to improve the utilization rate of the hydrogen peroxide.

[0023] The present invention can also be improved as follows: a temperature control system is added to control the temperature of the reaction liquid so that the oxidation reaction can be carried out at a safe temperature.

[0024] The present invention can also be improved as follows: in order to speed up the oxidation reaction of the reaction liquid in the reaction tank, two or more flow-type hydrogen peroxide mixers can be installed in the reaction tank in parallel to meet the technical requirements of large-scale oxidation device production.

[0025] The present invention can also be improved as follows: ultrasonic waves are used to stir the reaction liquid and break bubbles, so that the oxygen decomposed in the hydrogen peroxide can be more easily dissolved in the reaction liquid, thereby improving the utilization rate of hydrogen peroxide and increasing the solubility of gas-liquid mixing and the mixing of the reaction liquid and hydrogen peroxide, thereby promoting the oxidation reaction.

[0026] The second object of the present invention is achieved through the following technical solutions.

[0027] An oxidation reaction device for reducing the decomposition of hydrogen peroxide is characterized by comprising a reaction tank, a flowing hydrogen peroxide mixer, a hydrogen peroxide supplier, and a reaction liquid introducer.

[0028] The reaction tank is used to load the reaction liquid to be oxidized with hydrogen peroxide; the reaction liquid can be a common solution or an alkaline solution or a metal salt solution that can easily cause the decomposition of hydrogen peroxide.

[0029] The mobile hydrogen peroxide mixer is as follows Figure 1 , Figure 2 , Figure 3 The component No. 2 in the embodiment is used for mixing the reaction liquid and hydrogen peroxide for compression reaction therein, and comprises a mainstream pipeline, a hydrogen peroxide input branch pipe and a pressure dynamic balance branch pipe. An interface is provided between the mainstream pipeline and the hydrogen peroxide input branch pipe for communication. The pressure dynamic balance branch pipe is communicated with the hydrogen peroxide input branch pipe and / or is communicated with the mainstream pipeline and the hydrogen peroxide input branch pipe at the interface. The mainstream pipeline outlet is communicated with the reaction tank or toward the inlet of the reaction tank.

[0030] The flow-type hydrogen peroxide mixer is constructed by using the principle of Bernoulli flow dynamics. The discharge outlet of the mainstream pipeline in the flow-type hydrogen peroxide mixer can be respectively arranged inside the reaction liquid for discharge or above the liquid surface of the reaction liquid. When the reaction liquid in the reaction tank is a solid-liquid mixture and there are large solid reactants in the solution that cannot flow into the mixer with the reaction liquid, the discharge outlet of the mainstream pipeline is preferentially sprayed toward the solid matter participating in the reaction to promote the oxidation reaction of the solid reactants.

[0031] The hydrogen peroxide supplier is composed of a pump, a pipeline and a hydrogen peroxide storage container, and the pipeline outlet is connected to the hydrogen peroxide input branch pipe of the mobile hydrogen peroxide mixer. Preferably, the hydrogen peroxide supplier is additionally equipped with a flow regulating valve to better accurately control the addition of hydrogen peroxide. The hydrogen peroxide storage container is used to store hydrogen peroxide materials. The hydrogen peroxide supplier is connected to the mobile hydrogen peroxide mixer through a pipeline and extracts hydrogen peroxide to supply the mobile hydrogen peroxide mixer.

[0032] The reaction liquid introducer includes a pipeline and a pump, which is used to pump the reaction liquid into the mainstream pipeline of the flowing hydrogen peroxide mixer for flow reaction. The outlet of the reaction liquid introducer is connected to the inlet of the mainstream pipeline of the flowing hydrogen peroxide mixer, or its outlet is connected to the inlet of the mainstream pipeline of the flowing hydrogen peroxide mixer and its inlet is connected to the reaction tank. When the outlet of the reaction liquid introducer is connected to the inlet of the mainstream pipeline of the flowing hydrogen peroxide mixer and its inlet is connected to the reaction tank, it is a liquid flow circulator. Preferably, the reaction liquid introducer also includes a valve.

[0033] The above-mentioned reaction tank, flowing hydrogen peroxide mixer, hydrogen peroxide supplier and liquid flow circulator form a basic type of oxidation reaction device for reducing the decomposition of hydrogen peroxide; wherein the materials of the equipment in the device are metal and / or non-metal materials that are not corroded by the reaction liquid.

[0034] The present invention can be improved as follows: a one-way valve is installed on the connecting pipe between the hydrogen peroxide storage container and the hydrogen peroxide input branch pipe of the mobile hydrogen peroxide mixer to prevent the reaction liquid from flowing back into the hydrogen peroxide storage container to cause a dangerous accident.

[0035] The present invention can also be improved as follows: the pump of the hydrogen peroxide supply device is preferably a metering pump, and the hydrogen peroxide is metered according to the process so that the oxidation reaction can proceed stably. The metering pump is specifically installed on the connecting pipe between the mixer and the hydrogen peroxide storage container.

[0036] The present invention can also be improved as follows: adding sensors and automatic detection and feeding controllers, wherein the sensors are selected from at least one of an oxidation-reduction potentiometer (ORP meter), a pH meter, an acidity meter, a liquid level meter, a thermometer, a hydrometer, a photoelectric colorimeter, an ammonia detector, and a COD detector; after adding the automatic detection and feeding controller and the sensors, the production process is automated; the sensors are specifically installed at a position where they can contact the object to be measured.

[0037] The present invention can also be improved as follows: an exhaust gas treatment tank is added to treat the waste gas discharged from each tank in the device in an environmentally friendly manner; the air intake pipe opening of the exhaust gas treatment tank is connected to the exhaust gas escape pipe openings of each tank by pipelines. The exhaust gas treatment tank can be selected from a bubbling exhaust gas treatment tank, a vacuum jet exhaust gas treatment tank, and a spray tower exhaust gas treatment tank.

[0038] The present invention can also be improved as follows: a temporary storage tank is added to temporarily store materials. The temporary storage tank can be connected to each tank and solid-liquid separator in the device by pipeline.

[0039] The present invention can also be improved as follows: a chemical reaction tank is added to adjust the preparation and reaction of the reactants. The chemical reaction tank is connected to other tanks in the device by pipelines.

[0040] The present invention can also be improved as follows: a solid-liquid separator is added, which has a filter, a filter press and a centrifuge in structure. During the operation, the solid-liquid separator separates the solid-liquid mixture into solid and liquid; the solid-liquid separator is connected to various tanks by pipelines.

[0041] The present invention can also be improved as follows: an overflow buffer tank is added to solve the problem of solution flow between tanks in the device. The overflow buffer tank is connected to other tanks or solid-liquid separators through a pump and a pipeline.

[0042] The present invention can also be improved as follows: a liquid flow agitator is added to make the concentration and temperature of the reaction liquid uniform and controllable. The liquid flow agitator is installed on a tank body with process requirements in the device.

[0043] The present invention can also be improved as follows: a reaction liquid temperature control system is added, which is a set of components of a cold and hot temperature exchanger and a thermometer to control the temperature of the reaction liquid. The reaction liquid temperature control system is installed in a tank body required by the process.

[0044] The present invention can also be improved as follows: an ultrasonic generator is added, and the ultrasonic generator is directly mounted on the corrosion-resistant metal reaction tank body containing the reaction liquid or on the corrosion-resistant metal pipe in which the reaction liquid flows; or an ultrasonic generator auxiliary liquid tank is fixed on the polymer resin reaction tank or the polymer resin pipe, and the ultrasonic generator is placed in the ultrasonic generator auxiliary liquid tank containing clean water or solution, and the ultrasonic generator is used to vibrate in the clean water or solution so that the ultrasonic wave passes through the clean water or solution and the resin layer of the tank body or pipe to be transmitted to the reaction liquid to play the function of the ultrasonic wave. Preferably, the material of the ultrasonic generator auxiliary liquid tank is polymer resin, so as to better connect with the polymer resin reaction tank or pipe.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] 1. The method of the present invention adopting a mobile hydrogen peroxide feeding device to carry out oxidation reaction can reduce the decomposition of hydrogen peroxide when it is fed into a common oxidation reaction liquid or even an alkaline solution and / or a metal salt solution, thereby improving the utilization rate of hydrogen peroxide raw materials and the reaction efficiency.

[0047] 2. The method of the present invention is safe and controllable, and can collect and utilize the oxygen decomposed from hydrogen peroxide to save production costs.

[0048] 3. The method of the present invention uses equipment with small construction capital and low operating cost, and creates high economic benefits.

[0049] 4. The method of the present invention does not add any new pollution source or hazard source during the reaction process, and meets the new process requirements of safe production and environmental protection and energy saving. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a schematic structural diagram of an oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 1.

[0051] Figure 2 This is a schematic structural diagram of an oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 2.

[0052] Figure 3 This is a schematic structural diagram of an oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 3.

[0053] Figure 4 This is a schematic structural diagram of an oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 4.

[0054] Figure 5 This is a schematic structural diagram of an oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 5.

[0055] Figure 6 This is a schematic diagram of the structure of the oxidation reaction device for reducing the decomposition of hydrogen peroxide in Example 6.

[0056] Reference numerals:

[0057] 1-reaction tank, 2-flowing hydrogen peroxide mixer, 3-hydrogen peroxide storage container, 4-reaction liquid introducer, 5-hydrogen peroxide dosing pump, 6-mainstream pipeline diameter narrowing compression section, 7-valve, 8-pump, 9-sensor, 10-automatic detection and feeding control machine, 11-exhaust treatment tank, 12-circuit board etching machine, 13-overflow buffer tank, 14-cold and hot temperature exchanger, 15-temporary storage tank, 16-circuit board etching liquid, 17-metal salt solution, 18-reaction liquid, 19-hydrogen peroxide, 20-etching copper-clad circuit board, 21-circuit board etching supplementary liquid, 22-circuit board etching copper-containing waste liquid, 23 - sulfuric acid, 24 - sodium hydroxide solution, 25 - hydrochloric acid, 26 - mainstream pipeline, 27 - hydrogen peroxide input water branch, 28 - air pressure dynamic balance branch, 29 - mainstream pipeline outlet, 30 - interface between mainstream pipeline and hydrogen peroxide input branch, 31 - one-way valve, 32 - vacuum ejector, 33 - electrolytic cell partition, 34 - electroplating anode, 35 - electroplating parts, 36 - electrolytic power supply, 37 - electroplating tank, 38 - solution after oxidation reaction treatment, 39 - solid matter participating in oxidation reaction, 40 - liquid flow agitator, 41 - solid-liquid separator, 42 - ultrasonic generator, 43 - ultrasonic generator auxiliary liquid tank.

[0058] In the drawings and the following embodiments, multiple components of the same component type in the device are represented by "reference numeral-number sequence". For example, the flowing hydrogen peroxide mixer 2-1 means one of the flowing hydrogen peroxide mixers, and the flowing hydrogen peroxide mixer 2-2 means the second of the flowing hydrogen peroxide mixers. DETAILED DESCRIPTION

[0059] The present invention is further described below by means of specific examples.

[0060] In the following embodiments, the reaction tank, mobile hydrogen peroxide mixer, liquid flow circulator in the mixer, hydrogen peroxide storage container, temporary storage tank, liquid flow buffer tank, liquid flow agitator, tail gas treatment tank used are all products of Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd., Guangdong Province, China. Etching production line, electroplating line, hot and cold temperature exchanger, electroplating power supply, sensor, automatic detection and feeding controller, copper clad circuit board, valve, pump, chemical raw materials are all commercially available products. In addition to the above-mentioned, those skilled in the art can also select other products with similar performance to the above-mentioned products listed in the present invention according to conventional selection, which can achieve the purpose of the present invention.

[0061] Example 1

[0062] like Figure 1As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, a flowing hydrogen peroxide mixer 2, a reaction liquid introducer 4, a temporary storage tank 15, and a hydrogen peroxide supplier composed of a hydrogen peroxide storage container 3, a hydrogen peroxide adding pump 5 and a pipeline.

[0063] The mobile hydrogen peroxide mixer 3 is Figure 1 The component numbered 2 includes a mainstream pipeline 26 and a hydrogen peroxide input branch pipe 27 connected thereto, forming an interface 30 between the mainstream pipeline and the hydrogen peroxide input branch pipe; it also includes an air pressure dynamic balance branch pipe 28, which is connected to the mainstream pipeline of the flowing hydrogen peroxide mixer and the interface between the hydrogen peroxide input branch pipe; and the mainstream pipeline outlet 29 is connected to the reaction tank 1.

[0064] The reaction liquid introducer 4 is composed of a pipeline and a pump, and its outlet is connected to the inlet of the mainstream pipeline 26 , and the inlet is connected to the temporary storage tank 15 .

[0065] The pipe outlet of the hydrogen peroxide supplier is connected to the hydrogen peroxide input branch pipe 27 .

[0066] The solution to be treated in this embodiment, that is, the reaction solution 18 is an alkaline solution, specifically landfill leachate, the COD of the waste liquid is 6500 mg / L, and the pH value is pH 7.1.

[0067] The hydrogen peroxide 19 is commercially available 27.5% industrial grade hydrogen peroxide.

[0068] This embodiment adopts the process reaction of adding hydrogen peroxide at a constant rate per unit time. The discharge liquid from the mainstream pipeline falls on the liquid surface in the reaction tank. The COD concentration value of the reaction liquid before and after the addition of hydrogen peroxide is compared to illustrate the degradation effect on organic waste liquid.

[0069] The operation steps of this embodiment to reduce the oxidation reaction of hydrogen peroxide decomposition are as follows:

[0070] 1. Put the landfill leachate to be treated into the temporary storage tank 15, start the reaction liquid introducer 4 to make the temporary storage tank

[0071] The landfill leachate to be treated in 15 is put into the mainstream pipeline 26 of the mobile hydrogen peroxide mixer 2.

[0072] 2. Start the hydrogen peroxide adding pump 5 to add hydrogen peroxide to the hydrogen peroxide injection branch pipe 27, so that the hydrogen peroxide enters the mainstream pipe 26 at the interface 30 between the mainstream pipe and the hydrogen peroxide injection branch pipe and is subjected to negative pressure to participate in the oxidation reaction.

[0073] 3. The reaction liquid flowing out of the main pipeline 26 still contains hydrogen peroxide and / or oxygen that have not participated in the reaction. The liquid flow introduces the remaining oxidant into the solution of the reaction tank 1 to continue the oxidation reaction.

[0074] 4. After three hours of oxidation reaction, samples were taken for manual inspection and the COD result was

[0075] 4300mg / L.

[0076] The reaction conditions, materials and the comparison results of the two COD values ​​before and after the reaction are listed in Table 1.

[0077] Example 2

[0078] like Figure 2 As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, a flowing hydrogen peroxide mixer 2, a reaction liquid introducer 4, and a hydrogen peroxide supplier composed of a hydrogen peroxide storage container 3, a hydrogen peroxide adding pump 5 and a pipeline.

[0079] The mobile hydrogen peroxide mixer is Figure 2 The component No. 2 in the figure includes a mainstream pipeline 26 and a hydrogen peroxide injection branch pipe 27 connected thereto, forming an interface 30 between the mainstream pipeline and the hydrogen peroxide injection branch pipe, and the diameter of the mainstream pipeline 26 section at the interface is narrowed; the mainstream pipeline outlet 29 is connected to the liquid surface below the reaction tank 1, and the part of the pipeline below the liquid surface is provided with air holes; the hydrogen peroxide injection branch pipe 27 is provided with an air pressure dynamic balance branch pipe 28.

[0080] The reaction liquid introducer 4 is composed of a pipeline and a pump, and its outlet is connected to the inlet of the mainstream pipeline 26, and its inlet is connected to the reaction tank 1, making it a liquid flow circulator.

[0081] The pipe outlet of the hydrogen peroxide supplier is connected to the hydrogen peroxide input branch pipe 27 .

[0082] The material used in the device of this embodiment is corrosion-resistant titanium metal.

[0083] In this embodiment, the 1000 liter reaction solution 18 in the reaction tank 1 is a mixture of hydrochloric acid and ferrous chloride, wherein the acidity is 3M, and Fe 2+ The concentration is 45g / L; among them, the solid matter 39 participating in the oxidation reaction is iron powder, 1 gram.

[0084] The hydrogen peroxide is commercially available 27.5% industrial grade hydrogen peroxide.

[0085] In this embodiment, the chemical reaction formula for adding hydrogen peroxide into the flowing hydrogen peroxide mixer 2 for reaction is as follows:

[0086] 2FeCl2+2HCl+H2O2→2FeCl3+2H2O

[0087] Iron powder is added during the reaction:

[0088] Fe+2FeCl3→3FeCl2

[0089] Fe+2HCl→FeCl2+H2↑

[0090] This embodiment uses comparative data, one of which is the result of oxidation reaction by directly adding hydrogen peroxide to the liquid surface of the reaction liquid using the prior art, and the other is the result of oxidation reaction by adding hydrogen peroxide using the device of the present invention. The comparison of the two results can intuitively reflect the utilization rate of hydrogen peroxide.

[0091] The operation steps of this embodiment to reduce the oxidation reaction of hydrogen peroxide decomposition are as follows:

[0092] 1. Put the prepared ferrous chloride mixed solution into the reaction tank 1, start the reaction solution introducer 4 to make the reaction solution circulate in the mobile hydrogen peroxide mixer 2 and the reaction tank 1.

[0093] 2. Start the hydrogen peroxide adding pump 5, add hydrogen peroxide to react with the acid solution to make Fe 2+ Oxidized to Fe 3+ At the same time, solid iron powder is added into the process for oxidation reaction.

[0094] 3. Add 8 liters of 27.5% hydrogen peroxide to 1000 liters of reaction solution, and the reaction takes 30 minutes. Sampling for manual testing shows that the ferric chloride content is 18 g / L.

[0095] The reaction conditions, materials and results of the two addition methods are listed in Table 1.

[0096] Example 3

[0097] like Figure 3 As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, a flowing hydrogen peroxide mixer 2, a container reaction liquid introducer 4, and a hydrogen peroxide supplier composed of a hydrogen peroxide storage container 3, a hydrogen peroxide adding pump 5, a one-way valve 31 and a pipeline.

[0098] The mobile hydrogen peroxide mixer is Figure 3 The component numbered 2 includes a mainstream pipeline 26 and a hydrogen peroxide injection branch pipe 27 connected thereto, forming an interface 30 between the mainstream pipeline and the hydrogen peroxide injection branch pipe, and a pressure dynamic balance branch pipe 28 is also provided at the interface; wherein, the mainstream pipeline 26 adopts a venturi tube structure to simplify the structure of the flow-type hydrogen peroxide mixer and adapt to the needs of large-scale oxidation reactions, and utilizes a pipe section with a smaller flow cross-sectional area in the venturi tube structure as a pipe section with a narrowed diameter in the mainstream pipeline 26, and the front section of the pipe section is used as the interface 30 between the mainstream pipeline and the hydrogen peroxide injection branch pipe, and the mainstream pipeline outlet 29 is connected to the reaction tank 1, toward the solid matter 39 participating in the oxidation reaction in the tank.

[0099] The reaction liquid introducer 4 is composed of a pipeline and a pump, and its outlet is connected to the inlet of the mainstream pipeline 26, and its inlet is connected to the reaction tank 1, making it a liquid flow circulator.

[0100] The pipe outlet of the hydrogen peroxide supplier is connected to the hydrogen peroxide input branch pipe 27 .

[0101] The reaction liquid 18 in the reaction tank 1 of this embodiment is a stripping liquid used in an electroplating line, and its main components are sulfuric acid, hydrogen peroxide, and a copper ion concentration of 35 g / L. The volume of the reaction liquid is 1500 liters; the solid object 39 participating in the oxidation reaction is a fixture.

[0102] The hydrogen peroxide 19 is commercially available 27.5% industrial grade hydrogen peroxide.

[0103] This embodiment uses the cleaning fixture tank on the electroplating line as a reaction tank. During the electroplating process, a stripping liquid is used to corrode and peel off the excess copper layer on the fixture. After removing the excess copper layer, the fixture is re-hanged for use. During the production process, hydrogen peroxide needs to be added to the solution in the reaction tank to replenish the decomposed loss part so that the stripping liquid can restore the chemical activity of corrosion.

[0104] The operation steps of this embodiment to reduce the oxidation reaction of hydrogen peroxide decomposition are as follows:

[0105] 1. Start the reaction liquid introducer 4 to allow the reaction liquid in the cleaning fixture tank to be introduced into the main flow pipe 26 of the flowing hydrogen peroxide mixer 2 for circulation.

[0106] 2. Start the hydrogen peroxide adding pump 5 to add hydrogen peroxide into the hydrogen peroxide feeding branch pipe 27, so that the hydrogen peroxide enters the mobile hydrogen peroxide mixer 2 for mixing and compression.

[0107] 3. The reaction liquid flowing out of the flowing hydrogen peroxide mixer 2 still contains hydrogen peroxide and / or oxygen that have not participated in the reaction. The liquid flow containing the oxidant is sprayed onto the excess copper layer on the fixture to promote the reaction with the copper layer. The solution in the reaction tank 1 corrodes the copper layer at the same time.

[0108] 4. After 20 minutes of oxidation treatment, the fixture was taken out and checked to find that the excess copper layer originally electroplated on the fixture was corroded and cleaned.

[0109] The conditions, materials and reaction results of the corrosion cleaning reaction process are listed in Table 1.

[0110] Example 4

[0111] like Figure 4As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, a flowing hydrogen peroxide mixer 2, a hydrogen peroxide supply device composed of a hydrogen peroxide storage container 3, a hydrogen peroxide adding pump 5, valves and pipelines, a reaction liquid introducer 4, an overflow buffer tank 13, four sensors 9, a cold and hot temperature exchanger 14, two temporary storage tanks 15, an etched copper-clad circuit board 20, multiple valves and pumps. Among them, the sensor 9-1 is a thermometer, 9-2 is a pH meter, 9-3 is a hydrometer, and 9-4 is an ORP meter, all of which are arranged in the reaction tank 1.

[0112] The reaction tank 1 is a circuit board etching machine 12, which is used to perform copper oxidation etching on the circuit board. The etching working liquid is loaded with 1500 liters; the reaction tank 1 is also provided with a cold and hot temperature exchanger 14, which forms a reaction liquid temperature control system with a thermometer.

[0113] The mobile hydrogen peroxide mixer 2 is Figure 2 The structure numbered 2 includes a mainstream pipeline 26 and a hydrogen peroxide injection branch pipe 27 connected thereto, forming an interface 30 between the mainstream pipeline and the hydrogen peroxide injection branch pipe, and the diameter of the mainstream pipeline 26 section at the interface is narrowed; the mainstream pipeline outlet 29 is connected to the liquid surface below the reaction tank 1, and the part of the pipeline below the liquid surface is provided with air holes; the hydrogen peroxide injection branch pipe 27 is provided with an air pressure dynamic balance branch pipe 28.

[0114] The reaction liquid introducer 4 is composed of a pipeline and a pump, and its outlet is connected to the inlet of the mainstream pipeline 26, and its inlet is connected to the reaction tank 1, making it a liquid flow circulator.

[0115] The pipe outlet of the hydrogen peroxide supplier is connected to the hydrogen peroxide input branch pipe 27 .

[0116] The reaction liquid 18 in the reaction tank 1 is an alkaline copper-ammonium chloride etching working liquid for circuit boards, and its main components are a mixture of copper-ammonium chloride, ammonia water, and ammonium chloride, with a pH value of pH 7.2 and a copper ion concentration of 100 g / L. The working temperature of the reaction liquid is 50°C.

[0117] The main component of the circuit board etching sub-liquid 16 is an alkaline mixed solution of ammonia water and ammonium chloride.

[0118] The hydrogen peroxide is commercially available 50% industrial grade hydrogen peroxide.

[0119] The temporary storage tank 15 - 1 stores alkaline copper chloride ammonium etching sub-liquid 16 and is connected to the reaction tank 1 ; the temporary storage tank 15 - 2 stores circuit board etching copper-containing waste liquid 22 and is connected to the liquid outlet of the reaction tank 1 through the overflow buffer tank 13 .

[0120] In this embodiment, the etched copper-clad circuit board 20 is put into the circuit board etching machine 12 for copper etching reaction. During the process, the pH value of the reaction solution will decrease. In order to maintain the stability of the concentration of each component of the etching reaction solution, a pH meter 9-2 is used to control the pump 8-1 to add the etching sub-liquid 16 into the etching machine to maintain the pH of the etching working solution at 7.2. The hydrometer 9-3 is used to detect the copper ion concentration of the oxidation reaction solution, and the ORP meter 9-4 controls the hydrogen peroxide addition pump 5 to add hydrogen peroxide to the flowing hydrogen peroxide mixer 2 to mix and compress the reaction solution 18 for oxidation reaction.

[0121] The chemical reaction is as follows:

[0122] Cu+H2O2→CuO+H2O

[0123] Cu(NH3)4Cl2+Cu→2Cu(NH3)2Cl

[0124] The etching solution undergoes an oxidation regeneration reaction, that is, the reaction solution 18 undergoes an oxidation reaction:

[0125] 4Cu(NH3)2Cl+4NH4Cl+4NH4OH+O2→4Cu(NH3)4Cl2+6H2O

[0126] CuO+2NH4OH+2NH4Cl→Cu(NH3)4Cl2+3H2O

[0127] This example uses a comparison method to illustrate the advantages of the present invention; the first method is to add hydrogen peroxide to the reaction liquid surface in the existing way and obtain the change value of the redox potential increase before and after the reaction, and the second method is to add hydrogen peroxide to obtain the ORP change before and after the reaction. By comparing the values ​​of the two ORP changes, the method of adding hydrogen peroxide with high utilization rate is obtained.

[0128] The operation steps of reducing the oxidation of hydrogen peroxide decomposition in this embodiment are as follows:

[0129] 1. Put the circuit board alkaline copper chloride ammonium etching solution, i.e. reaction solution 18, into the circuit board etching machine

[0130] In step 12, pump 8-2 is started to circulate the reaction solution and spray it, and the copper-clad circuit board is etched.

[0131] 20. Carry out etching in the etching machine.

[0132] 2. Add circuit board etching sub-liquid 16 according to the pH meter, and add hydrogen peroxide to the hydrogen peroxide injection branch pipe 27 according to the ORP meter control, start the reaction liquid introducer 4 to inject the reaction liquid into the mainstream pipeline 26 for circulation, and perform oxidation regeneration reaction on the reaction liquid 18.

[0133] 3. As the etching reaction liquid overflows into the overflow buffer tank 13, it is pumped to the tank 8-3 to send the waste liquid to the overflow buffer tank 13.

[0134] 15-2 Temporarily saved.

[0135] The above two etching process tests were carried out using etching copper clad circuit boards. During the process, the results were compared by comparing the changes in the respective ORP count values, and it was found that the hydrogen peroxide utilization rate was high when using the dosing method of the present invention. The process parameters and results are listed in Table 1.

[0136] Example 5

[0137] like Figure 5 As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, which is a circuit board etching machine 12, a mobile hydrogen peroxide dosing device 2, a hydrogen peroxide supply device composed of a hydrogen peroxide storage container 3, a hydrogen peroxide dosing pump 5, a valve and a pipeline, a reaction liquid introducer 4, four sensors 9, an automatic detection and feeding controller 10, an exhaust gas treatment tank 11, an overflow buffer tank 13, a cold and hot temperature exchanger 14, a temporary storage tank 15, an ultrasonic generator 42, an ultrasonic generator auxiliary liquid tank 43, a plurality of valves and pumps. Sensor 9-1 is a thermometer, 9-2 is a hydrometer, 9-3 is an ORP meter, 9-4 is an acidity meter, and 9-5 is an air chlorine concentration detector. Except for sensor 9-4 which is arranged in the exhaust gas treatment tank 11, the others are all arranged in the reaction tank 1.

[0138] The reaction tank 1 is a circuit board etching machine 12, which is used to perform copper etching reaction on the circuit board, and is loaded with 1500 liters of etching working liquid; wherein the reaction tank 1 is made of polymer resin material. The reaction tank 1 is also provided with a cold and hot temperature exchanger 14, which forms a reaction liquid temperature control system with a thermometer.

[0139] The mobile hydrogen peroxide mixer is Figure 5 The component numbered 2 in the figure includes a mainstream pipeline 26 and a hydrogen peroxide input branch pipe 27 connected thereto, forming an interface 30 between the mainstream pipeline and the hydrogen peroxide input branch pipe; the mainstream pipeline outlet 29 is connected to the liquid level in the reaction tank 1, and part of the pipeline below the liquid level is provided with air holes; the hydrogen peroxide input branch pipe 27 is provided with a pressure dynamic balance branch pipe 28, and the pressure dynamic balance branch pipe 28 is connected to at least one exhaust port of the reaction tank 1, so that the reaction tank 1 becomes a pressure dynamic balance absorption tank. When the internal pressure of the mobile hydrogen peroxide mixer is high, it is discharged to the reaction tank. When the mobile hydrogen peroxide mixer works normally, the remaining oxygen in the reaction tank can be re-introduced into the mobile hydrogen peroxide mixer for gas-liquid mixing and reused.

[0140] The reaction liquid introducer 4 is composed of a pipeline and a pump, and its outlet is connected to the inlet of the mainstream pipeline 26, and its inlet is connected to the reaction tank 1, making it a liquid flow circulator.

[0141] The ultrasonic generator 42 is installed on the reaction tank 1 through the ultrasonic generator auxiliary liquid tank 43, wherein the ultrasonic generator 42 is placed in the clean water in the ultrasonic generator auxiliary liquid tank 43, and the material of the ultrasonic generator auxiliary liquid tank 43 is a polymer resin.

[0142] The tail gas treatment tank 11 is provided with a spray tower to perform environmental protection treatment on the waste gas discharged from each tank in the device, and its air intake pipe opening is respectively connected to the tail gas escape pipe opening of each tank by pipeline.

[0143] The reaction liquid 18 in the reaction tank 1 is a circuit board acid copper chloride etching working liquid, the main components of which are a mixture of hydrochloric acid, copper chloride and chloride salt, with an acidity of 2M and a copper ion concentration of 130 g / L. The working temperature of the reaction liquid is 50°C.

[0144] The main component of the circuit board etching sub-liquid 21 is hydrochloric acid.

[0145] The hydrogen peroxide is commercially available 27.5% industrial grade hydrogen peroxide.

[0146] The temporary storage tank 15 - 1 is filled with hydrochloric acid 25 and connected to the reaction tank 1 ; the temporary storage tank 15 - 2 is filled with circuit board etching copper-containing waste liquid 22 and connected to the liquid outlet of the reaction tank 1 through the overflow buffer tank 13 .

[0147] The sensor signal input end of the automatic detection feeding controller 10 is connected to the signal output end of each sensor, and the control signal output end of the automatic detection feeding controller 10 is connected to the control signal input end of each pump, valve, ultrasonic generator, and hot and cold temperature exchanger in the device.

[0148] In this embodiment, the etched copper-clad circuit board 20 is put into the etching machine for copper etching reaction. The specific gravity of the oxidation reaction liquid will increase. In order to maintain the constant concentration of each component of the reaction liquid, the acidity meter is used to control the pump 8-1 to add hydrochloric acid into the etching machine to reduce the specific gravity of the etching working liquid. The ORP meter controls the hydrogen peroxide addition pump 5 to add hydrogen peroxide to the flowing hydrogen peroxide mixer 2 to mix and compress the reaction liquid 18 for oxidation reaction.

[0149] The chemical reaction is as follows:

[0150] CuCl2+Cu→2CuCl

[0151] 2CuCl+2HCl+H2O→2CuCl2+2H2O

[0152] This example uses a comparison method to illustrate the advantages of the process of the present invention; the first method is based on the existing hydrogen peroxide method, that is, directly adding it to the liquid surface of the reaction liquid and obtaining the numerical change of its ORP before and after the reaction, and the second method is based on the numerical change of ORP before and after the reaction of the hydrogen peroxide adding method of the present invention. The two ORP changes are compared, and the larger the change, the higher the utilization rate of hydrogen peroxide.

[0153] The operation steps of this embodiment to reduce the oxidation reaction of hydrogen peroxide decomposition are as follows:

[0154] 1. Put the circuit board alkaline copper chloride etching working solution, that is, the reaction solution 18, into the circuit board etcher 12, start the pump 8-3 to make the reaction solution circulate and spray, put the etched copper-clad circuit board 20 into the etcher for etching, and start the ultrasonic generator at the same time.

[0155] 2. According to the acidity meter, control the pump 8-1 to add hydrochloric acid, and according to the ORP meter, control the hydrogen peroxide to be added to the hydrogen peroxide injection branch pipe 27, start the reaction liquid introducer 4 to inject the reaction liquid into the main pipeline 26 for circulation, and perform oxidation regeneration reaction on the reaction liquid 18.

[0156] 3. As the etching reaction liquid overflows into the overflow buffer tank 13, it is pumped to the tank 8-2 to send the waste liquid to the overflow buffer tank 13.

[0157] 15-2 Temporarily saved.

[0158] The above two etching process tests were carried out using etching copper clad circuit boards. During the process, the results were compared by comparing the changes in the respective ORP count values, and it was found that the hydrogen peroxide utilization rate was high when using the dosing method of the present invention. The process parameter changes and results are listed in Table 1.

[0159] Example 6

[0160] like Figure 6 As shown, the oxidation reaction device for reducing the decomposition of hydrogen peroxide in this embodiment includes a reaction tank 1, two flowing hydrogen peroxide mixers 2, a hydrogen peroxide storage container 3, a reaction liquid introducer 4, two hydrogen peroxide adding pumps 5-1 and 5-2, four sensors 9, a cold and hot temperature exchanger 14, two temporary storage tanks 15, two one-way valves 31, a vacuum ejector 32, three ultrasonic generators 42, and a plurality of valves and pumps.

[0161] The reaction tank 1 is made of stainless steel material resistant to corrosion by the reaction liquid. The reaction tank 1 is provided with a cold and hot temperature exchanger 14, which together with a thermometer forms a reaction liquid temperature control system.

[0162] The two flow-type hydrogen peroxide mixers 2-1 and 2-2 are both Figure 2The structure shown in No. 2 includes a mainstream pipeline and a hydrogen peroxide injection branch connected thereto, the diameter of the mainstream pipeline section at the interface between the mainstream pipeline and the hydrogen peroxide injection branch is narrowed; the outlet of the mainstream pipeline is connected to the liquid level in the reaction tank 1, and the part of the pipeline below the liquid level is provided with air holes; the hydrogen peroxide injection branches 27-1 and 27-2 are respectively provided with air pressure dynamic balance branches 28-1 and 28-2. Two mobile hydrogen peroxide mixers are installed in parallel, and the materials used are both stainless steel.

[0163] The reaction liquid introducer 4 is composed of a pipeline, a pump and a valve, and its outlet is connected to the mainstream pipeline inlet of the two flowing hydrogen peroxide mixers, and its inlet is connected to the reaction tank 1, so that it becomes a liquid flow circulator. The outlet of the reaction liquid introducer 4 is also connected to the vacuum ejector 32, and is used in combination with the flowing hydrogen peroxide mixer; the air intake of the vacuum ejector 32 is connected to one of the exhaust ports of the reaction tank 1, and the liquid outlet is connected to one of the liquid inlets of the reaction tank 1, which is used to absorb the oxygen escaping from the liquid surface in the reaction tank and return it to the reaction liquid through gas-liquid mixing to participate in the oxidation reaction, thereby improving the utilization rate of the oxidant.

[0164] The hydrogen peroxide storage container 3, the hydrogen peroxide adding pump 5-1, the one-way valve 31-1 and the pipeline constitute a first hydrogen peroxide supplier, and its pipeline outlet is connected to the hydrogen peroxide input branch of the flowing hydrogen peroxide mixer 2-2; the hydrogen peroxide storage container 3, the hydrogen peroxide adding pump 5-2, the one-way valve 31-2 and the pipeline respectively constitute a second hydrogen peroxide supplier, and its pipeline outlet is connected to the hydrogen peroxide input branch of the flowing hydrogen peroxide mixer 2-1.

[0165] The ultrasonic generators 42-1 and 42-2 are respectively installed at the outlet sections of the mainstream pipes of the flowing hydrogen peroxide mixers 2-1 and 2-2 to fully mix the reaction liquid with the hydrogen peroxide.

[0166] The hydrogen peroxide is commercially available 27.5% industrial grade hydrogen peroxide.

[0167] The acidic chloride-free metal salt solution 17 is an organic waste liquid of ferrous sulfate with a pH of 3.2 and a COD of 620 mg / L. It is temporarily stored in a temporary storage tank 15-1 and sent to the reaction tank 1 through a pipeline.

[0168] The reaction solution 18 in the reaction tank 1 is a solution obtained by adding hydrogen peroxide to the metal salt solution 17 to perform a Fenton reaction, and a sodium hydroxide solution 24 is added to maintain the pH value of the reaction solution at 3.2.

[0169] The sodium hydroxide solution 24 is used to maintain the pH value of the reaction solution at 3.2 during the Fenton reaction. The sodium hydroxide solution 24 is stored in the temporary storage tank 15-2 and is sent to the reaction tank 1 through a pipeline.

[0170] The sensor 9 - 1 is a liquid level meter, 9 - 2 is an ORP meter, 9 - 3 is a thermometer, and 9 - 4 is a pH meter, all of which are arranged in the reaction tank 1 .

[0171] This embodiment adopts the method of the present invention to perform Fenton reaction on organic waste liquid, wherein the liquid level meter in the device controls pump 8-1 to add metal salt solution 17 to reaction tank 1, the ORP meter controls pumps 5-1 and 5-2 to add hydrogen peroxide, the thermometer controls the working state of the hot and cold temperature exchanger 14 to maintain the reaction liquid at 45°C according to the process requirements, and the pH meter 9-4 is used to control pump 8-2 to add sodium hydroxide solution so that the reaction conditions of the reaction liquid meet the requirements of Fenton reaction.

[0172] The operation steps of this embodiment to reduce the oxidation reaction of hydrogen peroxide decomposition are as follows:

[0173] 1. Add the metal salt solution 17 in the temporary storage tank 15-1 into the reaction tank 1 under the control of the liquid level meter, start the hot and cold temperature exchanger 14 to control the temperature of the reaction liquid under temperature control, start the reaction liquid introducer 4 to make the vacuum ejector 32 and the two flowing hydrogen peroxide mixers work normally.

[0174] 2. Start pumps 5-1 and 5-2 under the control of ORP meter and time, add hydrogen peroxide to two mobile hydrogen peroxide mixers to participate in the oxidation reaction of reaction solution 18, start the ultrasonic generator to make the solution in the reaction tank better defoam and dissolve oxygen. At the same time, add sodium hydroxide from temporary storage tank 15-2 to the reaction tank to maintain the pH of the reaction solution at 3.2.

[0175] 3. According to the process conditions, when the ORP value of the reaction liquid reaches 500mv, the Fenton reaction is completed. The COD result of the reaction liquid sampling test is 70mg / L; the operation of all equipment in the device is stopped.

[0176] 4. Open valve 7-7 to draw out solution 38 in the reaction tank.

[0177] The above oxidation reaction results are listed in Table 1.

[0178] Table 1

[0179]

[0180]

[0181] Note: The method of adding hydrogen peroxide directly on the liquid surface of the reaction liquid according to the prior art described in Table 1 is to directly add hydrogen peroxide into the reaction liquid to be oxidized in the oxidation tank.

Claims

1. An oxidation reaction method for reducing the decomposition of hydrogen peroxide, characterized in that: The steps include: A flowing hydrogen peroxide mixer is used to add hydrogen peroxide to the reaction liquid; the reaction liquid is a solution that needs to undergo oxidation reaction with hydrogen peroxide; The mobile hydrogen peroxide mixer comprises a mainstream pipeline, a pressure dynamic balance branch and a hydrogen peroxide injection branch connected to the mainstream pipeline; a reaction liquid is sent into the mainstream pipeline of the mobile hydrogen peroxide mixer, and hydrogen peroxide is added to the hydrogen peroxide injection branch, and the negative pressure generated by the reaction liquid flow in the mainstream pipeline at the interface between the mainstream pipeline and the hydrogen peroxide injection branch is used to absorb hydrogen peroxide or hydrogen peroxide and its decomposition gas into the mainstream pipeline, so that the reaction liquid and hydrogen peroxide and / or the oxygen obtained by the decomposition of hydrogen peroxide are mixed and compressed under the force in the mainstream pipeline and undergo oxidation reaction, and then flow out of the mainstream pipeline.

2. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 1, characterized in that: The reaction liquid is one or a mixture of more than one of an alkaline solution, a solution containing a metal salt, an alkaline solid-liquid mixture, a solid-liquid mixture containing a metal salt, and a solid-liquid mixture containing a heavy metal oxide.

3. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 2, characterized in that: The main pipeline outlet of the mobile hydrogen peroxide mixer discharges the mixture undergoing oxidation reaction into the reaction tank. There are two discharge methods: one is to insert the outlet of the main pipeline into the reaction tank below the liquid surface for discharge; the other is to discharge the outlet of the main pipeline above the liquid surface in the reaction tank.

4. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 3, characterized in that: The air pressure dynamic balance branch pipe is communicated with the hydrogen peroxide input branch pipe, and / or is communicated with the interface between the mainstream pipeline and the hydrogen peroxide input branch pipe.

5. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 4, characterized in that: The diameter of the pipe is narrowed at the interface between the mainstream pipe and the hydrogen peroxide injection branch pipe or the pipe section behind the interface to reduce the cross-sectional area of ​​the liquid flow, so as to accelerate the flow rate of the reaction liquid at the interface while stabilizing the liquid flow at the inlet of the mainstream pipe to generate a greater negative pressure suction.

6. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 4, characterized in that: The outlet of the mainstream pipeline of the flow-type hydrogen peroxide mixer is connected to the reaction tank or faces the inlet of the reaction tank, and the air pressure dynamic balance branch pipe is connected to at least one exhaust port of the reaction tank, so that the reaction tank becomes an air pressure dynamic balance absorption tank.

7. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 3, characterized in that: Ultrasonic waves were used to stir the reaction solution and break bubbles.

8. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 3, characterized in that: A vacuum ejector is added and used in combination with the flowing hydrogen peroxide mixer, wherein the air intake port of the vacuum ejector is connected to at least one exhaust port of the reaction tank to absorb the remaining oxygen in the reaction tank for reuse.

9. The oxidation reaction method for reducing the decomposition of hydrogen peroxide according to claim 3, characterized in that: A temperature control system is added to control the temperature of the reaction liquid so that the oxidation reaction can proceed at a safe temperature.

10. An oxidation reaction device for reducing the decomposition of hydrogen peroxide, characterized in that: It includes a reaction tank, a flowing hydrogen peroxide mixer, a hydrogen peroxide supplier, and a reaction liquid introducer; The reaction tank is used to load the reaction liquid to be oxidized with hydrogen peroxide; The mobile hydrogen peroxide mixer is used to mix and compress the reaction liquid and hydrogen peroxide therein, and comprises a mainstream pipeline, a hydrogen peroxide input branch pipe and a pressure dynamic balance branch pipe. An interface is provided between the mainstream pipeline and the hydrogen peroxide input branch pipe for communication. The pressure dynamic balance branch pipe is communicated with the hydrogen peroxide input branch pipe and / or is communicated with the mainstream pipeline and the hydrogen peroxide input branch pipe at the interface. The mainstream pipeline outlet is communicated with the reaction tank or toward the inlet of the reaction tank. The hydrogen peroxide supplier is composed of a pump, a pipeline and a hydrogen peroxide storage container, and the pipeline outlet is connected to the hydrogen peroxide input branch pipe of the mobile hydrogen peroxide mixer to extract hydrogen peroxide and supply it to the mobile hydrogen peroxide mixer; The reaction liquid introducer includes a pipeline and a pump, which is used to pump the reaction liquid into the mainstream pipeline of the flowing hydrogen peroxide mixer for flow reaction. The outlet of the reaction liquid introducer is connected to the inlet of the mainstream pipeline of the flowing hydrogen peroxide mixer, or its outlet is connected to the inlet of the mainstream pipeline of the flowing hydrogen peroxide mixer and its inlet is connected to the reaction tank.

11. The oxidation reaction device for reducing the decomposition of hydrogen peroxide according to claim 10, characterized in that: A one-way valve is additionally installed on the connecting pipe between the hydrogen peroxide storage container and the hydrogen peroxide input branch pipe of the mobile hydrogen peroxide mixer.

12. The oxidation reaction device for reducing decomposition of hydrogen peroxide according to claim 10, characterized in that: The pump of the hydrogen peroxide supply device adopts a metering pump, and the hydrogen peroxide is metered according to the process so that the oxidation reaction can proceed stably.

13. The oxidation reaction device for reducing decomposition of hydrogen peroxide according to claim 10, characterized in that: A reaction liquid temperature control system is added, which is a set of components including a hot and cold temperature exchanger and a thermometer to control the temperature of the reaction liquid.

14. The oxidation reaction device for reducing decomposition of hydrogen peroxide according to claim 10, characterized in that: An ultrasonic generator is added, and the ultrasonic generator is directly installed on a corrosion-resistant metal reaction tank body containing a reaction liquid or a corrosion-resistant metal pipe through which a reaction liquid flows; or an ultrasonic generator auxiliary liquid tank is fixed on a polymer resin reaction tank or a polymer resin pipe, and the ultrasonic generator is placed in the ultrasonic generator auxiliary liquid tank containing clean water or a solution, and the ultrasonic generator is used to vibrate in the clean water or the solution so that the ultrasonic wave is transmitted through the clean water or the solution and the resin layer of the tank body or the pipe to the reaction liquid to exert the function of the ultrasonic wave.

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